WO2006094148A1 - Process for the preparation of transparent, shaped articles - Google Patents

Process for the preparation of transparent, shaped articles Download PDF

Info

Publication number
WO2006094148A1
WO2006094148A1 PCT/US2006/007489 US2006007489W WO2006094148A1 WO 2006094148 A1 WO2006094148 A1 WO 2006094148A1 US 2006007489 W US2006007489 W US 2006007489W WO 2006094148 A1 WO2006094148 A1 WO 2006094148A1
Authority
WO
WIPO (PCT)
Prior art keywords
residues
acid
mole percent
component
diol
Prior art date
Application number
PCT/US2006/007489
Other languages
French (fr)
Inventor
Wesley Raymond Hale
Thomas Joseph Pecorini
Mark Edward Stewart
Martin Emerson Rogers
Spencer Allen Gilliam
Michael Duane Cliffton
Original Assignee
Eastman Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to AT06736755T priority Critical patent/ATE527315T1/en
Priority to JP2007558234A priority patent/JP5243047B2/en
Priority to CA 2598563 priority patent/CA2598563C/en
Priority to EP20060736755 priority patent/EP1871837B1/en
Publication of WO2006094148A1 publication Critical patent/WO2006094148A1/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B29B17/0042Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/62Plastics recycling; Rubber recycling
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • Y10T428/1359Three or more layers [continuous layer]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • Y10T428/1383Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31725Of polyamide
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31725Of polyamide
    • Y10T428/31736Next to polyester
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31725Of polyamide
    • Y10T428/31739Nylon type

Definitions

  • This invention pertains to a process for the preparation of shaped articles from transparent, immiscible polymer blends comprising at least two polymer components. More specifically, this invention pertains to a process for the preparation of transparent, shaped articles from immiscible blends comprising at least one thermoplastic polymer, a copolyamide or a homogeneous blend of at least two polyamides, and recovered scrap polymer regrind.
  • oxygen barriers include polyethylene vinyl alcohol) (“EVOH”), polyvinyl alcohol) (“PVOH”), polyamides (nylons), and blends of these materials.
  • EVOH polyethylene vinyl alcohol
  • PVH polyvinyl alcohol
  • Polyamides polyamides
  • Poly(vinylidene chloride), vinyl chloride copolymers, and vinylidene chloride-methyl acrylate copolymers also are useful as moisture and oxygen barriers.
  • barrier polymers may be overcome by using a blend of the barrier polymer with another polymer.
  • barrier polymers and other thermoplastic polymers are immiscible and are opaque or hazy. Such blends are not satisfactory for applications requiring clarity such as, for example, beverage containers.
  • Polyester polymers such as, for example, poly(ethylene terephthalate) (“PET”), are commonly used in packaging applications. PET has a number of properties that make it useful as a packaging material, including acceptable carbon dioxide barrier properties for soft drinks packaged in bottles containing multiple servings. However, improvements in the carbon dioxide barrier of PET are needed for soft drinks packaged in smaller bottles and in its oxygen barrier, which is not well-suited for packaging oxygen sensitive products such as, for example, beer, citrus products, tomato-based products, and aseptically packed meat.
  • Polyethylene naphthalate) (“PEN”) is 3-1 0 times more effective as a barrier than PET but is more expensive.
  • Multilayer structures can be used to improve the gas barrier characteristics of PET.
  • polymers that have excellent oxygen barrier also referred to as “passive barrier” or scavenging properties (also referred to as “active barrier”) may be combined with PET to produce a layered structure consisting of the individual polymers.
  • These multilayer structures are expensive to produce.
  • Blends of barrier polymers with PET also have been used to improve the oxygen barrier of packages but, as noted above, often have poor transparency and are not suitable for many packaging applications. The poor transparency of blends also makes it difficult to recycle manufacturing scrap from polymer blends into virgin polymer.
  • Copolyester films and extrusion blow molded (“EBM”) bottles are often desired for toughness, and are commonly used instead of PET for - A -
  • a polymer blend that provides good passive and/or active barrier properties, is economical, and can be recycled efficiently is needed in the art.
  • Such blends should be transparent, contain thermoplastic and barrier polymers that provide a high barrier for oxygen, water, and carbon dioxide, and can be used economically in article forming processes which incorporate a high level of regrind.
  • barrier and thermoplastic polymer compositions that can be used to economically produce multilayered articles having high transparency and can tolerate a high level of regrind.
  • Polymer compositions having high transparency and high barrier properties can be prepared from a immiscible blend of one or more thermoplastic polymers and a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides in which the difference in refractive index between the polyamide component and thermoplastic polymer component is about 0.006 to about -0.0006.
  • the present invention provides a polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference, in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
  • the first component comprises at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends of these polymers, while the second component comprises a blend of at least 2 polyamides which have been transamidized to produce a homogeneous blend.
  • refractive indices of the first and second components can be closely matched by selecting at least 2 polyamides having different levels of aliphatic and aromatic residues and transamidizing these polyamides to form a homogeneous blend.
  • homogeneous blends of the thermoplastic polymers and the polymamides can be used to tailor refractive indices of the second component and the first component to within their desired ranges such that the difference in refractive indices is about 0.006 to about - 0.0006.
  • a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A can be used as the first component and a transamidized, homogeneous blend of first polyamide comprising the residues of m-xylylenediamine and adipic acid, and a second aliphatic polyamide can be used as the barrier polymer.
  • the first and second components form clear, immiscible blends that are suitable for the preparation of high clarity, shaped articles that can be used in many packaging applications.
  • Multilayered articles may also be prepared by a variety of processes known in the art.
  • the first and second components may be coextruded or coinjected from the melt into separate layers, or the layers may be formed individually and brought together in a subsequent process such as, for example, lamination.
  • the second component can also comprise a copolyamide having a ratio of aromatic and aliphatic dicarboxylic acid and diamine residues that can be varied to closely match the refractive indices of the first and second components.
  • a polymer composition comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and
  • a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Ri(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
  • COOI 3 Another aspect of our invention is a polymer composition prepared by prepared by a process comprising melt blending:
  • a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
  • compositions of our invention show excellent barrier properties.
  • the oxygen barrier properties may be enhanced by incorporating transition metal catalysts such as, for example, cobalt, manganese, iron, ruthenium, copper, nickel, palladium, and platinum into the blends to produce oxygen scavenging compositions.
  • transition metal catalysts such as, for example, cobalt, manganese, iron, ruthenium, copper, nickel, palladium, and platinum into the blends to produce oxygen scavenging compositions.
  • the invention thus, further provides an oxygen-scavenging composition comprising: (A) an immiscible blend comprising
  • thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
  • a second component comprising a transamidized, homogeneous blend of at least two polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less; and (B) at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic
  • Typical metal catalysts are cobalt, manganese, and iron.
  • the blends of the present invention are useful for producing clear, shaped articles having improved barrier properties, melt processability, and excellent mechanical properties, and which can be prepared using a high proportion of regrind to virgin polymer. These shaped articles may have a single layer or multiple layers and have numerous packaging applications. Accordingly, the invention further provides a process for forming a shaped article, comprising:
  • a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein the first component (i) and second component (ii) form an immiscible blend, the second component and the first component have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
  • shaped articles which may be prepared by the process of the invention include, but are not limited to, sheets, films, tubes, bottles, or profiles.
  • the shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
  • the shaped articles may have a one or more layers comprising an immiscible blend of the first and second components or can have multiple layers in which the first and second components are in separate layers.
  • the invention also provides a multilayered, shaped article, comprising: (i) a first layer comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof; and (ii) a second layer comprising a transamidized homogeneous blend of at least two polyamides; wherein the second layer (ii) and the first layer (i) have a difference in refractive index, Rl(second layer) - Rl(first layer), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 1 0% or less.
  • the invention further provides a process for forming a multilayered shaped article, comprising: (i) heating a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof to a temperature of about Tg +100°C to about Tg + 300 0 C of the first component; (ii) heating a second component comprising a copolyamide or a transamidized, homogeneous blend of at least two polyamides to a temperature of about Tg + T OO 0 C to about Tg + 300 0 C of the second component; (iii) forming a shaped article having the first and second components in separate layers;
  • step (v) grinding the scrap first and second components to produce a regrind; (vi) optionally, drying the regrind; and (vii) combining the regrind with the first component, second component, or a combination thereof, of steps (i) and (ii); wherein the second component of step (ii) and the first component of step (i) of have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
  • the regrind may be incorporated into the first or second layer and may be from about 5 to about 60 weight percent of the article.
  • Polymer compositions having high clarity and good barrier properties can be prepared from an immiscible blend of one or more - Tl -
  • thermoplastic polymers and a transamidized, homogeneous blend of at least two polyamides, in which the difference in refractive index between the blend of polyamides and the thermoplastic polymers is about 0.006 to about -0.0006.
  • the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
  • the present invention provides polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
  • thermoplastic polymers and polyamides may be selected from a wide variety of polymers.
  • the refractive indices of the second component and the first component can be adjusted to give a difference of about 0.006 to about -0.0006 by the selection and ratio of the polyamides of the second component or, alternatively, by blending the thermoplastic polymers of the first component to form a homogeneous blend.
  • Our novel compositons can be used to manufacture shaped articles having one or more layers such as, for example, sheets, films, tubes, bottles, and profiles.
  • the shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
  • Multilayer articles can be prepared in which the immiscible blend is present in one or more layers or the first and second components are in separate layers. Because of the small difference in the refractive indices of the first and second components, shaped articles prepared from the composition of the invention can incorporate substantial quantities of regrind and retain good transparency. The clarity and barrier properties of these shaped articles produced make them particularly useful for packaging applications.
  • a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1 , 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1 1 13, etc., and the endpoints 0 and 10.
  • a range associated with chemical substituent groups such as, for example, "Ci to Cs hydrocarbons”, is intended to specifically include and disclose Ci and Cs hydrocarbons as well as C 2 , C3, and C 4 hydrocarbons.
  • polyester is intended to include homopolyesters, copolyesters, and terpolyesters.
  • polyesters are synthetic polymers prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional hydroxyl compounds.
  • the difunctional carboxylic acid is a dicarboxylic acid or a hydroxycarboxyiic acid
  • the difunctional hydroxyl compound is a dihydric alcohol such as, for example, glycols and diols.
  • the difunctional carboxylic acid may be an aliphatic or cycloaliphatic dicarboxylic acid such as, for example, adipic acid, or an aromatic dicarboxylic acid such as, for example, terephthalic acid.
  • the difunctional hydroxyl compound may be cycloaliphatic diol such as, for example, 1 ,4-cyclohexanedimethanol, a linear or branched aliphatic diol such as, for example, 1 ,4-butanediol, or an aromatic diol such as, for example, hydroquinone.
  • polyamide is intended to include synthetic polymers prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional amines or by the ring-opening polymerization of a lactam and may include homopolymers and copolymers.
  • the difunctional carboxylic acid can be a dicarboxylic acid such as adipic acid or isophthalic acid
  • the difunctional amines can be a diamine such as, for example, hexamethylene diamine or m-xylylenediamine.
  • copolyamide as used herein, is understood to mean a polyamide comprising at least 2, chemically distinct repeating units.
  • MXD6 nylon is not a copolyamide because it contains only a single, chemically distinct repeating unit containing the residues of adipic acid and m-xylylenediamine.
  • poly(hexamethylene adipamide-co-isophthalamide) prepared by the condensation of hexamethylenediamine with adipic and isophthalic acid, has two chemically distinct repeating units, that is, a repeating unit containing the residues of hexamethylenediamine and adipic acid, and another repeating unit containing the residues of hexamethylene diamine and isophthalic acid.
  • polycarbonate is herein defined as the condensation product of a carbonate source and a diol source, having a carbonate component containing 100 mole percent carbonate units and a diol component containing 100 mole percent diol units, for a total of 200 mole percent monomeric units or 100 mole percent "repeating units".
  • the polycarbonate portion of the first component is based upon the polycarbonate of 4,4'-isopropylidenediphenol, commonly known as bisphenol A polycarbonate.
  • linear or branched polycarbonates that may be utilized in the present invention may be derived from bisphenol A and can be prepared according to procedures well known in the art such as, for example, as disclosed in U.S. Patent No.'s 3,030,335 and 3,31 7,466.
  • Examples of bisphenol A polycarbonates that may be used in the present invention and are available commerically include the materials marketed under the tradenames LEXAN ® , available from the General Electric Company, and MAKROLON ® , available from Bayer, Inc.
  • polyesters prepared by the polycondensation of one or more difunctional aromatic dicarboxylic acids with one or more dihydric phenols.
  • typical aromatic dicarboxylic acids are terephthalic and isophthalic acid
  • typical aromatic diphenols are bisphenol A and hydroquinone.
  • residue as used herein in reference to the polymers of the invention, means any organic structure incorporated into a polymer through a polycondensation or ring opening reaction involving the corresponding monomer.
  • the term “repeating unit”, as used herein, means shortest sequence of monomer residues that can be found repeatedly in a polymer.
  • a repeating unit is an organic structure having dicarboxylic acid residue and a diol residue, or hydroxycarboxylic acid residues bonded through a carbonyloxy group.
  • a repeating unit is an organic structure having a dicarboxylic acid and a diamine residue, lactam, or aminoacid residues, bonded through a amide group.
  • the residues associated within the various polyesters, polyamide, polycarbonates, and polyarylates of the invention can be derived from the parent monomer compound itself or any derivative of the parent compound.
  • the dicarboxylic acid and amino acid residues referred to in the polymers of the invention may be derived from a dicarboxylic acid or aminoacid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof.
  • dicarboxylic acid or “aminoacid” is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester or polyamide.
  • Hydroxycarboxylic acid is intended to include aliphatic and cycloaliphatic hydroxycarboxylic acids as well as monohydroxy-monocarboxylic acids and any derivative thereof, including their associated acid halides, esters, cyclic esters (including dimers such as lactic acid lactides), salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process or ring opening reaction to make a high molecular weight polyester.
  • aminoacid is intended to include aliphatic, aromatic, and cycloaliphatic aminoacids and any derivative thereof, including their associated acid halides, amides, cyclic amides (lactams), salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process or ring opening reaction to make a high molecular weight polyamide.
  • diamine is intended to include diamines as well as their associated salts, amides, or any other derivative thereof that are useful for the preparation of polyamides.
  • I.V. inherent viscosity
  • refractive index refers to refractive index measurements obtained according to standard methods well known in the art.
  • the refractive indices reported herein were determined at a wavelength of 633 nm using a Metricon Prism CouplerTM model 2010 refractometer (available from Metricon Inc.) and are reported as the average of the refractive indices measured in 3 orthogonal directions (extrusion or stretch, transverse, and thickness directions).
  • difference in refractive index as used herein in the context of the compositions, processes, and shaped articles of the invention always means the value obtained by subtracting the refractive index of the polyester, polycarbonate, or polyarylate- containing component (typically referred to herein as the "first component” or “first layer” in multilayered articles) from the refractive index of the polyamide- or copolyamide-containing component (typically referred to herein as the "second component” or “second layer” in multilayered articles).
  • ⁇ RI difference in refractive index
  • refractive index is provided in the Examples.
  • haze is determined by molding or casting the composition into a sheet or film having a thickness of l /8 inch or less and measuring the haze according to the procedure described in the examples.
  • the haze can be determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze according the procedure described herein.
  • DSC differential scanning calorimetry
  • An example of a DSC instrument is TA Instruments 2920 Differential Scanning Calorimeter.
  • the compositions of the present invention comprise a first component comprising one or more thermoplastic polymers selected from polyesters, polycarbonates, polyary ⁇ ates, and homogeneous blends thereof.
  • thermoplastic polymer is intended to have its plain meaning as would be understood by persons having ordinary skill in the art, that is, a polymer that softens when exposed to heat and returns to its original condition when cooled to room temperature.
  • the first component may comprise a single thermoplastic polymer or may comprise a blend of 2 or more polymers provided that the blend is a homogeneous blend.
  • homogeneous blend as used herein, is synonymous with the term “miscible”, and is intended to mean that the blend has a single, homogeneous phase as indicated by a single, composition-dependent Tg.
  • a first polymer that is miscible with second polymer may be used to "plasticize" the second polymer as illustrated, for example, in U.S. Patent No. 6,21 1 ,309.
  • Homogeneous blends may be formed by simply blending two or polymers or, in the case of condensation polymers such as for example, polyesters or polyamides, by transesterifying or transamidating two or more polymers.
  • condensation polymers such as for example, polyesters or polyamides
  • transesterifying or transamidating two or more polymers by transesterifying or transamidating two or more polymers.
  • the term "immiscible" denotes a blend that shows at least 2, randomly mixed, phases and exhibits more than one Tg. Some polymers may be immiscible and yet compatible with each other.
  • the first component may comprise one or more thermoplastic polymers selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof.
  • the first component may comprise a polyester comprising (a) diacid residues, comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxyltc acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl
  • the diacid residues can comprise the residues of one or more dicarboxylic acids selected from terephthalic acid, isophthalic acid, or combinations thereof, and the diol residues comprise the residues of one or more diols selected from 1 ,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and combinations thereof.
  • the diacid residues may comprise the residues of terephthalic acid and isophthalic acid.
  • a higher concentration of terephthalic acid in the polyester than isophthalic acid is advantageous because the resulting polyester provides greater impact strength to the blend.
  • the diacid residues may comprise from about 60 to about 100 mole percent of the residues terephthalic acid and 0 to about 40 mole percent of the residues isophthalic acid and the diol residues may comprise about 100 mole percent of the residues of 1 ,4-cyclohexanedimethanol.
  • dicarboxylic acid content include about 80 to about 100. mole percent terephthalic acid and 0 to 20 mole percent isophthalic acid, and about 100 mole percent terephthalic acid.
  • polyesters comprising: (a) diacid residues comprising 80 to 100 mole percent of the residues of terephthalic acid and diol residues comprising about 50 to about 90 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 10 to about 50 mole percent of the residues of neopentyl glycol; (b) diacid residues comprising 100 mole percent of the residues of terephthalic acid and diol residues comprising about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexanedimethanol and 60 to about 90 mole percent of the residues of ethylene glycol; (c) diacid residues comprising 100 mole percent terephthalic acid and diol residues comprising about 10 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol, 0 to about 90 mo
  • the dicarboxylic acid may be selected from terephthalic acid and isophthalic acid, and the diol is selected from 1 ,4-cyclohexanedimethanol and ethylene glycol.
  • the dicarboxylic acid is terephthalic acid and the diol is 1 ,4-cyclohexanedimethanol.
  • the diacid residues may comprise at least 95 mole percent of the residues of terephthalic acid and the diol residues may comprise about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexane- dimethanol, about 1 to about 25 mole percent of the residues of diethylene glycol, and about 35 to about 89 mole percent of the residues of ethylene glycol.
  • the polyester may further comprise 0 to about 20 mole percent of one or more residues of a modifying diacid containing 2 to 20 carbon atoms if desired.
  • a modifying diacid containing 2 to 20 carbon atoms if desired.
  • from 0 to about 30 mole % of other aromatic dicarboxylic acids containing 8 to about 16 carbon atoms, cycloaliphatic dicarboxylic acids containing 8 to about 16 carbon atoms, aliphatic dicarboxylic acids containing about 2 to about 16 carbon atoms, or mixtures thereof may be used.
  • modifying carboxylic acids include, but are not limited to, one or more of 4,4'-biphenyldicarboxylic acid, 1 ,4- naphthalenedicarboxylic acid, 1 ,5- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 2,7- naphthalenedicarb ⁇ xylic acid, 4,4'-oxybenzoic acid, trans-4,4 1 - stilbenedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
  • the polyester can comprise about 1 to about 99 mole percent, based on the total moles of diol residues, of the residues of 1 ,4-cyclohexanedimethanol, about 99 to about 1 mole percent of the residues ethylene glycol.
  • Typical mole percentages for the residues of 1 ,4- cyclohexanedimethanol for the polyesters of the invention include from about 1 to about 10 mole percent, from about 1 to about 25 mole percent, from about 1 to about 40 mole percent, 50 mole percent and greater, and 100 mole percent.
  • the dicarboxylic acid is 1 ,4-cyclohexane- dicarboxylic acid and the diol is 1 ,4-cyclohexanedimethanol.
  • the polyester may comprise the residues of 1 ,4-cyclohexane- dimethanol units and the neopentyl glycol.
  • the polyester may comprise the residues of 1 ,4-cyclohexanedimethanol units and 2,2,4,4- tetramethyi-l ,3-cyclobutanediol.
  • the diol component of the polyester also may be modified from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons.
  • Other ranges of modifying diol include, but are not limited to, from 0 to about 10 mole percent, and less than 5 mole percent.
  • the modifying diol may be selected from one or more of 1 ,2-propanediol, 1 ,3- propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,4- cyclohexanedimethanol, p-xylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, and 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol.
  • polyalkylene glycols examples include poly(tetramethylene glycol) (“PTMC”) and poly(ethylene glycol) (“PEG”) having molecular weights up to about 2,000.
  • the diol component for example, can be modified with 0 to about 10 mole percent polyethylene glycol or polytetramethylene glycol to enhance elastomeric behavior.
  • the diol residues may comprise about 10 to about 99 mole percent of residues of 1 ,4-cyclohexanedimethanol, 0 to about 90 mole percent of residues of ethylene glycol, and about 1 to about 25 mole percent of residues of diethylene glycol.
  • the polyester also may contain up to about 5 mole percent, typically from about 0.1 to about 2.0 mole%, based on the acid or diol component, of the residues of a pol ⁇ functional branching agent derived from a compound having at least three carboxyl and/or hydroxy groups to form a branched polyester.
  • a pol ⁇ functional branching agent derived from a compound having at least three carboxyl and/or hydroxy groups to form a branched polyester.
  • examples of such compounds include trimellitic acid or anhydride, trimesic acid, pyromellitc anhydride, trimethylolethane, trimethylolpropane, a trimer acid, and the like. It will be understood by persons skilled in the art that the final composition can be arrived at by blending various resins or by direct reactor copolymerization. The latter is desirable to minimize compositional variability but economic necessities often make blending more cost effective.
  • polyesters are those containing 100 mole percent terephthalic residues, based on the total diacid residues, and any one of the following diol residue compositions, based on the total diol residues: (i) about 1 to about 5 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 99 to about 95 mole percent of the residues of ethylene glycol; (ii) about 29 to about 33 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 71 to about 67 mole percent of the residues of ethylene glycol; (iii) about 45 to about 55 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 55 to about 45 mole percent of the residues of ethylene glycol; (iv) about 60 to about 65 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 40 to about 35 mole percent of the
  • the polyesters generally will have inherent viscosity (LV.) values in the range of about 0.4 dL/g to about 1 .4 dL/g. Additional examples of LV. ranges include about 0.65 dL/g to about 1.0 dL/g and about 0.7 dL/g to about 0.85 dL/g. As described previously, inherent viscosity is measured at 25 0 C using 0.5 grams of polymer per 100 ml of a solvent comprising 60 weight percent phenol and 40 weight % tetrachloroethane
  • the polymers of the invention may be crystalline, semicrystalline, or amorphous polymers.
  • the term "semicrystalline”, as used herein, means that the polymer contains two phases: an ordered crystalline phase and an unordered amorphous phase.
  • Polymers with a semicrystalline morphology exhibit both a crystalline melting temperature (Tm) and a glass transition temperature (Tg) and may be distinguished from “amorphous" polymers, which exhibit only a glass transition temperature.
  • the polyesters used in the present invention typically are prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues.
  • the polyesters derived from dicarboxylic acid and diol residues of the present invention therefore, contain substantially equal molar proportions of acid residues (100 mole percent) and diol residues (100 mole percent) such that the total moles of repeating units is equal to 100 mole percent.
  • the mole percentages provided in the present disclosure therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units.
  • a copolyester containing 30 mole percent terephthalic acid means that the copolyester contains 30 mole percent terephthalic residues out of a total of 100 mole percent acid residues.
  • a copolyester containing 30 mole percent 1 ,4-cyclohexanedimethanol means that the copolyester contains 30 mole percent 1 ,4-cyclohexane- dimethanol residues out of a total of 100 mole percent diol residues.
  • copolyesters of terephthalic acid, ethylene glycol, and 1 ,4-cyclohexandimethanol may be referred to as "PET” when the glycol component is primarily ethylene glycol, "PCT” when the glycol component is primarily 1 ,4-cyclohexanedimethanol, "PETC” when the ratio of ethylene glycol to 1 ,4-cyclohexanedimethanol is greater than 1 and "PCTG” when the ratio of ethylene glycol to 1 ,4-cyclohexanedimethanol ratio is less than 1.
  • the polyesters of the instant invention are readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, and the appropriate diol or diol mixtures using typical polycondensation reaction conditions.
  • the dicarboxylic acid component of the polyesters of the present invention can be derived from dicarboxylic acids, their corresponding esters, or mixtures thereof.
  • esters of the dicarboxylic acids useful in the present invention include the dimethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters, and the like.
  • the polyesters of the present invention are prepared by procedures known to persons skilled in the art. They may be made by continuous, semi- continuous, and batch modes of operation and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors.
  • the reaction of the diol and dicarboxylic acid may be carried out using conventional polyester polymerization conditions or by melt phase processes, but those with sufficient crystal Unity may be made by melt phase followed by solid phase polycondensation techniques.
  • the reaction process may comprise two steps.
  • the diol component and the dicarboxylic acid component such as, for example, dimethyl terephthalate
  • the reaction process may comprise two steps.
  • the diol component and the dicarboxylic acid component such as, for example, dimethyl terephthalate
  • the diol component and the dicarboxylic acid component are reacted at elevated temperatures, typically, about 1 5O 0 C to about 25O 0 C for about 0.5 to about 8 hours at pressures ranging from about 0.0 kPa gauge to about 41 4 kPa gauge (60 pounds per square inch, "psig").
  • the temperature for the ester interchange reaction ranges from about 1 SO 0 C to about 23O 0 C for about 1 to about 4 hours while the preferred pressure ranges from about 1 03 kPa gauge (1 5 psig) to about 276 kPa gauge (40 psig).
  • the reaction product is heated under higher temperatures and under reduced pressure to form the polyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system.
  • This second step, or polycondensation step is continued under higher vacuum and a temperature which generally ranges from about 23O 0 C to about 35O 0 C, preferably about 250°C to about 310 0 C and, most preferably, about 26O 0 C to about 29O 0 C for about 0.1 to about 6 hours, or preferably, for about 0.2 to about 2 hours, until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained.
  • the polycondensation step may be conducted under reduced pressure which ranges from about 53 kPa (400 torr) to about 0.01 3 kPa (0.1 torr). Stirring or appropriate conditions are used in both stages to ensure adequate heat transfer and surface renewal of the reaction mixture.
  • reaction rates of both stages are increased by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
  • catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like.
  • a three-stage manufacturing procedure similar to that described in U.S. Patent No. 5,290,631 , may also be used, particularly when a mixed monomer feed of acids and esters is employed.
  • polyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components.
  • the reaction is conducted at a pressure of from about 7 kPa gauge (1 psig) to about 1379 kPa gauge (200 psig), preferably less than 689 kPa (100 psig) to produce a low molecular weight polyester product having an average degree of polymerization of from about 1 .4 to about 10.
  • the temperatures employed during the direct esterification reaction typically range from about 18O 0 C to about 280 0 C, more preferably ranging from about 22O 0 C to about 27O 0 C.
  • This low molecular weight polymer may then be polymerized by a polycondensation reaction.
  • thermoplastic polymers of the invention may also comprise a polyarylate.
  • Polyarylates are obtained by polymerization of a dihydric phenol and a dicarboxylic acid. Examples of polyarylates that can be used in the compositions, processes, and shaped articles of the instant invention are described in U.S. Patent No.'s 4,598,130; 5,034,502; and 4,374,239.
  • dihydric phenols that can be used to prepare the polyarylates are bisphenols such as bis(4-hydroxyphenyl)methane; 2,2-bis(4-hydroxyphenyl) propane (“bisphenol-A”); 2,2-bis(4-hydroxy-3-methylphenyl)propane; 4,4-bis(4- hydroxyphenyOheptane; 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; 2,2- bis(4 ⁇ hydroxy ⁇ 3,5-dibromophenyl)propane; dihydric phenol ethers such as, for example, bis(4-hydroxyphenyl)ether; bis(3,5-dichloro-4-hydroxyphenyl)ether;; dihydroxydiphenyls such as, for example, p,p'-dihydroxydiphenyl, 3,3'- dichloro-4, 4'-dihydroxydiphenyl; dihydroxyaryl sulfones such as, for example, bis(4- hydroxyphenyl)
  • dihydric phenols are also available such as are disclosed, for example, in U.S. Pat. Nos. 2,999,835; 3,028,365 and 3,1 53,008. Also suitable are copolymers prepared from the above dihydric phenols copolymerized with halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane.
  • halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane.
  • dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids such as phthalic, isophthalic, terephthalic, o-phthalic, o-, m-, and p-phenylenediacetic acids, and polynuclear aromatic acids such as, for example, diphenic acid and 1 ,4-naphthalic acid.
  • the polyarylates of the present invention can be prepared by any polyester forming reactions well known in the art such as, for example, interfacial polymerization by mixing a solution of an aromatic dicarboxylic acid dihalide in an organic solvent with an alkaline aqueous solution of a bisphenol under stirring to react these materials; solution polymerization by reacting an aromatic dicarboxylic acid dihalide with a bisphenol in the presence of a deacidifying agent such as pyridine in an organic solvent; molten polymerization by reacting an aromatic dicarboxylic acid diphenyl ester with a bisphenol; molten polymerization by reacting an aromatic dicarboxylic acid, diphenyl carbonate and a bisphenol; molten polymerization by reacting an aromatic dicarboxylic acid with a bisphenol diacetate; and polymerization by reacting an aromatic dicarboxylic acid with a bisphenol diacetate.
  • a deacidifying agent such as pyridine
  • polyarylates of the invention typically have inherent viscosities of about 0.5 to about 1.1 dL/gm.
  • the polyester, polycarbonates, and polyarylates may further comprise one or more of the following: antioxidants, melt strength enhancers, branching agents (e.g., glycerol, trimellitic acid and anhydride), chain extenders, flame retardants, fillers, acid scavengers, dyes, colorants, pigments, antiblocking agents, flow enhancers, impact modifiers, antistatic agents, processing aids, mold release additives, plasticizers, slips, stabilizers, waxes, UV absorbers, optical brighteners, lubricants, pinning additives, foaming agents, antistats, nucleators, and the like.
  • branching agents e.g., glycerol, trimellitic acid and anhydride
  • chain extenders e.g., flame retardants, fillers, acid scavengers, dyes, colorants, pigments, antiblocking agents, flow enhancers, impact modifiers, antistatic agents, processing aids, mold release additives, plasticizers, slips
  • Colorants may be added to impart a desired neutral hue and/or brightness to the polyester.
  • the polyester compositions may comprise 0 to about 30 weight percent of one or more processing aids to alter the surface properties of the composition and/or to enhance flow.
  • processing aids include calcium carbonate, talc, clay, mica, zeolites, wollastonite, kaolin, diatomaceous earth, TiO 2 , NH4CI, silica, calcium oxide, sodium sulfate, and calcium phosphate.
  • Use of titanium dioxide and other pigments or dyes might be included, for example, to control whiteness of the film, or to make a colored articles.
  • An antistat or other coating may also be ⁇ applied to the surface of the article.
  • the second component (ii) of the compositions of the invention comprises a transamidized, homogeneous blend of at least two polyamides.
  • the homogeneous blend will comprise from 2 to about 10 different polyamides.
  • the homogeneous blend can comprise from 2 to 4 polyamides.
  • polyamides that display a melting point below about 300°C can be used as at least one polyamide.
  • polyamides with the melting point less than about 275°C and glass transition temperature greater than about 25 0 C may be used.
  • the polyamides have an I. V. between about 0.3 dL/g and about 2.0 dL/g and, preferably at least 0.5 dL/g.
  • transamidized is intended to be synonymous with the terms “trans am id ate” and “transamidation”, and means the process of exchanging am/do groups between two different poiyamides.
  • Transamidation between two or more polyamides can be accomplished by contacting the polyamides at elevated temperatures, typically from about 27O 0 C to about 35O°C. Other examples of transamidation temperatures are about 280 0 C to about 35O 0 C and about 290 0 C to about 34O 0 C.
  • Transamidation between the polyamides is indicated by the presence of a single glass transition temperature (“Tg") for the blend as determined by differential scanning calorimetry ("DSC") using standard techniques well known to persons skilled in the art such as, for example, described in ASTM Method D341 8.
  • Tg glass transition temperature
  • DSC differential scanning calorimetry
  • the polyamides may be heated together directly at these temperature or in the presence of the thermoplastic polymers of the first component (i).
  • the contacting and, hence, transamidation of the polyamides can take place by melt blending of the first and second components, during extrusion, or other high temperature processing of the polymer composition and its components.
  • the polyamides may be heated together in a separate vessel and then melt blended with the first component.
  • the first and second polyamides of the second component may be selected from a wide range of polyamides.
  • the polyamides can comprise partially aromatic polyamides and aliphatic polyamides having a number average molecular weight of 7,000 or less. Combinations of such polyamides are included also within the scope of the invention.
  • Partially aromatic polyamides comprise amide linkages between at least one aromatic ring and at least one nonaromatic species.
  • wholly aromatic polyamides generally are liquid crystalline, the blends of such resins having melting points less than 300°C can be used for this invention.
  • the rapid transamidization (amide-amide interchange) of aliphatic nylon with aromatic or partially aromatic polyamide permits the tailoring of refractive index of the polyamide blend by adjusting the ratios of aliphatic polyamide to aromatic, or partially aromatic, polyamide.
  • This technique enables a matching of the refractive index of the homogeneous polyamide blend to the thermoplastic polymer such as, for example, one or more polyesters, of the first component.
  • a reference for transamidization can be found in the work by Y. Takeda, et.al., Polymer, 1992 vol. 33, pg. 3394.
  • the second component can be a transamidized, homogeneous blend of 2 or more polyamides such as, for example, a first polyamide and a second polyamide which are selected to give a refractive index in the second component such that second and first components have a difference in refractive index (Rl(second component) - RKfirst component)) of about 0.006 to about -0.0006.
  • the first and second polyamide have different amounts of aromatic and aliphatic residues.
  • the second component (ii) can comprise a homogeneous blend of a first polyamide, comprising aromatic residues, and of a second polyamide comprising aliphatic residues.
  • aliphatic as used herein with respect to the diamine and dicarboxylic acid monomers of the polyamides of the present invention, means that carboxyl or amino groups of the monomer are not connected through an aromatic nucleus.
  • adipic acid contains no aromatic nucleus in its backbone, i.e., the chain of carbon atoms connecting the carboxylic acid groups; thus, it is “aliphatic”.
  • aromatic means the dicarboxylic acid or diamine contains an aromatic nucleus in the backbone such as, for example, terephthalic acid or ⁇ ,4-metaxylylenediamine.
  • aromatic polyamides are those polyamids comprising at least 70 mole % of residues comprising diamines such as m- xylylenediamine or a xylylenediamine mixture comprising m-xylylenediamine and up to 30% of p-xylylenediamine and an aliphatic dicarbox ⁇ c acid having 6 to 10 carbon atoms.
  • aliphatic therefore, is intended to include both aliphatic and cycloaliphatic structures such as, for example, diamine, diacids, lactams, aminoalcohols.and aminocarboxylic acids, that contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffinic in nature, unsaturated (i.e., containing non-aromatic carbon-carbon double bonds), or acetylenic (i.e., containing carbon-carbon triple bonds).
  • diamine diacids
  • lactams aminoalcohols.and aminocarboxylic acids
  • aminocarboxylic acids that contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffinic in nature, unsaturated (i.e., containing non-aromatic carbon-carbon double bonds), or acetylenic (i.e., containing carbon-carbon triple bonds).
  • aliphatic is intended to include linear and branched, chain structures (referred to herein as “aliphatic”) and cyclic structures (referred to herein as “alicyclic” or “cycloaliphatic”).
  • aliphatic is not intended to exclude any aromatic substituents that may be attached to the backbone of an aliphatic or cycloaliphatic diol or diacid or hydroxycarboxylic acid.
  • the weight percentage ratio of the first and second polyamides present in the transamidized, homogeneous blend may range from about 1 :50 to about 50:1 based on the total weight of the second component.
  • Other examples of weight percentage ratios are 1 :20 to about 20:1 and about 1 :10 to about 10:1.
  • polyamide forming diacids and diamines can be used.
  • the polyamides also may contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride, or other polyamide forming polyacids and polyamines known in the art.
  • partially aromatic polyamides include, but are not limited to: poly(m-xylylene adipamide) (referred to herein as "MXD6" nylon), poly(hexamethylene isophthalamide), poly(hexamethylene adipamide-co- isophthalamide), poly(hexamethylene adipamide-co-terephthalamide), and poly(hexamethylene isophthalamide-co-terephthalamide).
  • the partially aromatic polyamide is poly(m-xylylene adipamide).
  • the partially aromatic polyamides may have a number average molecular weight of 7000 or less.
  • Representative examples of aliphatic polyamides include poly(2-pyrrolidinone) (nylon 4, 6; CAS No.
  • polycapramide (nylon 6; CAS No. 1 8,1 1 1 -0), poly(2-piperidone) (nylon 5, CAS No. 24938-57-6); poly(7-aminoheptanoic acid) (nylon 7; CAS No. 25035-01 -2); poly(nonanamide) (nylon 9; CAS No. 25748-72-5); poly(l 1 -aminoundecanoic acid) (nylon 1 1 ; CAS No. 25035-04-5); poly(12-aminolauric acid) (nylon 12, CAS No.
  • poly(ethyleneadipamide) (nylon 2,6); polytetramethylene- adipamide (nylon 4,6; CAS No. 50327-22-5); polyhexamethylene-adipamide (nylon 6,6; CAS No. 42,917-1), (nylon 6,9; CAS No. 18,806-9) poly- (hexamethylene-sebacamide) (nylon 6,10; CAS No. 9008-66-6), poly(hexamethylene-undecanamide) (nylon 6, 1 1 ) poly (hexamethylene- dodecamide) (nylon 6,12; CAS No.
  • poly(octamethylene- adipamide) (nylon 8,6); adipic acid-decamethylenediamine copolymer (nylon 10,6; CAS No. 26123-27-3); polydecamethylene- dodecamide (nylon 10, 12); poly(dodecamethyiene-adipamide) (nylon 12,6); and poly(dodecamethylene- sebacamide) (nylon 12,8).
  • the second component (ii) can comprise a homogeneous blend comprising a first polyamide comprising the residues of m- xylylenediamine and adipic acid, and a second polyamide comprising the residues of at least one aliphatic or cycloaliphatic monomer selected from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioc acid, dodecanedioc acid, caprolactam, butyrolactam, 1 1 -aminoundecanedioc acid, isophthalic acid, and hexamethylene diamine.
  • the first polyamide for example, can comprise MXD6 nylon, which is commerically available from Mitsubishi Corporation.
  • the second polyamide can comprise at least one polyamide selected from from nylon 4; nylon 6; nylon 9; nylon 1 1 ; nylon 12; nylon 6,6; nylon 5,10; nylon 6,12; nylon 6,11 ; nylon 10,12; and combinations thereof.
  • the second polyamide can comprise nylon 6, nylon 6,6, or blends thereof.
  • the second component also may comprise a single copolyamide in which the composition of monomer residues is chosen to give a refractive index that closely matches the refractive index of the first component.
  • the invention provides a polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and
  • the copolyamide can the residues of m- xylylenediamine, p-xylylenediamine, or a combination thereof; and the residues of at least one monomer selected from terephthalic acid, isophthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioc acid, dodecanedioc acid, caprolactam, butyrolactam, 1 1 -amino-undecanedioc acid, and 1 ,6-hexamethylenediamine.
  • the copolyamide can comprise about 1 5 to about 100 mole percent of the residues of m- xylylenediamine, based on a total diamine residue content of 1 00 mole%, and about 1 5 to about 85 mole percent of the residues adipic acid and about 85 to about 1 5 mole percent of the residues of one or more aliphatic or cycloaliphatic dicarboxylic acids selected from pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and 1 ,4-cyclohexanedicarboxylic acid, based on a total diacid residue content of 1 00 mole%. It is understood that the various embodiments of homogeneous blends of polyamides and copolyamides referred to herein can be combined with any of the embodiments of the polyesters discussed hereinabove.
  • copolyamides that can be used as in composition of the invention, either alone or as part of a homogeneous blend with another polyamide, include, but are not limited to, copolyamides comprising from about 1 5 to about 1 00 mole percent of the residues of m- xylylenediamine, based on a total diamine residue content of 1 00 mole%, and the residues of adipic acid.
  • Typical amounts of adipic acid residues which may be present in these copolyamides, based on the total moles of diacid residues are about 5 to about 85 mole percent, about 20 to about 80 mole percent, and about 25 to about 75 mole percent.
  • the remainder of the dicarboxylic acid residues can comprise residues from one or more aliphatic dicarboxylic acids having from 7-12 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, or 1 ,4-cyclohexanedicarboxylic acid.
  • the polyamide acid also may comprise residues from isophthalic acid and terephthalic acid.
  • the copolyamides of the invention also may comprise other diamines or lactam residues in addition to m-xylyienediamine residues.
  • the copolyamide can comprise at least 1 5 mole percent, or at least about 20 mole percent of the residues of m-xylylenediamine with the remainder of the diamines residues comprising the residues of one or more aliphatic or aromatic diamines.
  • the copolyamide may comprise about 80 mole percent or about 85 mole %, of the residues of 1 ,6-hexamethylene diamine, based on the total moles of diamine residues. Varying amounts of p-xylylene- diamine, l ,3-cyclohexanebis(methylamine), or 1 ,4-cyclohexanebis(methyl- amine), also may be used.
  • the copolyamide may comprise the residues of a lactam, such as caprolactam, or lactams based on gamma-amino-butyric acid or 11 -amino-undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or from about 10 mole percent to about 70 mole percent based on the total moles of repeating units.
  • a lactam such as caprolactam
  • the copolyamides of the invention can comprise from about 1 5 mole percent to about 85 mole percent, about 20 to about 80 mole percent, or about 25 to about 75 mole percent of the residues from m-xylylenediamine, based on the total moles of diamine residues with the remainder of the diamine residues content comprising residues from one or more diamines, such as aliphatic diamines, and especially 1 ,6-hexamethylene diamine.
  • the diamine residues may further comprise minor amounts of the residues of other diamines, for example p-xylylenediamine, or a cyclic aliphatic diamine such as, for example, one or more of: 1 ,3-cyclohexanebis(methylamine) or 1 ,4- cyclohexanebis(methylamine).
  • other diamines for example p-xylylenediamine
  • a cyclic aliphatic diamine such as, for example, one or more of: 1 ,3-cyclohexanebis(methylamine) or 1 ,4- cyclohexanebis(methylamine).
  • the polyamide may optionally include, in place of a portion of the adipic acid, residues from one or more aliphatic or aromatic dicarboxylic acids having from 7-12 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, 1 ,4-cyclohexanedicarboxylic acid, or isophthalic acid, which may be present in an amount from about 1 5 mole percent to about 85 mole percent, optionally with minor amounts of terephthalic acid.
  • residues from one or more aliphatic or aromatic dicarboxylic acids having from 7-12 carbon atoms such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, 1 ,4-cyclohexanedicarboxylic acid, or isophthalic acid, which may be present in an amount from about 1 5
  • the polyamide also may comprise the residues of a lactam, such as caprolactam, or lactams based on gamma-amino-butyric acid or 1 l -amino ⁇ undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or about 10 mole% to 70 mole percent, based on the total moles repeating units.
  • a lactam such as caprolactam
  • the copolyamides according to the invention may comprise from about 15 mole percent up to about 90 mole percent of residues from adipic acid, with the remaining diacid residues comprising the about 10 to about 85 mole percent of the residues of isophthalic acid, based on the total moles of dicarboxylic acid residues.
  • Additional examples of adipic acid and isophthalic acid residue content include about 20 to 80 mole percent, and about 25 to about 75 mole percent.
  • the polyamide may optionally comprise minor amounts of residues from one or more aliphatic dicarboxylic acids having from 7-12 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, or 1 ,4-cyclohexanedicarboxylic acid, optionally with minor amounts of terephthalic acid.
  • the polyamides may comprise m- xylylenediamine residues. Examples of m-xylylenediame residue concentrations include about 1 5 to about 90 mole percent, about 20 to about 85 mole percent, or about 25 to about 80 mole percent.
  • the remaining residues can comprise from one or more aliphatic diamines, such as, for example, 1 ,6-hexamethylene diamine, one or more aromatic diamines such as, for example, p-xylylene- diamine.
  • the copolyamide also may comprise the residues of a lactam - 47 -
  • caprolactam such as, for example, caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino-undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent or about 10 mole percent to about 70 mole percent, based on the total moles of repeating units.
  • the copolyamides of the invention may comprise the residues of one or more lactams such as, for example, caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino- undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or from about 10 mole percent to about 70 mole percent, or from about 1 5 mole percent to about 60 mole percent, based on the total moles of repeating units.
  • lactams such as, for example, caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino- undecanoic acid
  • the residues of one or more aliphatic dicarboxylic acids having from 7-12 carbon atoms such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, or 1 ,4-cyclohexanedicarboxylic acid, also may be present in amounts from about 20 mole percent to about 80 mole percent, based on the total moles of repeating units.
  • the copolyamide may comprise residues from isophthalic acid or terephthalic acid.
  • the copolyamides can comprise from about 1 5 mole percent to about 85 mole percent of the residues from m-xylylenediamine, based on the total moles of diamine residues.
  • m- xylylenediamine content are about 20 to about 80 mole percent and about 25 to about 75 mole percent.
  • the remainder of the diamine residues may comprise the residues of one or more diamines aliphatic diamines such as, for example, 1 ,6-hexamethylene diamine.
  • the diamine residues may further comprise minor amounts of the residues of other diamines, for example p-xylyienediamine, or a cyclic aliphatic diamine such as, for example, one or more of. 1 ,3-cyclohexanebis(metriylamine) or 1 ,4-cyciohexanebis(methylamine).
  • other diamines for example p-xylyienediamine
  • a cyclic aliphatic diamine such as, for example, one or more of. 1 ,3-cyclohexanebis(metriylamine) or 1 ,4-cyciohexanebis(methylamine).
  • minor amounts of one or more of: p-xylylenediamine, 1 ,3- cyclohexanebis(methylamine), or l ,4-cyclohexanebis(methylamine), may be used.
  • Another embodiment of the invention is polymer composition, consisting essentially of an immiscible blend of:
  • a first component consisting essentially of at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component consisting essentially of a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - RI(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of ⁇ Q% or less.
  • compositions which are immiscible blends, that is, having at least 2, composition-dependent Tg's as measured by DSC, and which have first component containing a polyester, polycarbonate, polyaryiate, or homogeneous blends thereof and a second component containing a homogeneous, transamidized blend of at least 2 polyamides.
  • the composition is understood to exclude any elements that would substantially alter the essential properties of the composition to which the phrase refers.
  • compositions may include other components that do not alter the refractive index of the components, %haze of the blend, the %transmittance, or the miscibility of the blend.
  • a compatibilizer which may alter the miscibility and refractive index of the composition, would be excluded from this embodiment.
  • a second component containing a copolyamide prepared by copolymerization of the component monomers would be excluded because such a copolyamide would be considered to have different properties than a homogeneous, transamidized blend of at least 2 poiyamides, even if the mole percentage of the monomer residues are equivalent.
  • an oxygen-scavenging composition consisting essentially of:
  • first component consisting essentially of at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
  • second component consisting essentially of a copolyamide or a transamidized, homogeneous blend of at least two poiyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, RKsecond component) - Rl (f i rst component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less; and
  • composition at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements; wherein the first component and the second component have refractive indices which differ in absolute value by 0.008 or less and the shaped article has a % transmittance of at least 75%, and a haze of 10% or less.
  • the composition is understood to exclude any elements that would substantially alter the essential properties of the composition to which the phrase refers, such as, for example, the refractive index of the components, %haze of the blend, the %transmittance, the miscibility of the blend, or the oxygen-scavenging propertions of the composition.
  • an oxygen- scavenging component other than a copolyamide or a transmidized blend of polyamides such as, for example, a diene, polyether, or any easily oxidizable organic compound other than the components as listed in the claims would be excluded.
  • the polyamides used in the present invention typically are prepared from dicarboxylic acids and diamines, which react in substantially equal proportions, or by the ring-opening polymerization of lactams, and are incorporated into the polyamide polymer as their corresponding residues.
  • the polyamides derived from dicarboxylic acid and diamine residues of the present invention therefore, contain substantially equal molar proportions of acid residues (100 mole percent) and diamine residues (100 mole percent) such that the total moles of repeating units is equal to 100 mole percent.
  • the mole percentages provided in the present disclosure therefore, may be based on the total moles of acid residues, the total moles of diamine residues, or the total moles of repeating units.
  • a polyamide or copolyamide containing 30 mole percent terephthalic acid means that the copolyamide contains 30 mole percent terephthalic residues out of a total of 100 mole percent acid residues. Thus, there are 30 moles of terephthalic residues among every 100 moles of acid residues.
  • a copolyamide containing 30 mole percent m-xylylenediamine means that the copolyester contains 30 mole percent m- xylylenediamine residues out of a total of 100 mole percent diamine residues. Thus, there are 30 moles of m-xylylenediamine residues among every 100 moles of diamine residues.
  • the polyamides are generally prepared by melt phase polymerization from a diacid-diamine complex which may be prepared either in situ or in a separate step. In either method, the diacid and diamine are used as starting materials. Alternatively, an ester form of the diacid may be used, preferably the dimethyl ester. If the ester is used, the reaction must be carried out at a relatively low temperature, generally 80 to 120 0 C, until the ester is converted to an amide. The mixture is then heated to the polymerization temperature.
  • caprolactam either caprolactam or 6- aminocaproic acid can be used as a starting material and the polymerization may be catalyzed by the addition of adipic acid/hexamethylene diamine salt which results in a nylon 6/66 copolymer.
  • the diacid-diamine complex is used, the mixture is heated to melting and stirred until equilibration.
  • the molecular weight is controlled by the diacid-diamine ratio. An excess of diamine produces a higher concentration of terminal amino groups.
  • the second component and first component of the immiscible blend typically have refractive indices which differ by about 0.006 to about -0.0006, that is, the Rl(second component) - Rl(first component) is about 0.006 to about -0.0006.
  • differences in the absolute value of the refractive indices are about 0.005 to about -0.0006, about 0.004 to about -0.0006, about 0.003 to about -0.0006, about 0.005 to about -0.0005, and about 0.004 to about -0.0005.
  • the difference in refractive indices which may be acceptable depends on the blend composition, particle diameter, refractive index, wavelength, and particle structure as described by Biangardi et al., DieAngew. Makromole. Chemie, 183, 221 (1990).
  • the immiscible blend of the instant invention has excellent clarity and has a % transmittance of at least 75%, as determined by ASTM Method Dl 003, and a haze of 10% or less.
  • Other examples of % transmittance are at least 77%, at least 80%, and at least 85%.
  • Additional examples of haze values which may be exhibited by the blends of the invention are 9% or less, 7% or less, 5% or less, and 3% or less.
  • haze is determined by molding or casting the composition into a sheet or film having a thickness of 1 /8 inch or less and measuring the haze according to the procedure described in the examples.
  • the haze can be determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze according the procedure given in the examples.
  • the first component also may comprise homogeneous blend of one or more polymers.
  • the first component may comprise a homogeneous blend of a first polyester with one or more polymers chosen from a polycarbonate, a second polyester, and a polyarylate.
  • the polyester may be any polyester as described herein.
  • the first component may comprise a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A.
  • the polycarbonate may comprise about 90 to 100 mole percent, based on the total moles of diol residues, of the residues bisphenol A, and from 0 to about 10 mole percent of the residues of one or more modifying aliphatic diols or dihydric phenols having from 2 to 16 carbons.
  • Representative examples include bis(4-hydroxyphenyl)methane; 2,2-bis(4-hydroxyphenyl) propane ("bisphenol-A"); 2,2-bis(4-hydroxy-3 ⁇ methylphenyl)propane; 4,4-bis(4- hydroxyphenyl)heptane; 2,2-bis(4-hydroxy-3,5-dich!orophenyl)propane; 2,2- bis(4-hydroxy-3,5-dibromophenyl)propane; dihydric phenol ethers such as, for example, bis(4-hydroxyphenyl)ether; bis(3,5-dichloro-4-hydroxyphenyl)ether;; dihydroxydiphenyls such as, for example, p.p'-dihydroxydiphenyl, 3,3'- dichloro-4, 4'-dihydroxydiphenyl; dihydroxyary) sulfones such as, for example, bis(4- hydroxyphenyOsulfone; bis(3,5-dimethyl-4-hydroxyphenyl
  • dihydric phenols are also available such as are disclosed, for example, in U.S. Patent No.'s 2,999,835; 3,028,365 and 3,153,008. Also suitable are copolymers prepared from the above dihydric phenols copolymerized with halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane.
  • halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane.
  • dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids such as phthalic, isophthalic, terephthalic, o-phthalic, o-, m-, and p-phenylenediacetic acids, and polynuclear aromatic acids such as, for example, diphenic acid and 1 ,4-naphthalic acid.
  • aliphatic diofs include ethylene glycol, propanediols, butanediols, pentanediols, hexandiols, heptanediols, octanediols, neopentyl glycol, aryl-alkyl glycols such as styrene glycol, xylylene glycols, dihydroxy alkyl ethers of dihydric phenols such as the dihydroxy ethyl ether of Bisphenol-A, and the like.
  • aliphatic diols are higher molecular weight aliphatic dihydroxy compounds such as, for example, polyethylene glycols, polystyrene glycols, polypropylene glycols, polybutylene glycols, polythioglycols, poly-arylalkyl ether glycols and copolymer polyether glycols. Additional representative examples of dihydric phenols and aliphatic diols are described in U.S. Patent No.'s 3,030,335 and 3,317,466.
  • the polycarbonate may further comprise the residues of one or more branching agents such as, for example, tetraphenolic compounds, tri ⁇ (4-hydroxyphenyl) ethane, pentaerythritol triacrylate and others compounds as disclosed in U.S. Patent No.'s 6,160,082; 6,022,941 ; 5,262,51 1 ; 4,474,999; and 4,286,083.
  • branching agents such as, for example, tetraphenolic compounds, tri ⁇ (4-hydroxyphenyl) ethane, pentaerythritol triacrylate and others compounds as disclosed in U.S. Patent No.'s 6,160,082; 6,022,941 ; 5,262,51 1 ; 4,474,999; and 4,286,083.
  • branching agents are mentioned herein below.
  • the polycarbonate comprises at least 95 mole percent, based on the total moles of diol residues, of the residues of bisphenol A.
  • the inherent viscosity of the polycarbonate portion of the blends according to the present invention is preferably at least about 0.3 dL/g, more preferably at least 0.5 dL/g.
  • the melt flow of the polycarbonate portion of the blends according to the present invention is preferably between 1 and 20, and more preferably between 2 and 1 8, as measured according to ASTM Method Dl 238 at a temperature of 300 0 C and using a weight of 1.2 kg.
  • Processes for the preparation of polycarbonates are well known in the art.
  • the linear or branched polycarbonates that can be used in the invention and disclosed herein are not limited to or bound by the polycarbonate type or its production method.
  • a dihydric phenol such as bisphenol A
  • phosgene is reacted with phosgene with the use of optional mono-functional compounds as chain terminators and tri-functional or higher functional compounds as branching or crosslinking agents.
  • Monofunctional, difunctional, and trifunctional reactive acyl halides also can used in the preparation of polycarbonates as terminating compounds (mono-functional), comonomers (di-functional), or branching agents (tri-functional or higher).
  • the polycarbonate portion of the present blend can be prepared in the melt, in solution, or by interfacial polymerization techniques well known in the art. Suitable methods include the steps of reacting a carbonate source with a diol at a temperature of about O 0 C to 31 5 0 C at a pressure of about 0.1 to 760 mm Hg for a time sufficient to form a polycarbonate.
  • Commercially available polycarbonates that can be used in the present invention are normally made by reacting an aromatic diol with a carbonate source such as, for example, phosgene, dibutyl carbonate, or diphenyl carbonate, to incorporate 100 mole percent of carbonate units, along with 100 mole percent diol units into the polycarbonate.
  • a carbonate source such as, for example, phosgene, dibutyl carbonate, or diphenyl carbonate
  • Blends of the of polyesters and polycarbonates can be made by methods which include the steps of blending the polycarbonate and polyester portions at a temperature of about 25 °C to 35O 0 C for a time sufficient to form a clear blend composition.
  • Suitable conventional blending techniques include the melt method and the solution-prepared method.
  • Other suitable blending techniques include dry blending and/or extrusion.
  • the compositions of the present invention including the immiscible and homogeneous blends contained therein, may be prepared by any method known in the art and are useful as thermoplastic molding compositions and for formation of films and single and multilayered articles.
  • homogeneous polyesters blends may be prepared by transesterification of the polyester components.
  • homogeneous blends of polyamides may be prepared by transamination of the polyamide components.
  • the melt blending method includes blending the polymers at a temperature sufficient to melt the first component and second component portions, and thereafter cooling the blend to a temperature sufficient to produce a clear blend.
  • melt as used herein includes, but is not limited to, merely softening the polymers. Examples of melt mixing methods generally known in the polymers art are described in Mixing and Compounding of Polymers (I. Manas-Zloczower' & 2. Tadmor eds., Carl Hanser Verlag publisher, N.Y. 1 994).
  • the solution-prepared method includes dissolving the appropriate weight/weight ratio of the first component and second component in a suitable organic solvent such as methylene chloride or a 70/30 mixture of methylene chloride and hexafluoroisopropanol, mixing the solution, and separating the blend composition from solution by precipitation of the blend or by evaporation of the solvent.
  • a suitable organic solvent such as methylene chloride or a 70/30 mixture of methylene chloride and hexafluoroisopropanol
  • the melt blending method is the preferred method for producing the blend compositions of the present invention.
  • the melt blending method is more economical and safer than the solution method, which requires the use of volatile solvents.
  • the melt blending method also is more effective in providing clear blends.
  • Any of the clear blends of the present invention that can be prepared by solution blending also can be prepared by the melt method.
  • Some of the blends of the present invention can be prepared by the melt method, but not by the solution-prepared method. Any blending process which provides clear blends of the prese ⁇ t invention is suitable.
  • One of ordinary skill in the art will be able to determine appropriate blending methods for producing the clear blends of the present invention.
  • first and second components of the composition may be compounded in the melt, for example, by using a single screw or twin screw extruder. They may also be prepared by blending in solution. Additional components such as stabilizers, flame retardants, colorants, lubricants, release agents, impact modifiers, and the like may also be incorporated into the formulation.
  • the compositions can be produced via a melt extrusion compounding of the first component and the second component with any other composition components such as, for example, metal catalysts, dyes, toners, fillers, and the like.
  • the composition may be formed by dry blending solid particles or pellets of each of thermoplastic polymers and the polyamide components and then melt blending the mixture in a suitable mixing means such as an extruder, a roll mixer, or the like.
  • a suitable mixing means such as an extruder, a roll mixer, or the like.
  • transamidized, homogeneous blend of polyamides it is advantageous to conduct the processing at a temperature that will cause transamidation between the polyamides to occur.
  • these temperatures range from about 27O°C to about 35O 0 C.
  • Other examples of transamidation temperatures are about 28O 0 C to about 35O 0 C and about 29O 0 C to about 340°C.
  • Blending is conducted for a period of time that will yield a well dispersed, immiscible blend.
  • the composition may be cooled and cut into pellets for further processing, it may be extruded into films, sheets, profiles, and other shaped elements, injection or compression molded to form various shaped articles, or it may be formed into films and optionally uniaxially or biaxially stretched by means well known in the art.
  • the amounts of the first and second components in the immiscible blend may vary widely.
  • the immiscible blend of our novel composition may comprise about 5 to about 99 weight percent of the first component and about 95 to about 1 weight percent of the second component, based on the total weight of the composition.
  • Other non-limiting, representative examples of weight percentages of the first and second components include about 50 to about 99 weight percent of the first component and about 50 to about 1 weight percent of the second component, about 60 to about 99 weight percent of the first component and about 40 to about 1 weight percent of the second component, and about 70 to about 99 weight percent of the first component and about 30 to about 1 weight percent of the second component.
  • Our invention also provides a composition prepared by a process comprising melt blending: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
  • a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof
  • a second component comprising a homogeneous, transamidized blend of at least 2 polyamides
  • the composition includes the various embodiments of the polyesters, polycarbonates, polyarylates, homogeneous blends, and polyamides as described above and any combination thereof.
  • the second component of the composition can comprise a homogeneous, transamidized blend of at least 2 polyamides in which transamidation may be accomplished by contacting the polyamides at elevated temperatures, typically from about 27O 0 C to about 35O 0 C.
  • Other examples of transamidation temperatures are about 28O 0 C to about 35O 0 C and about 290 0 C to about 340 0 C.
  • the homogeneous blend of component (ii) can comprise a first polyamide, comprising aromatic residues, and a second polyamide comprising aliphatic residues, as described previously.
  • typical polyamides that can be used as the second polyamide include, but are not limited to, nylon 4; nylon 6; nylon 9; nylon 1 1 ; nylon 1 2; nylon 6,6; nylon 5,1 0; nylon 6,1 2; nylon 6,1 1 ; nylon 10,12; and combinations thereof.
  • the first component can comprise a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A.
  • Another aspect of the instant invention is a method for the preparation of a transparent polymer blend, comprising:
  • thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof;
  • Our method includes the various embodiments of the polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, and polyamides as described previously and any combination thereof.
  • Our method comprises selecting the first component which may be a polyester, polycarbonate, polyarylate or homogeneous blend thereof.
  • the refractive index of the first component may be determined using methods well known to persons skilled in the art.
  • the second component which may comprise as single copolyamide or a transamidized, homogeneous blend of at least two polyamides, is tailored to closely match the refractive index of the first component by selecting the appropriate mixture of aromatic and aliphatic monomers in the case of a copolyamide, or by selecting a mixture of polyamides containing the desired mixture of aromatic and aliphatic residues if a homogeneous blend of polyamides is used.
  • the choice of the proper ratio of monomers or of polyamides can be determined, for example, by trial and error, or, in another example, by plotting the refractive index of various polyamides or copolyamides containing varying amounts of aromatic residues and aliphatic residues, and selecting the molar ratio of aromaticaliphatic residues or the weight percentage ratio of polyamides that will give the targeted refractive index.
  • the first and second components may be melt blended.
  • the second component comprises a transamidized, homogeneous blend of at least 2 polyamides, it is desirable to carry out the melt blending step at a temperature effective for the transmidation process. Typical transamidation temperature ranges are as described previously.
  • the thermoplastic polymers also may be selected to match the refractive index of the second component.
  • another aspect of the invention is a method for the preparation of a transparent polymer blend, comprising: (A) selecting a second component comprising
  • thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof wherein the polyester, polycarbonate, polyarylate, or homogeneous blend thereof is selected to produce a first component refractive index that satisfies the following formula:
  • thermoplastic polymers to obtain a second component and first component that have a difference in refractive index of about 0.006 to about -0.0006 may be illustrated with particular reference to polycarbonate/polyester blends.
  • polycarbonate/polyester blends For example, the complete miscibility of a polycarbonate of bisphenol A and PCTG permits the tailoring of refractive index (Rl) of the polycarbonate/PCTG blend, by adjusting the polycarbonate/PCTG ratio.
  • the refractive index of the first component of the present invention may be matched to within about 0.006 to about -0.0006 of that of the second component comprising the polyamide barrier polymers.
  • a polymer may be determined to be a suitable modifying polymer of the homogeneous polyester/polycarbonate blends described hereinabove if a clear blend is formed by: 1 ) blending the modifying polymer with a pre-existing blend containing the polycarbonate and polyester portions, or 2) blending the modifying polymer with the polycarbonate portion prior to the introduction of the polyester portion, or 3) blending the modifying polymer with the polyester portion prior to the introduction of the polycarbonate portion, or 4) mixing the modifying polymer, polycarbonate portion and polyester portion all together prior to blending.
  • the clear blends of the present invention can still be modified by the incorporation of modifying polymers to produce performance blends, which may not necessarily be clear.
  • polyamides such as nylon 6,6 from DuPont, poly(ether-imides) such as ULTEM poly(ether-imide) from General Electric, polyphenylene oxides such as poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide) /polystyrene blends such as the NORYL resins from General Electric, polyesters, polyphenylene sulfides, polyphenylene sulfide/sulfones, poly(ester-carbonates) such as LEXAN 3250 poly(ester- carbonate) (General Electric), polycarbonates other than LEXAN polycarbonate from General Electric, polyarylates such as ARDEL Dl OO polyarylate (Amoco), polysulfones, polysulfone ethers, poly(ether-ketones) or aromatic dihydroxy compounds can be used as blend modifiers to modify properties or to reduce flammability.
  • polyamides such as nylon 6,6 from DuPont
  • poly(ether-imides) such as ULTEM
  • the copolyamide or homogeneous blend of polyamides of the composition of the invention can function as a barrier polymer and, as such, improve the barrier properties of the overall composition.
  • barrier polymer means a polymer having one or more of the following properties: (1) a water permeability of 2 gm-mils/100 sq in/24 hr or less, as measured by ASTM Method No.
  • the barrier properties may be enhanced by incorporating a metal catalyst to produce an oxygen scavenging composition which catalyzes the reaction of oxygen with one or more polyamides in the composition.
  • Our invention therefore, further provides an oxygen-scavenging composition comprising: (A) an immiscible blend comprising
  • thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
  • a second component comprising a transamidized, homogeneous blend of at least two polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less; and (B) at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic
  • the oxygen-scavenging compositions of the invention also may include a single copolyamide as described hereinabove for the other embodiments of the invention.
  • the invention also provides an oxygen-scavenging composition comprising:
  • thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
  • a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less; and
  • (B) at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements.
  • the oxygen scavenging compositions include any combination of the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, and polyamides described hereinabove.
  • the oxygen-scavenging compositions of the invention can include one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements as set forth in the 1 984 revision of the Periodic Table by the lnternation Union of Pure and Applied Chemistry .
  • Typical oxidation catalysts include transition metal catalysts which can readily interconvert between at least two oxidation states. Examples of metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof.
  • any amount of catalyst which is effective in catalyzing oxygen scavenging may be used but, typically, the metal will be used in amounts from about 10 ppm to about 1 ,000 ppm.
  • Other ranges of metal concentration include, about 50 ppm to about 750 ppm, about 10 to about 500 ppm, about 50 ppm to about 500 ppm, and about 50 to about 300 ppm based on the total weight of the oxygen-scavenging composition.
  • the metal typically may be used as the elemental metal itself, as a metal complex containing organic ligands, as an oxide, or as a metal salt.
  • counterions for metal salts include, but are not limited to, chloride, acetate, acetylacetonate, stearate, palmitate, 2-ethylhexanoate, neodecanoate, octanoate, or naphthenate, and mixtures thereof.
  • the metal salt may also be an ionomer, in which case a polymeric counterion is employed. Such ionomers are well known in the art.
  • the metal catalyst is cobalt or a compound containing cobalt such as, for example, a cobalt salt.
  • the cobalt may be in the +2 or +3 oxidation state.
  • Other examples of metal catalysts are rhodium in the +2 oxidation state and copper in the +2 oxidation state.
  • the metals may be added in salt form, conveniently as carboxylate salts such as, for example, cobalt octanoate, cobalt acetate, or cobalt neodecanoate. The reported amounts are based on the weight of the polymer blends and measured on the metal, not its compound weight as added to the composition.
  • cobalt as the metal typical amounts are at least 50 ppm, or at least 60 ppm, or at least 75 ppm, or at least 100 ppm, or at least 125 ppm.
  • the catalyst can be added neat or in a carrier (such as a liquid or wax) to an extruder or other device for making an article, or it can be added in a concentrate with a polyamide polymer, in a concentrate with a polyester polymer, or in a concentrate with the immiscible blend.
  • the carrier may either be reactive or non-reactive with the first and second component and either volatile or non-volatile carrier liquids may be employed.
  • the metal catalyst may be added at a variety of points and by way of a variety of blending protocols during the preparation of the oxygen scavenging composition.
  • a particularly useful approach is to bring the polyamide and transition metal together late in the preparation of the final blend composition, even as late as in the final melt step before forming the article, so that the oxygen scavenging activity of the polyamide is not prematurely initiated.
  • cobalt is provided as a transition metal
  • the first component of the oxygen-scavenging composition can comprise a polyester having any combination of monomer residues as described previously.
  • the polyester can comprise (a) diacid residues comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-piOpanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethy!-1 ,3
  • the diacid residues can comprise about 60 to 100 mole percent of the residues of terephthalic acid and 0 to about 40 mole percent of the residues of isophthalic acid and the diol residues can comprise about 100 mole percent of the residues of 1 ,4- cyclohexanedimethanol. In another example, the diacid residues can comprise about 100 mole percent, based on the total moles of diacid residues, of the residues of terephthalic acid.
  • polyesters that may be used as the first component include polyesters comprising: (i) about 80 to about 100 mole percent of the residues of terephthalic acid and about 50 to about 90 mole percent of the residues 1 ,4-cyclohexanedimethanol and about 10 to about 50 mole percent neopentyl glycol; (ii) about 100 mole percent of the residues of terephthalic acid and about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexanedimethanol and 60 to about 90 mole percent of the residues of ethylene glycol; and (iii) about 100 mole percent of the residues of terephthalic acid and about 10 to about 99 mole percent of the residues of 1 ,4- cyclohexanedimethanol, 0 to about 90 mole percent of the residues of ethylene glycol, and about 1 to about 25 mole percent of the residues of diethylene glycol.
  • the polyester may also further comprise about 0.1 to 2 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride as described hereinabove.
  • the first component may also comprise a homogeneous blend of at least one polyester and at least one polycarbonate.
  • the polycarbonates that can be used in these homogeneous blends have been described previously.
  • the transamidized, homogeneous blend or the copolyamide can comprise any polyamide as described previously such as for example, various nylons. It is advantageous, however, that the copolyamide or homogeneous blend of polyamides of the oxygen-scavenging composition comprise the residues of m-xylyienediamine, p-xylylenediamine, or a combination thereof.
  • the second component may comprise a homogeneous blend of a first polyamide comprising the residues of m-xylylenediamine and adipic acid, and a second polyamide comprising nylon 6, nylon 6,6, or blends thereof.
  • this homogeneous blend may be combined in an immiscible blend with a first component comprising a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A. It is desirable also for optimum oxygen scavenging properties that the copolyamide or homogeneous blend of polyamides contain 20 mmoles/kg or less of free amino groups. The concentration of free amino groups can be determined using techniques well known to persons having ordinary skill in the art such as, for example, by titration.
  • the oxygen scavenging composition comprises a copolyamide of m-xylylenediamine adipate.
  • a modified m- xylylenediamine adipate in which some of the adipic acid residues, or some of the m-xylylenediamine residues, or some of both, are replaced with other residues, can give an oxygen-scavenging composition with improved oxygen- scavenging properties when compared with compositions containing only the m-xylylenediamine adipate homopolymer.
  • Other polyamide barrier polymers, as described herein, may also be used as part of the oxygen scavenging composition.
  • compositions of the present invention described hereinabove may be used to fabricate shaped articles such as, for example, sheets, films, tubes, preforms, bottles, or profiles. Such articles may be formed by any means well known to persons skilled in the art such as, for example, by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
  • the compositions of the present invention may be fabricated into shaped articles such as, for example, films, by any technique known in the art. Formation of films can be achieved by melt extrusion, as described, for example, in U.S. Patent No.
  • films may be produced by the well known cast film, blown film and extrusion coating techniques, the latter including extrusion onto a substrate.
  • a substrate may also include a tie-layer.
  • Films produced by melt casting or blowing can be thermally bonded or sealed to a substrate using an adhesive.
  • the compositions may be fabricated into monolayer or multilayer films by any technique known in the art.
  • monolayer, or multilayer films may be produced by the well known cast film, blown film and extrusion coating techniques, the latter including extrusion onto a substrate.
  • Representative substrates include films, sheets, and woven and nonwoven fabrics.
  • Monolayer, or multilayer films produced by melt casting or blowing can be thermally bonded or sealed to a substrate using an adhesive.
  • the composition may be formed into a film using a conventional blown film apparatus.
  • the film forming apparatus may be one which is referred to in the art as a "blown film” apparatus and includes a circular die head for bubble blown film through which the composition is forced and formed into a film "bubble". The "bubble" is ultimately collapsed and formed into a film.
  • compositions also may be used to form shaped articles through extrusion blow molding and injection stretch-blow molding.
  • An injection molding process softens the copolyamide or homogeneous polyamide blend in a heated cylinder, injecting it while molten under high pressure into a closed mold, cooling the mold to induce solidification, and ejecting the molded preform from the mold.
  • Molding compositions are well suited for the production of preforms and subsequent reheat stretch-blow molding of these preforms into the final bottle shapes having the desired properties.
  • the injection molded preform is heated to suitable orientation temperature in the 100 0 C to 15O 0 C range and then stretch-blow molded.
  • the latter process consists of first stretching the hot preform in the axial direction by mechanical means such as by pushing with a core rod insert followed by blowing high pressure air (up to 500 psi) to stretch in the hoop direction. In this manner, a biaxially oriented blown bottle is made. Typical blow-up ratios range from 5/1 to 15/1.
  • the excellent transparency and low haze of the compositions of the invention enable the preparation of transparent, shaped articles with the incorporation of substantial amounts of scrap polymer or "regrind".
  • the term "regrind”, as used herein, is understood to have its commonly accepted meaning in art, that is, scrap polymer that recovered from an article forming process and ground into smaller particles.
  • regrind is sold as scrap for incorporation into shaped articles in which the transparency of the article is immaterial to its application.
  • shaped articles such as, for example, bottles and films used in packaging applications
  • low haze and high transparency are important features.
  • the manufacture of these articles, in particular, multilayered articles inherently produces large quantities of scrap polymer which frequently cannot -be returned to the article-forming process because of the formation of unacceptable levels of haze.
  • low haze, transparent, shaped articles may be produced from the compositions of the invention with the inclusion of regrind.
  • Another aspect of our invention is a process for forming a shaped article, comprising: (A) melt blending
  • a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein the first component (i) and second component (ii) form an immiscible blend, the second component and the first component have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
  • step (F) combining the polymer regrind with the first and second components (i) and (ii) of step (A).
  • the above process includes the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, and any combination thereof described hereinabove.
  • the immiscible blend formed from the first and second components may further comprise at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements.
  • metals include copper, nickel, cobalt, iron, manganese, and combinations thereof.
  • the metal is present in amounts of about 1 0 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
  • the preferred metal is cobalt.
  • the shaped article of our inventive process may be formed by any methods known in the art and described hereinabove.
  • the shaped article may be formed by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
  • any shaped article representative articles that may be produced are sheets, films, preforms, tubes, and bottles. These article may have a single layer or contain from 2 to about 7 layers.
  • the regrind may be incorporated into one or more of these layers which may comprise from about 50 to 100 weight percent regrind based on the weight of the one or more layers.
  • Other examples of regrind levels that can be present in the shaped article are 5 to about 95 weight percent, about 10 to about 60 weight percent, about 1 5 to about 50 weight, and about 20 to about 30 weight percent.
  • the shaped article may comprise multiple layers in which one or more of the layers comprise the first and second component as an immiscible blend or in which the first component and the second component are present in separate layers.
  • a multilayered, shaped article comprising: (i) a first layer comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof; and (ii) a second layer comprising a transamidized homogeneous blend of at least two polyamides; wherein the second layer (ii) and the first layer (i) have a difference in refractive index, Rl(second layer) - RKfirst layer), of about 0.006 to about
  • the shaped article has a percent transmittance of at least
  • the shaped article may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, and any combination thereof described hereinabove.
  • the multilayered shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
  • the multilayered article may further comprise a regrind comprising a mixture of the first and second layers, which may be incorporated into first layer, second layer, or a combination of the first and second layer.
  • the regrind is about 5 weight percent to about 60 weight percent of the multilayered article, based on the total weight of the article.
  • Other examples of weight percentages of regrind in the shaped article are about 10 weight percent to about 40 weight percent and about 20 weight percent to about 30 weight percent of the total weight of the article.
  • the multilayered article can have from 2 to about 7 layers depending on its intended application.
  • the shaped article may be a sheet, film, tube, bottle, or preform.
  • Complex layered structures are possible also.
  • the shaped article can have a layered structure represented by ABA, ABABA, ABCBA, or ACBCA in which layer A comprises the first layer (i), layer B comprises the second layer (ii), and layer C comprises a regrind comprising a mixture of scrap first and second layers (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
  • layer B and layer C have a difference in refractive index, RKlayer B) - R(layer C), of about 0.006 to about -0.0006 to maintain the transparency of the article and the ability to incorporate regrind.
  • layer A can comprise the second layer (ii)
  • layer B comprises the first layer (i)
  • layer C comprises a a mixture of scrap first and second layers (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
  • the second layer (ii) of our novel multilayered article can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
  • metals include copper, nickel, cobalt, iron, manganese, and combinations thereof.
  • the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
  • the preferred metal is cobalt.
  • the multilayered, shaped article of the invention can further comprise at least one additional layer comprising about 50 to about 100 weight percent of regrind, based on the total weight of the layer.
  • the additional layer containing the regrind can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
  • metals include copper, nickel, cobalt, iron, manganese, and combinations thereof.
  • the metal is present in amounts of about 10 to about 500 parts per million by weight of said metal, based on the total weight of said shaped article.
  • the preferred metal is cobalt.
  • the multilayered, shaped article may comprise the various embodiments of the shaped articles, thermoplastic polymers, polyamides, immiscible blends, homogeneous blends, and oxygen scavenging compositions as described earlier.
  • the at least one thermoplastic polymer may comprise a linear or branched polyester comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l
  • the multilayered, shaped articles of the present invention may be prepared by any method known to persons of ordinary skill in the art.
  • the shaped articles can be formed by any conventional technique for forming films, including lamination, extrusion lamination, coinjection, stretch- blow molding and coextrusion blowmolding, and may be illustrated with particular reference to a typical method for making multilayer film by coextrusion.
  • the first and second components, as well as any optional layers are fed into infeed hoppers of the extruders of like number, each extruder handling the material for one or more of the layers.
  • the first and second components each will be heated to a temperature of about Tg + 100 0 C to about Tg + 300 0 C before and during extrusion, wherein Tg is the glass transition temperature of the first or second component as measured by differential scanning calorimetry.
  • Tg is the glass transition temperature of the first or second component as measured by differential scanning calorimetry.
  • the melted streams from the individual extruders are fed into a single manifold co-extrusion die. While in the die, the layers are juxtaposed and combined, then emerge from the die as a single multiple layer film of polymeric material. After exiting the die, the film is cast onto a first controlled temperature casting roll, passes around the first roll, and then onto a second controlled temperature roll, which is normally cooler than the first roll.
  • the film forming apparatus may be one which is referred to in the art as a blown film apparatus and includes a multi-manifold circular die head for bubble blown film through which the film composition is forced and formed into a film bubble which may ultimately be collapsed and formed into a film.
  • Processes of coextrusion to form film and sheet laminates are generally known.
  • the individual layers may first be formed into sheets and then laminated together under heat and pressure with or without intermediate adhesive layers.
  • the transparency and low haze of the compositions of the invention also enable the preparation of multilayered, transparent, shaped articles with the incorporation of substantial amounts of scrap polymer or "regrind".
  • Our invention therefore, also provides a process for forming a multilayered, shaped article, comprising: (i) heating a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof to a temperature of about Tg +100 0 C to about Tg + 300 0 C of the first component; (ii) heating a second component comprising a copolyamide or a transamidized, homogeneous blend of at least two polyamides to a temperature of about Tg +100 0 C to about Tg + 300 0 C of the second component; (iii) forming a shaped article having the first and second components in separate layers;
  • step (iv) recovering scrap first and second components; (v) grinding the scrap first and second components to produce a regrind; (vi) optionally, drying the regrind; and (vii) combining the regrind with the first component, second component, or a combination thereof, of steps (i) and (ii); wherein the second component of step (ii) and the first component of step (i) of have a difference in refractive index, RKsecond component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
  • the process may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, article-forming processes, and any combination thereof described hereinabove.
  • Our process enables the incorporation of substantial amounts of regrind into shaped article while maintaining low haze and high transparency.
  • the regrind will typically comprise a mixture of the first and second components of steps (i) and (ii) that are produced as scrap during the article-forming process, but any polymer material can be used as long as its refractive index differs from the that second component by about 0.006 to about -0.0006.
  • the regrind material of the process can be combined with the first component of step (i), the second component of step (ii) or a combination of the first and second components.
  • the regrind can be from about 5 weight percent to about 60 weight percent of the shaped article, based on the total weight of the shaped article.
  • Other representative examples of regrind content for the shaped artice of the process of the invention are about 10 weight percent to about 40 weight percent of the shaped article and about 20 weight percent to about 30 weight percent of the shaped article.
  • the multilayered article of our process can have from 2 to about 7 layers depending on its intended application.
  • the multilayered, shaped article may be a sheet, film, tube, bottle, or preform.
  • Complex layered structures are possible also.
  • the shaped article can have a layered structure represented by ABA, ABABA, ABCBA, or ACBCA in which layer A comprises the first component of step (i), layer B comprises the second component of step (ii), and layer C comprises a regrind comprising a mixture of scrap first and second components from steps (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
  • layer B and layer C have a difference in refractive index, Rl(layer B) - R(layer C), of about 0.006 to about -0.0006 to maintain the transparency of the article and the ability to incorporate regrind.
  • layer A can comprise the second component of step (ii)
  • layer B comprises the first component of step (i)
  • layer C comprises a a mixture of scrap first and second components of steps (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
  • the second component of step (ii) of our novel multilayered article can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
  • metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof.
  • the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
  • the preferred metal is cobalt.
  • step (iii) of the process of the invention can further comprise forming at least one additional layer comprising about 50 to about 1 00 weight percent of regrind, based on the total weight of the layer.
  • the additional layer containing the regrind can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
  • metals include copper, nickel, cobalt, iron, manganese, and combinations thereof.
  • the metal is present in amounts of about 10 to about 500 parts per million by weight of said metal, based on the total weight of said shaped article.
  • the preferred metal is cobalt.
  • the multilayered, shaped article may comprise the various embodiments of the shaped articles, thermoplastic polymers, polyamides, immiscible blends, homogeneous blends, and oxygen scavenging compositions as described earlier.
  • the at least one thermoplastic polymer may comprise a polyester comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l ,3-cyclo
  • Another embodiment of our invention further is a process for forming a multilayered shaped article, comprising: (A) heating a first component comprising (i) at least one polyester comprising: (a) diacid residues comprising at least about 95 mole percent, based on the total diacid residues, of the residues of terephthalic acid; and (b) diol residues comprising at least 95 mole percent, based on the total moles of dio!
  • step (G) combining the regrind with the first component, second component, or a combination thereof, of steps (A) and (B); wherein the second component of step (B) and the first component of step (B) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less.
  • the process may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, article-forming processes, and any combination thereof described hereinabove.
  • the regrind may comprise a mixture of the first and second components (i) and (ii) and can be combined with the first component (i), second component (ii), or a combination thereof.
  • the regrind can be from about 5 weight percent to about 60 weight percent of the shaped article, based on the total weight of the shaped article.
  • Other representative examples of regrind content for the shaped artice of the process of the invention are about 1 0 weight percent to about 40 weight percent of the shaped article and about 20 weight percent to about 30 weight percent of the shaped article.
  • the polyester of the process can comprises diacid residues comprising at least about 95 mole percent of the residues of terephthalic acid and can have a range of diol compositions.
  • the polyester can comprise diol residues comprising about 1 to about 5 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 99 to about 95 mole percent of the residues of ethylene glycol.
  • diol compositions for the polyester of our process include, but are not limited to: (i) diol residues comprising about 29 to about 33 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 71 to about 67 mole percent of the residues of ethylene glycol; (b) diol residues comprising about 45 to about 55 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 55 to about 45 mole percent of the residues of ethylene glycol; (iii) residues comprising about 60 to about 65 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 40 to about 35 mole percent of the residues of ethylene glycol; (iv) diol residues comprising about 79 to about 83 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 21 to about 17 mole percent of the residues of ethylene glycol; and (v)
  • thermoplastic polymer may further comprise a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A.
  • a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A.
  • Each of the polyester and polycarbonate may be linear or branched.
  • the second component of step (ii) of our novel process can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements.
  • metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof.
  • the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article.
  • the preferred metal is cobalt.
  • step (C) of the process of the invention can further comprise forming at least one additional layer comprising about 50 to about 1 00 weight percent regrind, based on the total weight of the layer.
  • the additional layer containing the regrind can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements. Examples of metals include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 10 to about 500 parts per million by weight of said metal, based on the total weight of said shaped article. The preferred metal is cobalt.
  • the shaped articles of the invention may be further oriented by stretching which may improve the barrier properties of the article.
  • it may be desirable to incorporate other conventional additives or modifying polymers with the polymeric compositions of the present invention.
  • additives or modifying polymers for example, there may be added antioxidants, heat and light stabilizers, dyes, antistatic agents, lubricants, preservatives, processing aids, slip agents, antiblocking agents, pigments, flame retardants, blowing agents, and the like. More than one additive may be used.
  • the additive may be present in any desired amount, but typically are not present at more than about 20 weight percent, preferably not more than 10 weight percent, of the total weight of the shaped article.
  • the polymer compositions, oxygen-scavenging compositions, and shaped articles prepared therefrom also may comprise up to about 30 weight percent, preferably less than about 20 weight percent, of certain platelet particles derived from at least one layered silicate material to improve their barrier properties.
  • the platelet particles can be modified with at least one ammonium compound.
  • the amount of platelet particles may be determined by . measuring the residual ash of the polymer-platelet particle compositions when treated in accordance with ASTM D5630-94.
  • the gas barrier improvement typically increases with increasing concentration of platelet particles in the composite.
  • compositions having at least about 0.5 weight percent of the platelet particles are preferred because they display desirable improvements in gas permeability.
  • Generally layered silicate materials are a dense agglomeration of platelet particles which are closely stacked together like cards.
  • the platelet particles of the present invention have a thickness of less than about 2 nm and a diameter in the range of about 10 to about 5000 nm.
  • measurements refer only to the platelet particle and not to the ammonium compounds or any additional dispersing aids and treatment compounds which might be used.
  • Suitable platelet particles are derived from layered silicate materials that are typically free flowing powders having a cation exchange capacity between about 0.3 and about 3 meq/g and preferably between about 0.8 and about 1.5 meq/g.
  • suitable layered silicate materials include mica-type layered phyllosilicates, including clays, smectite clays, sodium montmorillonite, sodium hectorite, bentonites, nontronite, beidelite, volonsloite, saponite, sauconite, magadite, kenyaite, synthetic sodium hectorites, and the like. Clays of this nature are available from various companies including Southern Clay Products and Nanocor, Inc.
  • the most preferred platelet particles are derived for sodium bentonite or sodium montmorillonite.
  • Such clays are readily available in the U.S., known as Wyoming type montmorillonite, and other parts of the world, including the Kunipia clays available from Kunimine Industries, Inc.
  • the layered silicate materials are typically treated to improve dispersion into the polymer composition.
  • Many useful clay treatments are known in the art, and these treatments may also be used before, after, or during incorporation of the layered silicate materials into the composites of this invention without deviating from the scope of this invention.
  • Examples of useful treatments include, but are not limited to treatments with silane compounds, expanding agents, polymers and oligomers, dispersing aids, organic cation salts, and their combinations.
  • Examples of useful treatment with silane compounds include those treatments disclosed in International Publication No. WO 93/1 1 1 90.
  • Examples of useful silane compounds includes (3-glycidoxypropyl)trimethoxysilane, 2- methoxy (polyethyleneoxy)propyl heptamethyl trisiloxane, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride and the like.
  • Examples of useful treatment with expanding agents include oligomeric polymers well known in the art. Representative polymers and oligomers for treating clays include those disclosed in U.S. Patent No.'s 5,552,469 and 5,578,672. Many dispersing aids are known, covering a wide range of materials including water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents, and the like or combinations thereof.
  • the invention is further illustrated by the following examples.
  • the glass transition temperatures (Tg's) of the polyesters, polyamides, and blends were determined by ASTM Method D341 8 using a TA Instruments 2920 differential scanning calorimeter (DSC) at a scan rate of 20°C/min.
  • Heat Deflection Temperature was determined by ASTM Method D648, and Notched Izod Impact Strength was performed according to ASTM Method D256.
  • Flexural properties were determined according to ASTM Method D790.
  • the tensile properties of the blends were determined according to ASTM Method D638 at 23°C.
  • the inherent viscosity of the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 mL at 25 0 C.
  • the diol content of the polyester portion of these blends was determined by proton nuclear magnetic resonance spectroscopy ( 1 H NMR).
  • the miscibility of the blends was determined by differential scanning calorimetry of pressed films and molded objects.
  • haze was determined by forming the composition into a sheet, film, or plaque having a thickness of 1 /8 inch or less and measuring the haze according to the above procedure.
  • haze was determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze according the procedure described above.
  • Refractive index was measured at 633 nm with a Metricon Prism CouplerTM model 2010 refractometer (available from Metricon Inc.) and is reported as the average of the refractive indices measured in 3 orthogonal directions (extrusion or stretch, transverse, and thickness directions).
  • Oriented films were produced on a TM Long film stretcher (named for the producer) which uniaxially or biaxially stretches samples of pressed, blown, or extruded film. The operation of the film stretcher was based upon the movement of two drawbars at right angles to each other upon hydraulically driven rods. There was a fixed draw bar opposed to each moving draw bar.
  • Oxygen permeabilities of films were determined using Ox-Tran Oxygen Permeation instruments manufactured by MOCON, Inc. Minneapolis, MN. Oxygen permeabilities were calculated from the known area of the films in test, thickness of the film, partial pressure differential of oxygen across the film, and the measured steady state transmission rate. In the case of samples which exhibit active oxygen scavenging, the measured flux is not truly at steady state, since the transmission rate can slowly change as the efficiency of the oxygen scavenging reaction changes with time. However, in these instances, the oxygen transmission can often be considered to be at pseudo-steady state during the duration of permeation measurement.
  • Comparative Examples 1-12 The copolyesters listed in Table 1 were prepared from terephthalic acid, ethylene glycol, and 1 ,4-cyclohexane- dimethanol (CHDM). The amount of CHDM in the polyesters is shown in Table 1 .
  • Example F contains 1 00% CHDM (0% ethylene glycol) but 26 mole% of the acid portion is isophthalic acid instead of terephthalic acid
  • copolyesters and MXD6 6121 polyamide (containing 1 00 mole% m-xylylene and 100 mole% adipic acid, available from Mitsubishi Corporation) were dried overnight at 70 0 C.
  • MXD6 6121 polyamide containing 1 00 mole% m-xylylene and 100 mole% adipic acid, available from Mitsubishi Corporation
  • Each of these copolyesters were bag blended with a MXD6 at 1 , 3, and 5 wt% and fed to a Sterling 1 .5 inch single screw extruder at 90 rpm under the following temperature settings (degrees C) to form a blend:
  • Nylon 6 (availabe as Zytel ® 7335F from DuPont) and MXD6 (grade 61 21 ) were dried at 1 2O 0 C for 48 hours and bag blended in various ratios. Polyamide bag blends were then fed to a Sterling 1 .5 inch single screw extruder at 90 rpm under the following conditions ( 0 C) to form a homogeneous, transamidized blends as indicated by the presence of a single, composition dependent Tg value for each blend. The Tg values are shown in Table 3.
  • Example 40 In this prophetic example, a synthetic route to a polyamide with the appropriate refractive index is employed instead of blending two polyamides as in the above Examples 1 3-24. Any method known in the art can be used to produce these directly synthetic polyamides.
  • the polyamides are generally prepared by melt phase polymerization from a diacid-diamine complex which may be prepared either in situ or in a separate step. In either method, the diacid and diamine are used as starting materials. Alternatively, an ester form of the diacid may be used, preferably the dimethyl ester. If the ester is used, the reaction must be carried out at a relatively low temperature, generally 80 to 12O 0 C, until the ester is converted to an amide.
  • the polyamide synthesized is poly(m-xylylene pimelamide) which is synthesized from the diamine m-xylylenediamine and the diacid pimelic acid.
  • This polyamide is then blended with 90 wt% of the copolyester A in Table 1 , in accordance with methods disclosed in Examples 25-39.
  • the difference in refractive index between these the copolyester A and poly(m-xylylene pimelamide) is predicted to be 0.0034 and is predicted to be transparent.
  • the resulting blend is predicted to have a haze value of less 10% and a transmittance of greater than 75%.
  • Monolayer Films of blends and Oxygen-Scavenging Compositions Several MXD6/N6 transamidized blends were prepared in the manner discussed above for examples 1 3-24 and are given in Table 5. The refractive index values listed in Table 5 were measured on 1 5mil films of these transamidized blends in the manner discussed above for examples 13-24. Three wt% or 5 wt% of either these transamidized MXD6/N6 preblends or MXD6 were bag blended with several of the copolyesters from Table 1 as per Table 6.
  • a concentrate containing cobalt neodecanoate was added to two of the films.
  • This concentrate was prepared as follows. Separate feeds of polyester type C and cobalt neodecanoate, in the form of a pastille and supplied as Cobalt Ten-CemTM 22.5% (available from OMG Corp.) were fed into a 57mm twin-screw extruder and melt blended at barrel set points of approximately 235 0 C. Molten polymer exited the extruder in the form of approximate 0.08" diameter strands which were water quenched and cut into approximate 0.125" length pellets.
  • the ratio (by weight) of polyester to polyamide to concentrate was 93:5 to 5 to 1 .5 and the concentration of cobalt metal in the concentrate was such that this ratio resulted in about 140 to 150 ppm cobalt in the final blended film.
  • the samples which contained cobalt exhibited excellent oxygen scavenging capacity. These samples, which were mounted on the Ox-T ran permeation instrument 1 week after extrusion, had average apparent permeabilities under these conditions of less than 0.1 5 cc(STP)*mil/100 in 2 /day/atm for over 6 months. Table 6 - 30 mil Monolayer Film Results
  • Example 56 and Comparative Examples 54-55 - Regrind of Multilayer Films Multilayer films were prepared by co-extruding two 1 5 mil layers of polyester C around a 4 mil thick layer of either MXD6 or transamidized MXD6/30wt% N6 blend "X". This is referred to as an "ABA" structure where the "A" layers are the outer layers and the "B” layer is the interior layer. A Killian 1 extruder was used to extrude the outer layers from polyester C at a temperature of 265 0 C.
  • a 0.75 Killian extruder was used to extrude the inner layers at a temperature of 285 0 C for the MXD6 and 275 0 C for the transamidized MXD6/30wt% Nylon 6 blend "X".
  • these multilayer films were then ground up and dry blended with additional polyester C pellets at a 50/50 ratio.
  • This dry blend was then dried at 7OC and extruded on a Killian 1 " extruder at a temperature of 240 0 C into 20 mil films. Haze values are shown in table 7.
  • the coextruded films all have haze values less then 2%. However, when these films are reground and blended with neat polyester "C", the film containing the C/MXD6 regrind blend the values increase above 1 0%.
  • the film containing the "C/X" regrind remains clear.
  • Example and Comparative Examples 57 and 58 Adhesion of multilayer films: ABA films were prepared by co-extruding two 1 5 mil layers of polyester C around a 4 mil thick layer of either MXD6 or transamidized MXD6/30wt% N6 blend "X".
  • the Nylon 6 used in the transamidized blend in this example was Zytel 7301 .
  • a Killian 1 extruder was used to extrude the outer polyester C layers at a temperature of 265 0 C.
  • a 0.75 Killian extruder was used to extrude the inner layers at the temperatures indicated in Table 8.
  • the transamidized MXD6/3Owt% N6 blend "X" shows superior adhesion over MXD6 to polyester C. Furthermore, improved adhesion of the transamidized MXD6/30wt% N6 blend to polyester C was obtained when the inner layer melt, temperature was increased from 28O 0 C tO 285°C. MXD6 adhesion did not show any temperature dependency.

Abstract

Disclosed is a process for the preparation of shaped articles such as, for example, sheeting, films, tubes, bottles, preforms and profiles, having high transparency and low haze comprising immiscible blends of one or more thermoplastic polymers selected from polyesters, polycarbonates, and polyarylates, and a copolyamide or a transamidized, homogeneous blend of a least two polyamides. The components of the immiscible blend which have refractive indices which differ by about 0.006 to about -0.0006. The small difference in the refractive indices enable the incorporation of regrind into the polymer composition to produce transparent shaped articles. These articles may have one or more layers and can exhibit improved excellent barrier properties and good melt processability while retaining excellent mechanical properties. Metal catalysts can be incorporated into the compositions to produce shaped articles having oxygen-scavenging properties.

Description

PROCESS FOR THE PREPARATION OF TRANSPARENT SHAPED ARTICLES
CROSS REFERENCES TO RELATED APPLICATONS
[0001 ] This application claims the benefit of United States Provisional
Application Serial No.'s 60/657,746, filed March 2, 2005, and 60/657,747, filed March 2, 2005, each of which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
[0002] This invention pertains to a process for the preparation of shaped articles from transparent, immiscible polymer blends comprising at least two polymer components. More specifically, this invention pertains to a process for the preparation of transparent, shaped articles from immiscible blends comprising at least one thermoplastic polymer, a copolyamide or a homogeneous blend of at least two polyamides, and recovered scrap polymer regrind.
BACKGROUND OF THE INVENTION
[0003] Many products, in particular food products, are sensitive to the presence of oxygen and the loss or absorption of water. Packaged products with this sensitivity are susceptible to deterioration because of exposure to oxygen or absorption of moisture. Packaging materials which limit oxygen exposure to food articles, for example, help to maintain the quality of the food articles and to reduce spoilage. The use of such barrier packaging thus keeps the article in inventory longer and thereby reduces restocking costs and waste. Attempts to solve this problem have led to the widespread use of oxygen barriers and/or moisture barriers in packaging materials. Many polymeric materials are known to act as barriers to oxygen or moisture. For example, typical moisture barriers include polyethylene and polypropylene. Representative oxygen barriers include polyethylene vinyl alcohol) ("EVOH"), polyvinyl alcohol) ("PVOH"), polyamides (nylons), and blends of these materials. Poly(vinylidene chloride), vinyl chloride copolymers, and vinylidene chloride-methyl acrylate copolymers also are useful as moisture and oxygen barriers.
[0004] These conventional barrier materials, however, are expensive and have unstable structural characteristics or other deficiencies that make fabrication of packaging materials solely out of barrier materials difficult or undesirable. For example, EVOH, while having superior oxygen barrier properties, is not effective as a moisture barrier. Other barrier materials are prohibitively expensive to be used solely as a packaging material. To avoid these problems, it has become a common practice to use multilayer structures in which the amount of expensive barrier material may be reduced to a thin layer and used in conjunction with an inexpensive polymer on one or both sides of the barrier layer as structural layers. The use of multilayer structures also helps to protect the barrier layer from deterioration by structural layers. Multilayer products, however, can be expensive to produce. Further, multilayer articles can present difficulties in recycling because the different polymer components are difficult to separate. In addition, blending the recovered scrap polymer or "regrind" with virgin polymer often will cause unsatisfactory haze or opaqueness because of the incompatibility of the virgin materials with the regrind. [0005] The shortcomings of conventional barrier polymers also may be overcome by using a blend of the barrier polymer with another polymer. Unfortunately, as noted above, many blends of barrier polymers and other thermoplastic polymers are immiscible and are opaque or hazy. Such blends are not satisfactory for applications requiring clarity such as, for example, beverage containers.
[0006] Polyester polymers such as, for example, poly(ethylene terephthalate) ("PET"), are commonly used in packaging applications. PET has a number of properties that make it useful as a packaging material, including acceptable carbon dioxide barrier properties for soft drinks packaged in bottles containing multiple servings. However, improvements in the carbon dioxide barrier of PET are needed for soft drinks packaged in smaller bottles and in its oxygen barrier, which is not well-suited for packaging oxygen sensitive products such as, for example, beer, citrus products, tomato-based products, and aseptically packed meat. Polyethylene naphthalate) ("PEN") is 3-1 0 times more effective as a barrier than PET but is more expensive. [0007] Multilayer structures can be used to improve the gas barrier characteristics of PET. For example, polymers that have excellent oxygen barrier (also referred to as "passive barrier") or scavenging properties (also referred to as "active barrier") may be combined with PET to produce a layered structure consisting of the individual polymers. These multilayer structures, however, are expensive to produce. Blends of barrier polymers with PET also have been used to improve the oxygen barrier of packages but, as noted above, often have poor transparency and are not suitable for many packaging applications. The poor transparency of blends also makes it difficult to recycle manufacturing scrap from polymer blends into virgin polymer.
[0008] Copolyester films and extrusion blow molded ("EBM") bottles are often desired for toughness, and are commonly used instead of PET for - A -
extrusion blow molding and film applications. These applications often require barrier that is comparable to that of oriented PET. Unfortunately, however, the barrier properties of copolyesters are inferior to oriented PET. Multilayer structures can be produced by coextruding a thin, barrier film into the center of a thicker bulk structure to improve the overall barrier. To be economical, however, EBM and film processes typically require that high levels (up to 80%) of regrind (i.e., flash and trim) are reprocessed. Unfortunately, typical barrier materials are not miscible with copolyesters and blends of these barrier polymers with polyesters often show a high level of haze and poor clarity. The haze level of the overall film structure, therefore, is increased to unacceptable levels when scrap polymer (i.e., regrind) is incorporated back into the primary layer.
[0009] A polymer blend that provides good passive and/or active barrier properties, is economical, and can be recycled efficiently is needed in the art. Such blends should be transparent, contain thermoplastic and barrier polymers that provide a high barrier for oxygen, water, and carbon dioxide, and can be used economically in article forming processes which incorporate a high level of regrind. In addition, there is need for barrier and thermoplastic polymer compositions that can be used to economically produce multilayered articles having high transparency and can tolerate a high level of regrind.
SUMMARY OF THE INVENTION
[0010] Polymer compositions having high transparency and high barrier properties can be prepared from a immiscible blend of one or more thermoplastic polymers and a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides in which the difference in refractive index between the polyamide component and thermoplastic polymer component is about 0.006 to about -0.0006. Thus, the present invention provides a polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference, in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
[001 1] The first component comprises at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends of these polymers, while the second component comprises a blend of at least 2 polyamides which have been transamidized to produce a homogeneous blend. We have discovered that refractive indices of the first and second components can be closely matched by selecting at least 2 polyamides having different levels of aliphatic and aromatic residues and transamidizing these polyamides to form a homogeneous blend. Thus, homogeneous blends of the thermoplastic polymers and the polymamides can be used to tailor refractive indices of the second component and the first component to within their desired ranges such that the difference in refractive indices is about 0.006 to about - 0.0006. For example, a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A can be used as the first component and a transamidized, homogeneous blend of first polyamide comprising the residues of m-xylylenediamine and adipic acid, and a second aliphatic polyamide can be used as the barrier polymer. When the refractive indices are thus matched, the first and second components form clear, immiscible blends that are suitable for the preparation of high clarity, shaped articles that can be used in many packaging applications. Multilayered articles may also be prepared by a variety of processes known in the art. For example, the first and second components may be coextruded or coinjected from the melt into separate layers, or the layers may be formed individually and brought together in a subsequent process such as, for example, lamination.
[0012] The second component can also comprise a copolyamide having a ratio of aromatic and aliphatic dicarboxylic acid and diamine residues that can be varied to closely match the refractive indices of the first and second components. Thus, another aspect of the invention is a polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and
(ii) a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Ri(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less. COOI 3] Another aspect of our invention is a polymer composition prepared by prepared by a process comprising melt blending:
(i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less.
[0014] The compositions of our invention show excellent barrier properties. The oxygen barrier properties may be enhanced by incorporating transition metal catalysts such as, for example, cobalt, manganese, iron, ruthenium, copper, nickel, palladium, and platinum into the blends to produce oxygen scavenging compositions. The invention, thus, further provides an oxygen-scavenging composition comprising: (A) an immiscible blend comprising
(i) first component comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
(ii) a second component comprising a transamidized, homogeneous blend of at least two polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less; and (B) at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic
Table of the Elements. Typical metal catalysts are cobalt, manganese, and iron.
[001 5] The blends of the present invention are useful for producing clear, shaped articles having improved barrier properties, melt processability, and excellent mechanical properties, and which can be prepared using a high proportion of regrind to virgin polymer. These shaped articles may have a single layer or multiple layers and have numerous packaging applications. Accordingly, the invention further provides a process for forming a shaped article, comprising:
(A) melt blending
(i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein the first component (i) and second component (ii) form an immiscible blend, the second component and the first component have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
(B) forming a shaped article; (C) recovering a scrap polymer composition comprising the blended first and second components (i) and (ii) ;
(D) grinding the scrap polymer composition to produce a polymer regrind;
(E) optionally, drying the scrap polymer composition;and
(F) combining the polymer regrind with the first and second components (i) and (ii) of step (A). Examples of shaped articles which may be prepared by the process of the invention include, but are not limited to, sheets, films, tubes, bottles, or profiles. The shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
[001 6] The shaped articles may have a one or more layers comprising an immiscible blend of the first and second components or can have multiple layers in which the first and second components are in separate layers. The invention also provides a multilayered, shaped article, comprising: (i) a first layer comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof; and (ii) a second layer comprising a transamidized homogeneous blend of at least two polyamides; wherein the second layer (ii) and the first layer (i) have a difference in refractive index, Rl(second layer) - Rl(first layer), of about 0.006 to about -0.0006, and the shaped article has a percent transmittance of at least 75%, and a haze of 1 0% or less.
[001 7] The invention further provides a process for forming a multilayered shaped article, comprising: (i) heating a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof to a temperature of about Tg +100°C to about Tg + 3000C of the first component; (ii) heating a second component comprising a copolyamide or a transamidized, homogeneous blend of at least two polyamides to a temperature of about Tg + T OO0C to about Tg + 3000C of the second component; (iii) forming a shaped article having the first and second components in separate layers;
(iv) recovering scrap first and second components;
(v) grinding the scrap first and second components to produce a regrind; (vi) optionally, drying the regrind; and (vii) combining the regrind with the first component, second component, or a combination thereof, of steps (i) and (ii); wherein the second component of step (ii) and the first component of step (i) of have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less. The regrind may be incorporated into the first or second layer and may be from about 5 to about 60 weight percent of the article.
DETAILED DESCRIPTION
[0018] Polymer compositions having high clarity and good barrier properties can be prepared from an immiscible blend of one or more - Tl -
thermoplastic polymers and a transamidized, homogeneous blend of at least two polyamides, in which the difference in refractive index between the blend of polyamides and the thermoplastic polymers is about 0.006 to about -0.0006. The blend has a percent transmittance of at least 75%, and a haze of 10% or less. In a general embodiment, the present invention provides polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less. The thermoplastic polymers and polyamides may be selected from a wide variety of polymers. The refractive indices of the second component and the first component can be adjusted to give a difference of about 0.006 to about -0.0006 by the selection and ratio of the polyamides of the second component or, alternatively, by blending the thermoplastic polymers of the first component to form a homogeneous blend. Our novel compositons can be used to manufacture shaped articles having one or more layers such as, for example, sheets, films, tubes, bottles, and profiles. The shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing. Multilayer articles can be prepared in which the immiscible blend is present in one or more layers or the first and second components are in separate layers. Because of the small difference in the refractive indices of the first and second components, shaped articles prepared from the composition of the invention can incorporate substantial quantities of regrind and retain good transparency. The clarity and barrier properties of these shaped articles produced make them particularly useful for packaging applications.
[0019] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range specifically and not just the endpoint(s). For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1 , 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1 1 13, etc., and the endpoints 0 and 10. Also, a range associated with chemical substituent groups such as, for example, "Ci to Cs hydrocarbons", is intended to specifically include and disclose Ci and Cs hydrocarbons as well as C2, C3, and C4 hydrocarbons. [0020] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. [0021] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include their plural referents unless the context clearly dictates otherwise. For example, reference a "polymer," or a "shaped article," is intended to include the processing or making of a plurality of polymers, or articles. References to a composition containing or including "an" ingredient or "a" polymer is intended to include other ingredients or other polymers, respectively, in addition to the one named.
[0022] By "comprising" or "containing" or "including" we mean that at least the named compound, element, particle, or method step, etc., is present in the composition or article or method, but does not exclude the presence of other compounds, catalysts, materials, particles, method steps, etc, even if the other such compounds, material, particles, method steps, etc., have the same function as what is named, unless expressly excluded in the claims. [0023] It is also to be understood that the mention of one or more method steps does not preclude the presence of additional method steps before or after the combined recited steps or intervening method steps between those steps expressly identified. Moreover, the lettering of process steps or ingredients is a convenient means for identifying discrete activities or ingredients and the recited lettering can be arranged in any sequence, unless otherwise indicated. [0024] The term "polyester", as used herein, is intended to include homopolyesters, copolyesters, and terpolyesters. In general, polyesters are synthetic polymers prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional hydroxyl compounds. Typically, the difunctional carboxylic acid is a dicarboxylic acid or a hydroxycarboxyiic acid, and the difunctional hydroxyl compound is a dihydric alcohol such as, for example, glycols and diols. In the present invention, the difunctional carboxylic acid may be an aliphatic or cycloaliphatic dicarboxylic acid such as, for example, adipic acid, or an aromatic dicarboxylic acid such as, for example, terephthalic acid. The difunctional hydroxyl compound may be cycloaliphatic diol such as, for example, 1 ,4-cyclohexanedimethanol, a linear or branched aliphatic diol such as, for example, 1 ,4-butanediol, or an aromatic diol such as, for example, hydroquinone.
[0025] The term "polyamide", as used herein, is intended to include synthetic polymers prepared by the polycondensation of one or more difunctional carboxylic acids with one or more difunctional amines or by the ring-opening polymerization of a lactam and may include homopolymers and copolymers. For example, the difunctional carboxylic acid can be a dicarboxylic acid such as adipic acid or isophthalic acid, and the difunctional amines can be a diamine such as, for example, hexamethylene diamine or m-xylylenediamine. The term "copolyamide", as used herein, is understood to mean a polyamide comprising at least 2, chemically distinct repeating units. For example, MXD6 nylon, is not a copolyamide because it contains only a single, chemically distinct repeating unit containing the residues of adipic acid and m-xylylenediamine. By contrast, poly(hexamethylene adipamide-co-isophthalamide), prepared by the condensation of hexamethylenediamine with adipic and isophthalic acid, has two chemically distinct repeating units, that is, a repeating unit containing the residues of hexamethylenediamine and adipic acid, and another repeating unit containing the residues of hexamethylene diamine and isophthalic acid. [0026] The term "polycarbonate" is herein defined as the condensation product of a carbonate source and a diol source, having a carbonate component containing 100 mole percent carbonate units and a diol component containing 100 mole percent diol units, for a total of 200 mole percent monomeric units or 100 mole percent "repeating units". In one embodiment of the present invention, the polycarbonate portion of the first component is based upon the polycarbonate of 4,4'-isopropylidenediphenol, commonly known as bisphenol A polycarbonate. A wide variety of the linear or branched polycarbonates that may be utilized in the present invention may be derived from bisphenol A and can be prepared according to procedures well known in the art such as, for example, as disclosed in U.S. Patent No.'s 3,030,335 and 3,31 7,466. Examples of bisphenol A polycarbonates that may be used in the present invention and are available commerically include the materials marketed under the tradenames LEXAN®, available from the General Electric Company, and MAKROLON®, available from Bayer, Inc.
[0027] The term "polyarylate", as used herein polyesters prepared by the polycondensation of one or more difunctional aromatic dicarboxylic acids with one or more dihydric phenols. For example, typical aromatic dicarboxylic acids are terephthalic and isophthalic acid, and typical aromatic diphenols are bisphenol A and hydroquinone. [0028] The term "residue", as used herein in reference to the polymers of the invention, means any organic structure incorporated into a polymer through a polycondensation or ring opening reaction involving the corresponding monomer. The term "repeating unit", as used herein, means shortest sequence of monomer residues that can be found repeatedly in a polymer. For example, in polyesters, a repeating unit is an organic structure having dicarboxylic acid residue and a diol residue, or hydroxycarboxylic acid residues bonded through a carbonyloxy group. In a polyamide, a repeating unit is an organic structure having a dicarboxylic acid and a diamine residue, lactam, or aminoacid residues, bonded through a amide group.
[0029] It will also be understood by persons having ordinary skill in the art, that the residues associated within the various polyesters, polyamide, polycarbonates, and polyarylates of the invention can be derived from the parent monomer compound itself or any derivative of the parent compound. For example, the dicarboxylic acid and amino acid residues referred to in the polymers of the invention may be derived from a dicarboxylic acid or aminoacid monomer or its associated acid halides, esters, salts, anhydrides, or mixtures thereof. Thus, as used herein, the term "dicarboxylic acid" or "aminoacid" is intended to include dicarboxylic acids and any derivative of a dicarboxylic acid, including its associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process with a diol to make a high molecular weight polyester or polyamide. "Hydroxycarboxylic acid" is intended to include aliphatic and cycloaliphatic hydroxycarboxylic acids as well as monohydroxy-monocarboxylic acids and any derivative thereof, including their associated acid halides, esters, cyclic esters (including dimers such as lactic acid lactides), salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process or ring opening reaction to make a high molecular weight polyester. Similarly, "aminoacid" is intended to include aliphatic, aromatic, and cycloaliphatic aminoacids and any derivative thereof, including their associated acid halides, amides, cyclic amides (lactams), salts, anhydrides, mixed anhydrides, or mixtures thereof, useful in a polycondensation process or ring opening reaction to make a high molecular weight polyamide. In addition, the term "diamine" is intended to include diamines as well as their associated salts, amides, or any other derivative thereof that are useful for the preparation of polyamides. [0030] Whenever the term "inherent viscosity" (I.V.) is used in this application, it will be understood to refer to viscosity determinations made at 25 0C using 0.5 grams of polymer per 100 ml of a solvent comprising 60 weight percent phenol and 40 weight % tetrachloroethane.
[0031] The term "refractive index" (abbreviated herein as "Rl") as used herein, refers to refractive index measurements obtained according to standard methods well known in the art. The refractive indices reported herein were determined at a wavelength of 633 nm using a Metricon Prism Coupler™ model 2010 refractometer (available from Metricon Inc.) and are reported as the average of the refractive indices measured in 3 orthogonal directions (extrusion or stretch, transverse, and thickness directions). The phrase "difference in refractive index" as used herein in the context of the compositions, processes, and shaped articles of the invention always means the value obtained by subtracting the refractive index of the polyester, polycarbonate, or polyarylate- containing component (typically referred to herein as the "first component" or "first layer" in multilayered articles) from the refractive index of the polyamide- or copolyamide-containing component (typically referred to herein as the "second component" or "second layer" in multilayered articles). Thus, in accordance with the invention, the difference in refractive index ("ΔRI") should be calculated according to the following formula:
ΔRI ~ Rl (second component or layer) - Rl (first component or layer) It will be evident to persons skilled in the art that the difference in refractive index may be a positive or negative number.
[0032] The term "%haze", as used herein, refers to haze values determined according to ASTM Method Dl 003 using a HunterLab UltraScan Sphere 8000 Colorimeter manufactured by Hunter Associates Laboratory, Inc., Reston, Va using Hunter's Universal Software (version 3.8) ( %Haze = 100 * Diffuse Transmission / Total Transmission). The procedure for the determination of refractive index is provided in the Examples. For the compositions of the invention, haze is determined by molding or casting the composition into a sheet or film having a thickness of l /8 inch or less and measuring the haze according to the procedure described in the examples. For shaped articles, including multilayer shaped articles, the haze can be determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze according the procedure described herein. [0033] The term glass transition temperature ("Tg") as used herein, refers to the Tg values determined using differential scanning calorimetry ("DSC"), typically using a scan rate of 20°C/min. An example of a DSC instrument is TA Instruments 2920 Differential Scanning Calorimeter. [0034] The compositions of the present invention comprise a first component comprising one or more thermoplastic polymers selected from polyesters, polycarbonates, polyaryϊates, and homogeneous blends thereof. The term "thermoplastic polymer", as used herein, is intended to have its plain meaning as would be understood by persons having ordinary skill in the art, that is, a polymer that softens when exposed to heat and returns to its original condition when cooled to room temperature. The first component may comprise a single thermoplastic polymer or may comprise a blend of 2 or more polymers provided that the blend is a homogeneous blend. The term "homogeneous blend", as used herein, is synonymous with the term "miscible", and is intended to mean that the blend has a single, homogeneous phase as indicated by a single, composition-dependent Tg. For example, a first polymer that is miscible with second polymer may be used to "plasticize" the second polymer as illustrated, for example, in U.S. Patent No. 6,21 1 ,309. Homogeneous blends may be formed by simply blending two or polymers or, in the case of condensation polymers such as for example, polyesters or polyamides, by transesterifying or transamidating two or more polymers. By contrast, the term "immiscible", as used herein, denotes a blend that shows at least 2, randomly mixed, phases and exhibits more than one Tg. Some polymers may be immiscible and yet compatible with each other. A further general description of miscible and immiscible polymer blends and the various analytical techniques for their characterization may be found in Polymer Blends Volumes 1 and 2, Edited by D.R. Paul and CB. Bucknall, 2000, John Wiley & Sons, Inc. [0035] The first component may comprise one or more thermoplastic polymers selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof. For example, the first component may comprise a polyester comprising (a) diacid residues, comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxyltc acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l ,3-cyclobutanedioI; and from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons. Cyclic diols containing cis and trans isomers may be used as the pure cis or trans isomer or as a mixture of cis and trans isomers.
[0036] For example, the diacid residues can comprise the residues of one or more dicarboxylic acids selected from terephthalic acid, isophthalic acid, or combinations thereof, and the diol residues comprise the residues of one or more diols selected from 1 ,4-cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and combinations thereof. In one embodiment, for example, the diacid residues may comprise the residues of terephthalic acid and isophthalic acid. A higher concentration of terephthalic acid in the polyester than isophthalic acid is advantageous because the resulting polyester provides greater impact strength to the blend. For example, the diacid residues may comprise from about 60 to about 100 mole percent of the residues terephthalic acid and 0 to about 40 mole percent of the residues isophthalic acid and the diol residues may comprise about 100 mole percent of the residues of 1 ,4-cyclohexanedimethanol. Other examples of dicarboxylic acid content include about 80 to about 100. mole percent terephthalic acid and 0 to 20 mole percent isophthalic acid, and about 100 mole percent terephthalic acid. [0037] Other representative polyesters that may be used as the thermoplastic polymers of component (i) include polyesters comprising: (a) diacid residues comprising 80 to 100 mole percent of the residues of terephthalic acid and diol residues comprising about 50 to about 90 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 10 to about 50 mole percent of the residues of neopentyl glycol; (b) diacid residues comprising 100 mole percent of the residues of terephthalic acid and diol residues comprising about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexanedimethanol and 60 to about 90 mole percent of the residues of ethylene glycol; (c) diacid residues comprising 100 mole percent terephthalic acid and diol residues comprising about 10 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol, 0 to about 90 mole percent of the residues of ethylene glycol, and about 1 to about 25 mole percent of the residues of diethylene glycol; and (d) diacid residues comprising 1 00 mole percent terephthalic acid and diol residues comprising about 50 to about 90 mole percent 1 ,4-cyclohexanedimethanol and about 10 to about 50 mole percent ethylene glycol.
[0038] In yet another example, the dicarboxylic acid may be selected from terephthalic acid and isophthalic acid, and the diol is selected from 1 ,4-cyclohexanedimethanol and ethylene glycol. In one composition, for example, the dicarboxylic acid is terephthalic acid and the diol is 1 ,4-cyclohexanedimethanol. In yet another example, the diacid residues may comprise at least 95 mole percent of the residues of terephthalic acid and the diol residues may comprise about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexane- dimethanol, about 1 to about 25 mole percent of the residues of diethylene glycol, and about 35 to about 89 mole percent of the residues of ethylene glycol.
[0039] The polyester may further comprise 0 to about 20 mole percent of one or more residues of a modifying diacid containing 2 to 20 carbon atoms if desired. For example, from 0 to about 30 mole % of other aromatic dicarboxylic acids containing 8 to about 16 carbon atoms, cycloaliphatic dicarboxylic acids containing 8 to about 16 carbon atoms, aliphatic dicarboxylic acids containing about 2 to about 16 carbon atoms, or mixtures thereof may be used. Examples of modifying carboxylic acids include, but are not limited to, one or more of 4,4'-biphenyldicarboxylic acid, 1 ,4- naphthalenedicarboxylic acid, 1 ,5- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 2,7- naphthalenedicarbσxylic acid, 4,4'-oxybenzoic acid, trans-4,41- stilbenedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. [0040] In another embodiment, the polyester can comprise about 1 to about 99 mole percent, based on the total moles of diol residues, of the residues of 1 ,4-cyclohexanedimethanol, about 99 to about 1 mole percent of the residues ethylene glycol. Typical mole percentages for the residues of 1 ,4- cyclohexanedimethanol for the polyesters of the invention include from about 1 to about 10 mole percent, from about 1 to about 25 mole percent, from about 1 to about 40 mole percent, 50 mole percent and greater, and 100 mole percent. In another embodiment, for example, the dicarboxylic acid is 1 ,4-cyclohexane- dicarboxylic acid and the diol is 1 ,4-cyclohexanedimethanol. In a further example, the polyester may comprise the residues of 1 ,4-cyclohexane- dimethanol units and the neopentyl glycol. In yet another example, the polyester may comprise the residues of 1 ,4-cyclohexanedimethanol units and 2,2,4,4- tetramethyi-l ,3-cyclobutanediol.
[0041] The diol component of the polyester also may be modified from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons. Other ranges of modifying diol include, but are not limited to, from 0 to about 10 mole percent, and less than 5 mole percent. The modifying diol may be selected from one or more of 1 ,2-propanediol, 1 ,3- propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,4- cyclohexanedimethanol, p-xylene glycol, neopentyl glycol, polyethylene glycol, polytetramethylene glycol, and 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol. Examples of polyalkylene glycols include poly(tetramethylene glycol) ("PTMC") and poly(ethylene glycol) ("PEG") having molecular weights up to about 2,000. The diol component, for example, can be modified with 0 to about 10 mole percent polyethylene glycol or polytetramethylene glycol to enhance elastomeric behavior. In another example, the diol residues may comprise about 10 to about 99 mole percent of residues of 1 ,4-cyclohexanedimethanol, 0 to about 90 mole percent of residues of ethylene glycol, and about 1 to about 25 mole percent of residues of diethylene glycol. The polyester also may contain up to about 5 mole percent, typically from about 0.1 to about 2.0 mole%, based on the acid or diol component, of the residues of a polγfunctional branching agent derived from a compound having at least three carboxyl and/or hydroxy groups to form a branched polyester. Examples of such compounds .include trimellitic acid or anhydride, trimesic acid, pyromellitc anhydride, trimethylolethane, trimethylolpropane, a trimer acid, and the like. It will be understood by persons skilled in the art that the final composition can be arrived at by blending various resins or by direct reactor copolymerization. The latter is desirable to minimize compositional variability but economic necessities often make blending more cost effective.
[0042] Additional examples of polyesters are those containing 100 mole percent terephthalic residues, based on the total diacid residues, and any one of the following diol residue compositions, based on the total diol residues: (i) about 1 to about 5 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 99 to about 95 mole percent of the residues of ethylene glycol; (ii) about 29 to about 33 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 71 to about 67 mole percent of the residues of ethylene glycol; (iii) about 45 to about 55 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 55 to about 45 mole percent of the residues of ethylene glycol; (iv) about 60 to about 65 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 40 to about 35 mole percent of the residues of ethylene glycol; (v) about 79 to about 83 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 21 to about 1 7 mole percent of the residues of ethylene glycol; and (vi) about 100 mole percent of the residues of 1 ,4- cyclohexanedimethanol.
[0043] The polyesters generally will have inherent viscosity (LV.) values in the range of about 0.4 dL/g to about 1 .4 dL/g. Additional examples of LV. ranges include about 0.65 dL/g to about 1.0 dL/g and about 0.7 dL/g to about 0.85 dL/g. As described previously, inherent viscosity is measured at 25 0C using 0.5 grams of polymer per 100 ml of a solvent comprising 60 weight percent phenol and 40 weight % tetrachloroethane
[0044] The polymers of the invention may be crystalline, semicrystalline, or amorphous polymers. The term "semicrystalline", as used herein, means that the polymer contains two phases: an ordered crystalline phase and an unordered amorphous phase. Polymers with a semicrystalline morphology exhibit both a crystalline melting temperature (Tm) and a glass transition temperature (Tg) and may be distinguished from "amorphous" polymers, which exhibit only a glass transition temperature.
[0045] The polyesters used in the present invention typically are prepared from dicarboxylic acids and diols which react in substantially equal proportions and are incorporated into the polyester polymer as their corresponding residues. The polyesters derived from dicarboxylic acid and diol residues of the present invention, therefore, contain substantially equal molar proportions of acid residues (100 mole percent) and diol residues (100 mole percent) such that the total moles of repeating units is equal to 100 mole percent. The mole percentages provided in the present disclosure, therefore, may be based on the total moles of acid residues, the total moles of diol residues, or the total moles of repeating units. For example, a copolyester containing 30 mole percent terephthalic acid, based on the total acid residues, means that the copolyester contains 30 mole percent terephthalic residues out of a total of 100 mole percent acid residues. Thus, there are 30 moles of terephthalic residues among every 100 moles of acid residues. In another example, a copolyester containing 30 mole percent 1 ,4-cyclohexanedimethanol, based on the total diol residues, means that the copolyester contains 30 mole percent 1 ,4-cyclohexane- dimethanol residues out of a total of 100 mole percent diol residues. Thus, there are 30 moles of 1 ,4-cyclohexanedimethanol residues among every T OO moles of diol residues. As used herein, copolyesters of terephthalic acid, ethylene glycol, and 1 ,4-cyclohexandimethanol may be referred to as "PET" when the glycol component is primarily ethylene glycol, "PCT" when the glycol component is primarily 1 ,4-cyclohexanedimethanol, "PETC" when the ratio of ethylene glycol to 1 ,4-cyclohexanedimethanol is greater than 1 and "PCTG" when the ratio of ethylene glycol to 1 ,4-cyclohexanedimethanol ratio is less than 1.
[0046] The polyesters of the instant invention are readily prepared from the appropriate dicarboxylic acids, esters, anhydrides, or salts, and the appropriate diol or diol mixtures using typical polycondensation reaction conditions. Thus, the dicarboxylic acid component of the polyesters of the present invention can be derived from dicarboxylic acids, their corresponding esters, or mixtures thereof. Examples of esters of the dicarboxylic acids useful in the present invention include the dimethyl, dipropyl, diisopropyl, dibutyl, and diphenyl esters, and the like.
[0047] The polyesters of the present invention are prepared by procedures known to persons skilled in the art. They may be made by continuous, semi- continuous, and batch modes of operation and may utilize a variety of reactor types. Examples of suitable reactor types include, but are not limited to, stirred tank, continuous stirred tank, slurry, tubular, wiped-film, falling film, or extrusion reactors. The reaction of the diol and dicarboxylic acid may be carried out using conventional polyester polymerization conditions or by melt phase processes, but those with sufficient crystal Unity may be made by melt phase followed by solid phase polycondensation techniques. For example, when preparing the polyester by means of an ester interchange reaction, i.e., from the ester form of the dicarboxylic acid components, the reaction process may comprise two steps. In the first step, the diol component and the dicarboxylic acid component, such as, for example, dimethyl terephthalate, are reacted at elevated temperatures, typically, about 1 5O0C to about 25O0C for about 0.5 to about 8 hours at pressures ranging from about 0.0 kPa gauge to about 41 4 kPa gauge (60 pounds per square inch, "psig"). Preferably, the temperature for the ester interchange reaction ranges from about 1 SO0C to about 23O0C for about 1 to about 4 hours while the preferred pressure ranges from about 1 03 kPa gauge (1 5 psig) to about 276 kPa gauge (40 psig). Thereafter, the reaction product is heated under higher temperatures and under reduced pressure to form the polyester with the elimination of diol, which is readily volatilized under these conditions and removed from the system. This second step, or polycondensation step, is continued under higher vacuum and a temperature which generally ranges from about 23O0C to about 35O0C, preferably about 250°C to about 3100C and, most preferably, about 26O0C to about 29O0C for about 0.1 to about 6 hours, or preferably, for about 0.2 to about 2 hours, until a polymer having the desired degree of polymerization, as determined by inherent viscosity, is obtained. The polycondensation step may be conducted under reduced pressure which ranges from about 53 kPa (400 torr) to about 0.01 3 kPa (0.1 torr). Stirring or appropriate conditions are used in both stages to ensure adequate heat transfer and surface renewal of the reaction mixture. The reaction rates of both stages are increased by appropriate catalysts such as, for example, alkoxy titanium compounds, alkali metal hydroxides and alcoholates, salts of organic carboxylic acids, alkyl tin compounds, metal oxides, and the like. A three-stage manufacturing procedure, similar to that described in U.S. Patent No. 5,290,631 , may also be used, particularly when a mixed monomer feed of acids and esters is employed.
[0048] To ensure that the reaction of the diol component and dicarboxylic acid component by an ester interchange reaction is driven to completion, it is sometimes desirable to employ about 1.05 to about 2.5 moles of diol component to one mole dicarboxylic acid component. Persons of skid in the art will understand, however, that the ratio of diol component to dicarboxylic acid component is generally determined by the design of the reactor in which the reaction process occurs.
[0049] In the preparation of polyester by direct esterification, i.e., from the acid form of the dicarboxylic acid component, polyesters are produced by reacting the dicarboxylic acid or a mixture of dicarboxylic acids with the diol component or a mixture of diol components. The reaction is conducted at a pressure of from about 7 kPa gauge (1 psig) to about 1379 kPa gauge (200 psig), preferably less than 689 kPa (100 psig) to produce a low molecular weight polyester product having an average degree of polymerization of from about 1 .4 to about 10. The temperatures employed during the direct esterification reaction typically range from about 18O0C to about 2800C, more preferably ranging from about 22O0C to about 27O0C. This low molecular weight polymer may then be polymerized by a polycondensation reaction.
[0050] The thermoplastic polymers of the invention may also comprise a polyarylate. Polyarylates are obtained by polymerization of a dihydric phenol and a dicarboxylic acid. Examples of polyarylates that can be used in the compositions, processes, and shaped articles of the instant invention are described in U.S. Patent No.'s 4,598,130; 5,034,502; and 4,374,239. Examples of dihydric phenols that can be used to prepare the polyarylates are bisphenols such as bis(4-hydroxyphenyl)methane; 2,2-bis(4-hydroxyphenyl) propane ("bisphenol-A"); 2,2-bis(4-hydroxy-3-methylphenyl)propane; 4,4-bis(4- hydroxyphenyOheptane; 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; 2,2- bis(4~hydroxy~3,5-dibromophenyl)propane; dihydric phenol ethers such as, for example, bis(4-hydroxyphenyl)ether; bis(3,5-dichloro-4-hydroxyphenyl)ether;; dihydroxydiphenyls such as, for example, p,p'-dihydroxydiphenyl, 3,3'- dichloro-4, 4'-dihydroxydiphenyl; dihydroxyaryl sulfones such as, for example, bis(4- hydroxyphenyl)sulfone; bis(3,5-dimethyl-4-hydroxyphenyl)sulfone; dihydroxy benzenes such as, for example, resorcinol; hydroquinone; halo- and alkyl-substituted dihydroxy benzenes such as, for example, 1 ,4-dihydroxy-2,5- dichlorobenzene; 1 ,4- dihydroxy-3-methylbenzene; and dihydroxy diphenyl sulfoxides such as, for example, bis(4-hydroxyphenyl)suifoxide; and bis(3,5- dibromo-4-hydroxyphenyl) sulfoxide. A variety of additional dihydric phenols are also available such as are disclosed, for example, in U.S. Pat. Nos. 2,999,835; 3,028,365 and 3,1 53,008. Also suitable are copolymers prepared from the above dihydric phenols copolymerized with halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane. It is also possible to employ two or more different dihydric phenols or a copolymer of a dihydric phenol with a glycol, with hydroxy or acid terminated polyester, or with a dibasic acid as well as blends of any of the above materials. Suitable dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids such as phthalic, isophthalic, terephthalic, o-phthalic, o-, m-, and p-phenylenediacetic acids, and polynuclear aromatic acids such as, for example, diphenic acid and 1 ,4-naphthalic acid. [0051] Additional examples of polyarylates that can be used in the present invention include those polymers resulting from the polymerization of bisphenol A (2,2-bis-(4~hydroxyphenyl)propane) and a 50:50 mixture iso/terephthalic acids. Some of the polymers are commercially available under the trademark "U- Polymer U-I OO" (available from Unitika America Corporation). Other examples are polyarylates based on tetramethyl bisphenol-A; 4,4'-dihydroxy- benzophenone; and 5-tertiary-butyl isophthalic acid dichloride. [0052] The polyarylates of the present invention can be prepared by any polyester forming reactions well known in the art such as, for example, interfacial polymerization by mixing a solution of an aromatic dicarboxylic acid dihalide in an organic solvent with an alkaline aqueous solution of a bisphenol under stirring to react these materials; solution polymerization by reacting an aromatic dicarboxylic acid dihalide with a bisphenol in the presence of a deacidifying agent such as pyridine in an organic solvent; molten polymerization by reacting an aromatic dicarboxylic acid diphenyl ester with a bisphenol; molten polymerization by reacting an aromatic dicarboxylic acid, diphenyl carbonate and a bisphenol; molten polymerization by reacting an aromatic dicarboxylic acid with a bisphenol diacetate; and polymerization by reacting an aromatic dicarboxylic acid with a bisphenol diacetate. Examples of methods for preparation of polyarylates are disclosed in U.S. Patent No.'s 5,034,502, 4,321 ,355, and 4,374,239. The polyarylates of the invention typically have inherent viscosities of about 0.5 to about 1.1 dL/gm. [0053J (n addition, the polyester, polycarbonates, and polyarylates may further comprise one or more of the following: antioxidants, melt strength enhancers, branching agents (e.g., glycerol, trimellitic acid and anhydride), chain extenders, flame retardants, fillers, acid scavengers, dyes, colorants, pigments, antiblocking agents, flow enhancers, impact modifiers, antistatic agents, processing aids, mold release additives, plasticizers, slips, stabilizers, waxes, UV absorbers, optical brighteners, lubricants, pinning additives, foaming agents, antistats, nucleators, and the like. Colorants, sometimes referred to as toners, may be added to impart a desired neutral hue and/or brightness to the polyester. Preferably, the polyester compositions may comprise 0 to about 30 weight percent of one or more processing aids to alter the surface properties of the composition and/or to enhance flow. Representative examples of processing aids include calcium carbonate, talc, clay, mica, zeolites, wollastonite, kaolin, diatomaceous earth, TiO2, NH4CI, silica, calcium oxide, sodium sulfate, and calcium phosphate. Use of titanium dioxide and other pigments or dyes, might be included, for example, to control whiteness of the film, or to make a colored articles. An antistat or other coating may also be ^applied to the surface of the article.
[0054] The second component (ii) of the compositions of the invention comprises a transamidized, homogeneous blend of at least two polyamides. Typically, the homogeneous blend will comprise from 2 to about 10 different polyamides. In another example, the homogeneous blend can comprise from 2 to 4 polyamides. In accordance with the present invention, polyamides that display a melting point below about 300°C can be used as at least one polyamide. In another example, polyamides with the melting point less than about 275°C and glass transition temperature greater than about 250C may be used. Typically, the polyamides have an I. V. between about 0.3 dL/g and about 2.0 dL/g and, preferably at least 0.5 dL/g.
[0055] For the composition of the invention, it is advantageous that transamination occur between the polyamides to produce of homogeneous blend. The term "transamidized", as used herein, is intended to be synonymous with the terms "trans am id ate" and "transamidation", and means the process of exchanging am/do groups between two different poiyamides. Transamidation between two or more polyamides can be accomplished by contacting the polyamides at elevated temperatures, typically from about 27O0C to about 35O°C. Other examples of transamidation temperatures are about 2800C to about 35O0C and about 2900C to about 34O0C. Transamidation between the polyamides is indicated by the presence of a single glass transition temperature ("Tg") for the blend as determined by differential scanning calorimetry ("DSC") using standard techniques well known to persons skilled in the art such as, for example, described in ASTM Method D341 8. The polyamides may be heated together directly at these temperature or in the presence of the thermoplastic polymers of the first component (i). For example, the contacting and, hence, transamidation of the polyamides can take place by melt blending of the first and second components, during extrusion, or other high temperature processing of the polymer composition and its components. In another example, the polyamides may be heated together in a separate vessel and then melt blended with the first component.
[0056] The first and second polyamides of the second component may be selected from a wide range of polyamides. To better match the refractive index of the first component, it is desirable, but not essential, that at least one of the polyamides comprise aromatic residues. In one example, the polyamides can comprise partially aromatic polyamides and aliphatic polyamides having a number average molecular weight of 7,000 or less. Combinations of such polyamides are included also within the scope of the invention. Partially aromatic polyamides comprise amide linkages between at least one aromatic ring and at least one nonaromatic species. Although wholly aromatic polyamides generally are liquid crystalline, the blends of such resins having melting points less than 300°C can be used for this invention. When homogeneous blends of polyamides are used, the rapid transamidization (amide-amide interchange) of aliphatic nylon with aromatic or partially aromatic polyamide permits the tailoring of refractive index of the polyamide blend by adjusting the ratios of aliphatic polyamide to aromatic, or partially aromatic, polyamide. This technique enables a matching of the refractive index of the homogeneous polyamide blend to the thermoplastic polymer such as, for example, one or more polyesters, of the first component. A reference for transamidization can be found in the work by Y. Takeda, et.al., Polymer, 1992 vol. 33, pg. 3394.
[0057] In accordance with the invention, the second component can be a transamidized, homogeneous blend of 2 or more polyamides such as, for example, a first polyamide and a second polyamide which are selected to give a refractive index in the second component such that second and first components have a difference in refractive index (Rl(second component) - RKfirst component)) of about 0.006 to about -0.0006. To match the refractive index of the first component, it is advantageous that the first and second polyamide have different amounts of aromatic and aliphatic residues. For example, the second component (ii) can comprise a homogeneous blend of a first polyamide, comprising aromatic residues, and of a second polyamide comprising aliphatic residues. The term "aliphatic", as used herein with respect to the diamine and dicarboxylic acid monomers of the polyamides of the present invention, means that carboxyl or amino groups of the monomer are not connected through an aromatic nucleus. For example, adipic acid contains no aromatic nucleus in its backbone, i.e., the chain of carbon atoms connecting the carboxylic acid groups; thus, it is "aliphatic". By contrast, the term "aromatic" means the dicarboxylic acid or diamine contains an aromatic nucleus in the backbone such as, for example, terephthalic acid or λ ,4-metaxylylenediamine. Representative examples of aromatic polyamides are those polyamids comprising at least 70 mole % of residues comprising diamines such as m- xylylenediamine or a xylylenediamine mixture comprising m-xylylenediamine and up to 30% of p-xylylenediamine and an aliphatic dicarboxγ\\c acid having 6 to 10 carbon atoms. The term "aliphatic", therefore, is intended to include both aliphatic and cycloaliphatic structures such as, for example, diamine, diacids, lactams, aminoalcohols.and aminocarboxylic acids, that contain as a backbone a straight or branched chain or cyclic arrangement of the constituent carbon atoms which may be saturated or paraffinic in nature, unsaturated (i.e., containing non-aromatic carbon-carbon double bonds), or acetylenic (i.e., containing carbon-carbon triple bonds). Thus, in the context of the description and the claims of the present invention, aliphatic is intended to include linear and branched, chain structures (referred to herein as "aliphatic") and cyclic structures (referred to herein as "alicyclic" or "cycloaliphatic"). The term "aliphatic", however, is not intended to exclude any aromatic substituents that may be attached to the backbone of an aliphatic or cycloaliphatic diol or diacid or hydroxycarboxylic acid.
[0058] The weight percentage ratio of the first and second polyamides present in the transamidized, homogeneous blend may range from about 1 :50 to about 50:1 based on the total weight of the second component. Other examples of weight percentage ratios are 1 :20 to about 20:1 and about 1 :10 to about 10:1.
[0059] Examples of polyamides that may be used in the homogeneous blends of the present invention include polyamides comprising one or more of residues selected from isophthalic acid, terephthalic acid, cyclohexane- dicarboxylic acid, meta-xylylenediamine (also referred to herein as "m- xylylenediamine"), para-xylylenediamine (also referred to herein as "p- xylylenediamine"), 1 ,3- cyclohexane(bis)methylamine, 1 ,4-cyclohexane(bis)- methylamine, aliphatic diacids with 6 to 12 carbon atoms, aliphatic amino acids or lactams with 6 to 12 carbon atoms, aliphatic diamines with 4 to 12 carbon atoms. Other generally known polyamide forming diacids and diamines can be used. The polyamides also may contain small amounts of trifunctional or tetrafunctional comonomers such as trimellitic anhydride, pyromellitic dianhydride, or other polyamide forming polyacids and polyamines known in the art.
[0060] Examples of partially aromatic polyamides include, but are not limited to: poly(m-xylylene adipamide) (referred to herein as "MXD6" nylon), poly(hexamethylene isophthalamide), poly(hexamethylene adipamide-co- isophthalamide), poly(hexamethylene adipamide-co-terephthalamide), and poly(hexamethylene isophthalamide-co-terephthalamide). In one embodiment, the partially aromatic polyamide is poly(m-xylylene adipamide). In one embodiment, the partially aromatic polyamides may have a number average molecular weight of 7000 or less. Representative examples of aliphatic polyamides include poly(2-pyrrolidinone) (nylon 4, 6; CAS No. 44,299-2 ); polycapramide (nylon 6; CAS No. 1 8,1 1 1 -0), poly(2-piperidone) (nylon 5, CAS No. 24938-57-6); poly(7-aminoheptanoic acid) (nylon 7; CAS No. 25035-01 -2); poly(nonanamide) (nylon 9; CAS No. 25748-72-5); poly(l 1 -aminoundecanoic acid) (nylon 1 1 ; CAS No. 25035-04-5); poly(12-aminolauric acid) (nylon 12, CAS No. 24937-16-4); poly(ethyleneadipamide) (nylon 2,6); polytetramethylene- adipamide (nylon 4,6; CAS No. 50327-22-5); polyhexamethylene-adipamide (nylon 6,6; CAS No. 42,917-1), (nylon 6,9; CAS No. 18,806-9) poly- (hexamethylene-sebacamide) (nylon 6,10; CAS No. 9008-66-6), poly(hexamethylene-undecanamide) (nylon 6, 1 1 ) poly (hexamethylene- dodecamide) (nylon 6,12; CAS No. 24936-74-1), poly(octamethylene- adipamide) (nylon 8,6); adipic acid-decamethylenediamine copolymer (nylon 10,6; CAS No. 26123-27-3); polydecamethylene- dodecamide (nylon 10, 12); poly(dodecamethyiene-adipamide) (nylon 12,6); and poly(dodecamethylene- sebacamide) (nylon 12,8).
[0061] For example, the second component (ii) can comprise a homogeneous blend comprising a first polyamide comprising the residues of m- xylylenediamine and adipic acid, and a second polyamide comprising the residues of at least one aliphatic or cycloaliphatic monomer selected from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioc acid, dodecanedioc acid, caprolactam, butyrolactam, 1 1 -aminoundecanedioc acid, isophthalic acid, and hexamethylene diamine. The first polyamide, for example, can comprise MXD6 nylon, which is commerically available from Mitsubishi Corporation. In another example, the second polyamide can comprise at least one polyamide selected from from nylon 4; nylon 6; nylon 9; nylon 1 1 ; nylon 12; nylon 6,6; nylon 5,10; nylon 6,12; nylon 6,11 ; nylon 10,12; and combinations thereof. In yet another example, the second polyamide can comprise nylon 6, nylon 6,6, or blends thereof.
[0062] The second component also may comprise a single copolyamide in which the composition of monomer residues is chosen to give a refractive index that closely matches the refractive index of the first component. Thus, in another embodiment, the invention provides a polymer composition, comprising an immiscible blend of: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and
(Ii) a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, RKsecond component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less. For example, the copolyamide can the residues of m- xylylenediamine, p-xylylenediamine, or a combination thereof; and the residues of at least one monomer selected from terephthalic acid, isophthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioc acid, dodecanedioc acid, caprolactam, butyrolactam, 1 1 -amino-undecanedioc acid, and 1 ,6-hexamethylenediamine. In another example, the copolyamide can comprise about 1 5 to about 100 mole percent of the residues of m- xylylenediamine, based on a total diamine residue content of 1 00 mole%, and about 1 5 to about 85 mole percent of the residues adipic acid and about 85 to about 1 5 mole percent of the residues of one or more aliphatic or cycloaliphatic dicarboxylic acids selected from pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and 1 ,4-cyclohexanedicarboxylic acid, based on a total diacid residue content of 1 00 mole%. It is understood that the various embodiments of homogeneous blends of polyamides and copolyamides referred to herein can be combined with any of the embodiments of the polyesters discussed hereinabove.
[0063] Other examples of copolyamides that can be used as in composition of the invention, either alone or as part of a homogeneous blend with another polyamide, include, but are not limited to, copolyamides comprising from about 1 5 to about 1 00 mole percent of the residues of m- xylylenediamine, based on a total diamine residue content of 1 00 mole%, and the residues of adipic acid. Typical amounts of adipic acid residues which may be present in these copolyamides, based on the total moles of diacid residues, are about 5 to about 85 mole percent, about 20 to about 80 mole percent, and about 25 to about 75 mole percent. The remainder of the dicarboxylic acid residues can comprise residues from one or more aliphatic dicarboxylic acids having from 7-12 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, or 1 ,4-cyclohexanedicarboxylic acid. In another example, the polyamide acid also may comprise residues from isophthalic acid and terephthalic acid. [0064] The copolyamides of the invention also may comprise other diamines or lactam residues in addition to m-xylyienediamine residues. For example, the copolyamide can comprise at least 1 5 mole percent, or at least about 20 mole percent of the residues of m-xylylenediamine with the remainder of the diamines residues comprising the residues of one or more aliphatic or aromatic diamines. For example, the copolyamide may comprise about 80 mole percent or about 85 mole %, of the residues of 1 ,6-hexamethylene diamine, based on the total moles of diamine residues. Varying amounts of p-xylylene- diamine, l ,3-cyclohexanebis(methylamine), or 1 ,4-cyclohexanebis(methyl- amine), also may be used. Similarly, the copolyamide may comprise the residues of a lactam, such as caprolactam, or lactams based on gamma-amino-butyric acid or 11 -amino-undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or from about 10 mole percent to about 70 mole percent based on the total moles of repeating units. In another embodiment, the copolyamides of the invention can comprise from about 1 5 mole percent to about 85 mole percent, about 20 to about 80 mole percent, or about 25 to about 75 mole percent of the residues from m-xylylenediamine, based on the total moles of diamine residues with the remainder of the diamine residues content comprising residues from one or more diamines, such as aliphatic diamines, and especially 1 ,6-hexamethylene diamine. In this embodiment, the diamine residues may further comprise minor amounts of the residues of other diamines, for example p-xylylenediamine, or a cyclic aliphatic diamine such as, for example, one or more of: 1 ,3-cyclohexanebis(methylamine) or 1 ,4- cyclohexanebis(methylamine). Further, the polyamide may optionally include, in place of a portion of the adipic acid, residues from one or more aliphatic or aromatic dicarboxylic acids having from 7-12 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, 1 ,4-cyclohexanedicarboxylic acid, or isophthalic acid, which may be present in an amount from about 1 5 mole percent to about 85 mole percent, optionally with minor amounts of terephthalic acid. The polyamide also may comprise the residues of a lactam, such as caprolactam, or lactams based on gamma-amino-butyric acid or 1 l -amino~undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or about 10 mole% to 70 mole percent, based on the total moles repeating units.
[0065] in yet another embodiment, the copolyamides according to the invention may comprise from about 15 mole percent up to about 90 mole percent of residues from adipic acid, with the remaining diacid residues comprising the about 10 to about 85 mole percent of the residues of isophthalic acid, based on the total moles of dicarboxylic acid residues. Additional examples of adipic acid and isophthalic acid residue content include about 20 to 80 mole percent, and about 25 to about 75 mole percent. In this embodiment, the polyamide may optionally comprise minor amounts of residues from one or more aliphatic dicarboxylic acids having from 7-12 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, or 1 ,4-cyclohexanedicarboxylic acid, optionally with minor amounts of terephthalic acid. Optionally, the polyamides may comprise m- xylylenediamine residues. Examples of m-xylylenediame residue concentrations include about 1 5 to about 90 mole percent, about 20 to about 85 mole percent, or about 25 to about 80 mole percent. The remaining residues can comprise from one or more aliphatic diamines, such as, for example, 1 ,6-hexamethylene diamine, one or more aromatic diamines such as, for example, p-xylylene- diamine. Similarly, the copolyamide also may comprise the residues of a lactam - 47 -
such as, for example, caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino-undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent or about 10 mole percent to about 70 mole percent, based on the total moles of repeating units.
[0066] In yet another example, the copolyamides of the invention may comprise the residues of one or more lactams such as, for example, caprolactam, or lactams based on gamma-amino-butyric acid or 1 1 -amino- undecanoic acid, in an amount from about 10 mole percent to about 90 mole percent, or from about 10 mole percent to about 70 mole percent, or from about 1 5 mole percent to about 60 mole percent, based on the total moles of repeating units. The residues of one or more aliphatic dicarboxylic acids having from 7-12 carbon atoms, such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, or 1 ,4-cyclohexanedicarboxylic acid, also may be present in amounts from about 20 mole percent to about 80 mole percent, based on the total moles of repeating units. For example, the copolyamide may comprise residues from isophthalic acid or terephthalic acid. In this embodiment, the copolyamides can comprise from about 1 5 mole percent to about 85 mole percent of the residues from m-xylylenediamine, based on the total moles of diamine residues. Other examples of m- xylylenediamine content are about 20 to about 80 mole percent and about 25 to about 75 mole percent. The remainder of the diamine residues may comprise the residues of one or more diamines aliphatic diamines such as, for example, 1 ,6-hexamethylene diamine. In this embodiment, the diamine residues may further comprise minor amounts of the residues of other diamines, for example p-xylyienediamine, or a cyclic aliphatic diamine such as, for example, one or more of. 1 ,3-cyclohexanebis(metriylamine) or 1 ,4-cyciohexanebis(methylamine).
Optionally, minor amounts of one or more of: p-xylylenediamine, 1 ,3- cyclohexanebis(methylamine), or l ,4-cyclohexanebis(methylamine), may be used.
[0067] Another embodiment of the invention is polymer composition, consisting essentially of an immiscible blend of:
(i) a first component consisting essentially of at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component consisting essentially of a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - RI(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of \ Q% or less. The phrase "consisting essentially of", as used herein is intended to encompass compositions which are immiscible blends, that is, having at least 2, composition-dependent Tg's as measured by DSC, and which have first component containing a polyester, polycarbonate, polyaryiate, or homogeneous blends thereof and a second component containing a homogeneous, transamidized blend of at least 2 polyamides. In this embodiment, the composition is understood to exclude any elements that would substantially alter the essential properties of the composition to which the phrase refers. For example, compositions may include other components that do not alter the refractive index of the components, %haze of the blend, the %transmittance, or the miscibility of the blend. For example, the addition of a compatibilizer, which may alter the miscibility and refractive index of the composition, would be excluded from this embodiment. Similarly, a second component containing a copolyamide prepared by copolymerization of the component monomers would be excluded because such a copolyamide would be considered to have different properties than a homogeneous, transamidized blend of at least 2 poiyamides, even if the mole percentage of the monomer residues are equivalent.
[0068] Similarly, another embodiment of the instant invention is an oxygen-scavenging composition consisting essentially of:
(A) an immiscible blend consisting essentially of
(i) first component consisting essentially of at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof; (U) a second component consisting essentially of a copolyamide or a transamidized, homogeneous blend of at least two poiyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, RKsecond component) - Rl (f i rst component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less; and
(B) at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements; wherein the first component and the second component have refractive indices which differ in absolute value by 0.008 or less and the shaped article has a % transmittance of at least 75%, and a haze of 10% or less. In this embodiment, the composition is understood to exclude any elements that would substantially alter the essential properties of the composition to which the phrase refers, such as, for example, the refractive index of the components, %haze of the blend, the %transmittance, the miscibility of the blend, or the oxygen-scavenging propertions of the composition. For example, the addition an oxygen- scavenging component other than a copolyamide or a transmidized blend of polyamides such as, for example, a diene, polyether, or any easily oxidizable organic compound other than the components as listed in the claims would be excluded.
[0069] The polyamides used in the present invention typically are prepared from dicarboxylic acids and diamines, which react in substantially equal proportions, or by the ring-opening polymerization of lactams, and are incorporated into the polyamide polymer as their corresponding residues. The polyamides derived from dicarboxylic acid and diamine residues of the present invention, therefore, contain substantially equal molar proportions of acid residues (100 mole percent) and diamine residues (100 mole percent) such that the total moles of repeating units is equal to 100 mole percent. The mole percentages provided in the present disclosure, therefore, may be based on the total moles of acid residues, the total moles of diamine residues, or the total moles of repeating units. For example, a polyamide or copolyamide containing 30 mole percent terephthalic acid, based on the total acid residues, means that the copolyamide contains 30 mole percent terephthalic residues out of a total of 100 mole percent acid residues. Thus, there are 30 moles of terephthalic residues among every 100 moles of acid residues. In another example, a copolyamide containing 30 mole percent m-xylylenediamine, based on the total diamine residues, means that the copolyester contains 30 mole percent m- xylylenediamine residues out of a total of 100 mole percent diamine residues. Thus, there are 30 moles of m-xylylenediamine residues among every 100 moles of diamine residues.
[0070] Any method known in the art can be used to produce the polyamides. The polyamides are generally prepared by melt phase polymerization from a diacid-diamine complex which may be prepared either in situ or in a separate step. In either method, the diacid and diamine are used as starting materials. Alternatively, an ester form of the diacid may be used, preferably the dimethyl ester. If the ester is used, the reaction must be carried out at a relatively low temperature, generally 80 to 1200C, until the ester is converted to an amide. The mixture is then heated to the polymerization temperature. In the case of polycaprolactam, either caprolactam or 6- aminocaproic acid can be used as a starting material and the polymerization may be catalyzed by the addition of adipic acid/hexamethylene diamine salt which results in a nylon 6/66 copolymer. When the diacid-diamine complex is used, the mixture is heated to melting and stirred until equilibration. [0071] The molecular weight is controlled by the diacid-diamine ratio. An excess of diamine produces a higher concentration of terminal amino groups. For oxygen-scavenging compositions, it is advantageous to adjust the diacid- diamine ratio to produce the concentration of terminal amine groups to 20 mmole/kg or less. If the diacid-diamine complex is prepared in a separate step, excess diamine is added prior to the polymerization. The polymerization can be carried out either at atmospheric pressure or at elevated pressures. [0072] To exhibit satisfactory clarity and low haze, the second component and first component of the immiscible blend typically have refractive indices which differ by about 0.006 to about -0.0006, that is, the Rl(second component) - Rl(first component) is about 0.006 to about -0.0006. Other examples of differences in the absolute value of the refractive indices are about 0.005 to about -0.0006, about 0.004 to about -0.0006, about 0.003 to about -0.0006, about 0.005 to about -0.0005, and about 0.004 to about -0.0005. Persons of skill in the art will understand, however, that the difference in refractive indices which may be acceptable depends on the blend composition, particle diameter, refractive index, wavelength, and particle structure as described by Biangardi et al., DieAngew. Makromole. Chemie, 183, 221 (1990).
[0073] The immiscible blend of the instant invention has excellent clarity and has a % transmittance of at least 75%, as determined by ASTM Method Dl 003, and a haze of 10% or less. Other examples of % transmittance are at least 77%, at least 80%, and at least 85%. Additional examples of haze values which may be exhibited by the blends of the invention are 9% or less, 7% or less, 5% or less, and 3% or less. For the compositions of the invention, haze is determined by molding or casting the composition into a sheet or film having a thickness of 1 /8 inch or less and measuring the haze according to the procedure described in the examples. For shaped articles, including multilayer shaped articles, the haze can be determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze according the procedure given in the examples. [0074] The first component also may comprise homogeneous blend of one or more polymers. For example, the first component may comprise a homogeneous blend of a first polyester with one or more polymers chosen from a polycarbonate, a second polyester, and a polyarylate. The polyester may be any polyester as described herein. For example, the first component may comprise a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A.
[0075] The polycarbonate may comprise about 90 to 100 mole percent, based on the total moles of diol residues, of the residues bisphenol A, and from 0 to about 10 mole percent of the residues of one or more modifying aliphatic diols or dihydric phenols having from 2 to 16 carbons. Representative examples include bis(4-hydroxyphenyl)methane; 2,2-bis(4-hydroxyphenyl) propane ("bisphenol-A"); 2,2-bis(4-hydroxy-3~methylphenyl)propane; 4,4-bis(4- hydroxyphenyl)heptane; 2,2-bis(4-hydroxy-3,5-dich!orophenyl)propane; 2,2- bis(4-hydroxy-3,5-dibromophenyl)propane; dihydric phenol ethers such as, for example, bis(4-hydroxyphenyl)ether; bis(3,5-dichloro-4-hydroxyphenyl)ether;; dihydroxydiphenyls such as, for example, p.p'-dihydroxydiphenyl, 3,3'- dichloro-4, 4'-dihydroxydiphenyl; dihydroxyary) sulfones such as, for example, bis(4- hydroxyphenyOsulfone; bis(3,5-dimethyl-4-hydroxyphenyl)sulfone; dihydroxy benzenes such as, for example, resorcinol; hydroquinone; halo- and alkyl-substituted dihydroxy benzenes such as, for example, 1 ,4-dihydroxy-2,5- dichlorobenzene; 1 ,4- dihydroxy-3-methylbenzene; and dihydroxy diphenyl sulfoxides such as, for example, bis(4-hydroxyphenyl)sulfoxide; and bis(3,5- dibromo-4-hydroxyphenyl) sulfoxide. A variety of additional dihydric phenols are also available such as are disclosed, for example, in U.S. Patent No.'s 2,999,835; 3,028,365 and 3,153,008. Also suitable are copolymers prepared from the above dihydric phenols copolymerized with halogen-containing dihydric phenols such as 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo- 4-hydroxyphenyl)propane. It is also possible to employ two or more different dihydric phenols or a copolymer of a dihydric phenol with a glycol, with hydroxy or acid terminated polyester, or with a dibasic acid as well as blends of any of the above materials. Suitable dicarboxylic acids include, but are not limited to, aromatic dicarboxylic acids such as phthalic, isophthalic, terephthalic, o-phthalic, o-, m-, and p-phenylenediacetic acids, and polynuclear aromatic acids such as, for example, diphenic acid and 1 ,4-naphthalic acid. [0076J Representative examples of aliphatic diofs include ethylene glycol, propanediols, butanediols, pentanediols, hexandiols, heptanediols, octanediols, neopentyl glycol, aryl-alkyl glycols such as styrene glycol, xylylene glycols, dihydroxy alkyl ethers of dihydric phenols such as the dihydroxy ethyl ether of Bisphenol-A, and the like. Other examples of aliphatic diols are higher molecular weight aliphatic dihydroxy compounds such as, for example, polyethylene glycols, polystyrene glycols, polypropylene glycols, polybutylene glycols, polythioglycols, poly-arylalkyl ether glycols and copolymer polyether glycols. Additional representative examples of dihydric phenols and aliphatic diols are described in U.S. Patent No.'s 3,030,335 and 3,317,466. The polycarbonate may further comprise the residues of one or more branching agents such as, for example, tetraphenolic compounds, tri~(4-hydroxyphenyl) ethane, pentaerythritol triacrylate and others compounds as disclosed in U.S. Patent No.'s 6,160,082; 6,022,941 ; 5,262,51 1 ; 4,474,999; and 4,286,083. Other suitable branching agents are mentioned herein below. In a further example, the polycarbonate comprises at least 95 mole percent, based on the total moles of diol residues, of the residues of bisphenol A.
[0077] The inherent viscosity of the polycarbonate portion of the blends according to the present invention is preferably at least about 0.3 dL/g, more preferably at least 0.5 dL/g. The melt flow of the polycarbonate portion of the blends according to the present invention is preferably between 1 and 20, and more preferably between 2 and 1 8, as measured according to ASTM Method Dl 238 at a temperature of 3000C and using a weight of 1.2 kg. [0078] Processes for the preparation of polycarbonates are well known in the art. The linear or branched polycarbonates that can be used in the invention and disclosed herein are not limited to or bound by the polycarbonate type or its production method. Generally, a dihydric phenol, such as bisphenol A, is reacted with phosgene with the use of optional mono-functional compounds as chain terminators and tri-functional or higher functional compounds as branching or crosslinking agents. Monofunctional, difunctional, and trifunctional reactive acyl halides also can used in the preparation of polycarbonates as terminating compounds (mono-functional), comonomers (di-functional), or branching agents (tri-functional or higher).
[0079] For example, the polycarbonate portion of the present blend can be prepared in the melt, in solution, or by interfacial polymerization techniques well known in the art. Suitable methods include the steps of reacting a carbonate source with a diol at a temperature of about O0C to 31 50C at a pressure of about 0.1 to 760 mm Hg for a time sufficient to form a polycarbonate. Commercially available polycarbonates that can be used in the present invention, are normally made by reacting an aromatic diol with a carbonate source such as, for example, phosgene, dibutyl carbonate, or diphenyl carbonate, to incorporate 100 mole percent of carbonate units, along with 100 mole percent diol units into the polycarbonate. Other representative examples of methods of producing polycarbonates are described in U.S. Patent No.'s 5,498,688; 5,494,992; and 5,489,665.
[0080] Blends of the of polyesters and polycarbonates can be made by methods which include the steps of blending the polycarbonate and polyester portions at a temperature of about 25 °C to 35O0C for a time sufficient to form a clear blend composition. Suitable conventional blending techniques include the melt method and the solution-prepared method. Other suitable blending techniques include dry blending and/or extrusion. [0081] The compositions of the present invention, including the immiscible and homogeneous blends contained therein, may be prepared by any method known in the art and are useful as thermoplastic molding compositions and for formation of films and single and multilayered articles. In addition to physically blending the various components of the blend, homogeneous polyesters blends may be prepared by transesterification of the polyester components. Similarly, homogeneous blends of polyamides may be prepared by transamination of the polyamide components.
[0082] The melt blending method includes blending the polymers at a temperature sufficient to melt the first component and second component portions, and thereafter cooling the blend to a temperature sufficient to produce a clear blend. The term "melt" as used herein includes, but is not limited to, merely softening the polymers. Examples of melt mixing methods generally known in the polymers art are described in Mixing and Compounding of Polymers (I. Manas-Zloczower' & 2. Tadmor eds., Carl Hanser Verlag publisher, N.Y. 1 994). [0083] The solution-prepared method includes dissolving the appropriate weight/weight ratio of the first component and second component in a suitable organic solvent such as methylene chloride or a 70/30 mixture of methylene chloride and hexafluoroisopropanol, mixing the solution, and separating the blend composition from solution by precipitation of the blend or by evaporation of the solvent. Solution-prepared blending methods are generally known in the polymers art.
[0084] The melt blending method is the preferred method for producing the blend compositions of the present invention. The melt blending method is more economical and safer than the solution method, which requires the use of volatile solvents. The melt blending method also is more effective in providing clear blends. Any of the clear blends of the present invention that can be prepared by solution blending also can be prepared by the melt method. Some of the blends of the present invention, however, can be prepared by the melt method, but not by the solution-prepared method. Any blending process which provides clear blends of the preseηt invention is suitable. One of ordinary skill in the art will be able to determine appropriate blending methods for producing the clear blends of the present invention.
[0085] These first and second components of the composition may be compounded in the melt, for example, by using a single screw or twin screw extruder. They may also be prepared by blending in solution. Additional components such as stabilizers, flame retardants, colorants, lubricants, release agents, impact modifiers, and the like may also be incorporated into the formulation. For example, the compositions can be produced via a melt extrusion compounding of the first component and the second component with any other composition components such as, for example, metal catalysts, dyes, toners, fillers, and the like. The composition may be formed by dry blending solid particles or pellets of each of thermoplastic polymers and the polyamide components and then melt blending the mixture in a suitable mixing means such as an extruder, a roll mixer, or the like. When a transamidized, homogeneous blend of polyamides is used as the second component, it is advantageous to conduct the processing at a temperature that will cause transamidation between the polyamides to occur. Typically, these temperatures range from about 27O°C to about 35O0C. Other examples of transamidation temperatures are about 28O0C to about 35O0C and about 29O0C to about 340°C. Blending is conducted for a period of time that will yield a well dispersed, immiscible blend. Such may easily be determined by those skilled in the art. If desired, the composition may be cooled and cut into pellets for further processing, it may be extruded into films, sheets, profiles, and other shaped elements, injection or compression molded to form various shaped articles, or it may be formed into films and optionally uniaxially or biaxially stretched by means well known in the art.
[0086] The amounts of the first and second components in the immiscible blend may vary widely. For example, the immiscible blend of our novel composition may comprise about 5 to about 99 weight percent of the first component and about 95 to about 1 weight percent of the second component, based on the total weight of the composition. Other non-limiting, representative examples of weight percentages of the first and second components include about 50 to about 99 weight percent of the first component and about 50 to about 1 weight percent of the second component, about 60 to about 99 weight percent of the first component and about 40 to about 1 weight percent of the second component, and about 70 to about 99 weight percent of the first component and about 30 to about 1 weight percent of the second component. [0087] Our invention also provides a composition prepared by a process comprising melt blending: (i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a homogeneous, transamidized blend of at least 2 polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less. The composition includes the various embodiments of the polyesters, polycarbonates, polyarylates, homogeneous blends, and polyamides as described above and any combination thereof. For example, the second component of the composition can comprise a homogeneous, transamidized blend of at least 2 polyamides in which transamidation may be accomplished by contacting the polyamides at elevated temperatures, typically from about 27O0C to about 35O0C. Other examples of transamidation temperatures are about 28O0C to about 35O0C and about 2900C to about 3400C. f0088] The homogeneous blend of component (ii) can comprise a first polyamide, comprising aromatic residues, and a second polyamide comprising aliphatic residues, as described previously. For example, typical polyamides that can be used as the second polyamide include, but are not limited to, nylon 4; nylon 6; nylon 9; nylon 1 1 ; nylon 1 2; nylon 6,6; nylon 5,1 0; nylon 6,1 2; nylon 6,1 1 ; nylon 10,12; and combinations thereof. In addition to the polyesters described previously, the first component can comprise a homogeneous blend of a polyester and a polycarbonate comprising the residues of bisphenol A. [0089] Another aspect of the instant invention is a method for the preparation of a transparent polymer blend, comprising:
(A) selecting a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof;
(B) determining the refractive index of the first component;
(C) providing a second component comprising
(i) a copolyamide having a mole ratio of aliphatic and aromatic residues, wherein the mole ratio of aliphatic and aromatic residues is selected to produce a second component refractive index that satisfies the following formula:
0.006 ≥ RHsecond component) ~ Rl(first component) ≥ -0.0006 or;
(ii) a homogeneous, transamidized blend of a first and second polyamide, at least one of the polyamides having aromatic residues, wherein the weight percentage of the first and second polyamide is selected to produce a second component refractive index that satisfies the following formula: 0.006 ≥ RKsecond component) ~ Rl(first component) ≥ r 0.0006 wherein Rl is refractive index; and
(D) melt blending the first and second components to produce a blend having a percent transmittance of at least 75%, and a haze of 1 0% or less. Our method includes the various embodiments of the polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, and polyamides as described previously and any combination thereof. Our method comprises selecting the first component which may be a polyester, polycarbonate, polyarylate or homogeneous blend thereof. The refractive index of the first component may be determined using methods well known to persons skilled in the art. The second component, which may comprise as single copolyamide or a transamidized, homogeneous blend of at least two polyamides, is tailored to closely match the refractive index of the first component by selecting the appropriate mixture of aromatic and aliphatic monomers in the case of a copolyamide, or by selecting a mixture of polyamides containing the desired mixture of aromatic and aliphatic residues if a homogeneous blend of polyamides is used. The choice of the proper ratio of monomers or of polyamides can be determined, for example, by trial and error, or, in another example, by plotting the refractive index of various polyamides or copolyamides containing varying amounts of aromatic residues and aliphatic residues, and selecting the molar ratio of aromaticaliphatic residues or the weight percentage ratio of polyamides that will give the targeted refractive index. The first and second components may be melt blended. When the second component comprises a transamidized, homogeneous blend of at least 2 polyamides, it is desirable to carry out the melt blending step at a temperature effective for the transmidation process. Typical transamidation temperature ranges are as described previously. [0090] The thermoplastic polymers also may be selected to match the refractive index of the second component. Thus, another aspect of the invention is a method for the preparation of a transparent polymer blend, comprising: (A) selecting a second component comprising
(i) a copolyamide having a mole ratio of aliphatic and aromatic residues; or
(ii) a homogeneous, transamidized blend of a first and second polyamide, at least one of the polyamides having aromatic residues;
(B) determining the refractive index of the second component;
(C) providing a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof wherein the polyester, polycarbonate, polyarylate, or homogeneous blend thereof is selected to produce a first component refractive index that satisfies the following formula:
0.006 ≥ RKsecond component) - Rl(first component) ≥ -0.0006 wherein Rl is refractive index; and
(D) melt blending the first and second components to produce a blend having a percent transmittance of at least 75%, and a haze of 10% or less. It is further understood that the above method also includes any combination of the various embodiments of the polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides described previously.
[0091] In one example, the blending of thermoplastic polymers to obtain a second component and first component that have a difference in refractive index of about 0.006 to about -0.0006 may be illustrated with particular reference to polycarbonate/polyester blends. For example, the complete miscibility of a polycarbonate of bisphenol A and PCTG permits the tailoring of refractive index (Rl) of the polycarbonate/PCTG blend, by adjusting the polycarbonate/PCTG ratio. By adjusting the polycarbonate ratio, the refractive index of the first component of the present invention may be matched to within about 0.006 to about -0.0006 of that of the second component comprising the polyamide barrier polymers. For example, a polymer may be determined to be a suitable modifying polymer of the homogeneous polyester/polycarbonate blends described hereinabove if a clear blend is formed by: 1 ) blending the modifying polymer with a pre-existing blend containing the polycarbonate and polyester portions, or 2) blending the modifying polymer with the polycarbonate portion prior to the introduction of the polyester portion, or 3) blending the modifying polymer with the polyester portion prior to the introduction of the polycarbonate portion, or 4) mixing the modifying polymer, polycarbonate portion and polyester portion all together prior to blending. [0092] The clear blends of the present invention can still be modified by the incorporation of modifying polymers to produce performance blends, which may not necessarily be clear. For example, polyamides such as nylon 6,6 from DuPont, poly(ether-imides) such as ULTEM poly(ether-imide) from General Electric, polyphenylene oxides such as poly(2,6-dimethylphenylene oxide) or poly(phenylene oxide) /polystyrene blends such as the NORYL resins from General Electric, polyesters, polyphenylene sulfides, polyphenylene sulfide/sulfones, poly(ester-carbonates) such as LEXAN 3250 poly(ester- carbonate) (General Electric), polycarbonates other than LEXAN polycarbonate from General Electric, polyarylates such as ARDEL Dl OO polyarylate (Amoco), polysulfones, polysulfone ethers, poly(ether-ketones) or aromatic dihydroxy compounds can be used as blend modifiers to modify properties or to reduce flammability. Some of the aromatic dihydroxy compounds used to prepare these polymers are disclosed in U.S. Pat. No. 3,030,335 and U.S. Pat. 3,31 7,466. [0093] The copolyamide or homogeneous blend of polyamides of the composition of the invention can function as a barrier polymer and, as such, improve the barrier properties of the overall composition. The term "barrier polymer", as used herein, means a polymer having one or more of the following properties: (1) a water permeability of 2 gm-mils/100 sq in/24 hr or less, as measured by ASTM Method No. Fl 249 at 380C; (2) an oxygen permeability of 5 cc(STP)-mils/100 sq in/24 hrs-atm or less, as measured by ASTM Method No. D3985 at 230C, or (3) a carbon dioxide permeability of 25 cc(STP)-mils/l 00 sq in/24 hrs atm or less, as measured by ASTM Method No. Dl 434 at 230C. [0094] The barrier properties may be enhanced by incorporating a metal catalyst to produce an oxygen scavenging composition which catalyzes the reaction of oxygen with one or more polyamides in the composition. Our invention, therefore, further provides an oxygen-scavenging composition comprising: (A) an immiscible blend comprising
(i) first component comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
(ii) a second component comprising a transamidized, homogeneous blend of at least two polyamides; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less; and (B) at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic
Table of the Elements.
[0095] In addition to a homogeneous blend of one or polyamides, the oxygen-scavenging compositions of the invention also may include a single copolyamide as described hereinabove for the other embodiments of the invention. Thus, the invention also provides an oxygen-scavenging composition comprising:
(A) an immiscible blend comprising
(i) first component comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof;
(ii) a second component comprising a copolyamide; wherein the second component (ii) and the first component (i) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less; and
(B) at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements.
It should be further understood the oxygen scavenging compositions include any combination of the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, and polyamides described hereinabove. [0096] The oxygen-scavenging compositions of the invention can include one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements as set forth in the 1 984 revision of the Periodic Table by the lnternation Union of Pure and Applied Chemistry . Typical oxidation catalysts include transition metal catalysts which can readily interconvert between at least two oxidation states. Examples of metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof. Any amount of catalyst which is effective in catalyzing oxygen scavenging may be used but, typically, the metal will be used in amounts from about 10 ppm to about 1 ,000 ppm. Other ranges of metal concentration include, about 50 ppm to about 750 ppm, about 10 to about 500 ppm, about 50 ppm to about 500 ppm, and about 50 to about 300 ppm based on the total weight of the oxygen-scavenging composition. The metal typically may be used as the elemental metal itself, as a metal complex containing organic ligands, as an oxide, or as a metal salt. Examples of counterions for metal salts include, but are not limited to, chloride, acetate, acetylacetonate, stearate, palmitate, 2-ethylhexanoate, neodecanoate, octanoate, or naphthenate, and mixtures thereof. The metal salt may also be an ionomer, in which case a polymeric counterion is employed. Such ionomers are well known in the art.
[0097] In one example, the metal catalyst is cobalt or a compound containing cobalt such as, for example, a cobalt salt. The cobalt may be in the +2 or +3 oxidation state. Other examples of metal catalysts are rhodium in the +2 oxidation state and copper in the +2 oxidation state. The metals may be added in salt form, conveniently as carboxylate salts such as, for example, cobalt octanoate, cobalt acetate, or cobalt neodecanoate. The reported amounts are based on the weight of the polymer blends and measured on the metal, not its compound weight as added to the composition. In the case of cobalt as the metal, typical amounts are at least 50 ppm, or at least 60 ppm, or at least 75 ppm, or at least 100 ppm, or at least 125 ppm. The catalyst can be added neat or in a carrier (such as a liquid or wax) to an extruder or other device for making an article, or it can be added in a concentrate with a polyamide polymer, in a concentrate with a polyester polymer, or in a concentrate with the immiscible blend. The carrier may either be reactive or non-reactive with the first and second component and either volatile or non-volatile carrier liquids may be employed. The metal catalyst may be added at a variety of points and by way of a variety of blending protocols during the preparation of the oxygen scavenging composition. A particularly useful approach is to bring the polyamide and transition metal together late in the preparation of the final blend composition, even as late as in the final melt step before forming the article, so that the oxygen scavenging activity of the polyamide is not prematurely initiated. In some instances, such as when cobalt is provided as a transition metal, it may be preferred to add the cobalt during blending of first and second components, instead of, for example, during the preparation of the thermoplastic polymers. [0098] In one embodiment, for example, the first component of the oxygen-scavenging composition can comprise a polyester having any combination of monomer residues as described previously. For example, the polyester can comprise (a) diacid residues comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-piOpanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethy!-1 ,3-cyclobutanediol; and from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons. In another example, the diacid residues can comprise about 60 to 100 mole percent of the residues of terephthalic acid and 0 to about 40 mole percent of the residues of isophthalic acid and the diol residues can comprise about 100 mole percent of the residues of 1 ,4- cyclohexanedimethanol. In another example, the diacid residues can comprise about 100 mole percent, based on the total moles of diacid residues, of the residues of terephthalic acid. Other specific examples of polyesters that may be used as the first component include polyesters comprising: (i) about 80 to about 100 mole percent of the residues of terephthalic acid and about 50 to about 90 mole percent of the residues 1 ,4-cyclohexanedimethanol and about 10 to about 50 mole percent neopentyl glycol; (ii) about 100 mole percent of the residues of terephthalic acid and about 10 to about 40 mole percent of the residues of 1 ,4-cyclohexanedimethanol and 60 to about 90 mole percent of the residues of ethylene glycol; and (iii) about 100 mole percent of the residues of terephthalic acid and about 10 to about 99 mole percent of the residues of 1 ,4- cyclohexanedimethanol, 0 to about 90 mole percent of the residues of ethylene glycol, and about 1 to about 25 mole percent of the residues of diethylene glycol. The polyester may also further comprise about 0.1 to 2 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride as described hereinabove.
[0099] The first component may also comprise a homogeneous blend of at least one polyester and at least one polycarbonate. The polycarbonates that can be used in these homogeneous blends have been described previously. [0100] The transamidized, homogeneous blend or the copolyamide can comprise any polyamide as described previously such as for example, various nylons. It is advantageous, however, that the copolyamide or homogeneous blend of polyamides of the oxygen-scavenging composition comprise the residues of m-xylyienediamine, p-xylylenediamine, or a combination thereof. For example, the second component may comprise a homogeneous blend of a first polyamide comprising the residues of m-xylylenediamine and adipic acid, and a second polyamide comprising nylon 6, nylon 6,6, or blends thereof. As a further example, this homogeneous blend may be combined in an immiscible blend with a first component comprising a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A. It is desirable also for optimum oxygen scavenging properties that the copolyamide or homogeneous blend of polyamides contain 20 mmoles/kg or less of free amino groups. The concentration of free amino groups can be determined using techniques well known to persons having ordinary skill in the art such as, for example, by titration.
[0101] In another example, the oxygen scavenging composition comprises a copolyamide of m-xylylenediamine adipate. The use of a modified m- xylylenediamine adipate, in which some of the adipic acid residues, or some of the m-xylylenediamine residues, or some of both, are replaced with other residues, can give an oxygen-scavenging composition with improved oxygen- scavenging properties when compared with compositions containing only the m-xylylenediamine adipate homopolymer. Other polyamide barrier polymers, as described herein, may also be used as part of the oxygen scavenging composition.
[0102] The compositions of the present invention described hereinabove may be used to fabricate shaped articles such as, for example, sheets, films, tubes, preforms, bottles, or profiles. Such articles may be formed by any means well known to persons skilled in the art such as, for example, by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing. [0103] For example, the compositions of the present invention may be fabricated into shaped articles such as, for example, films, by any technique known in the art. Formation of films can be achieved by melt extrusion, as described, for example, in U.S. Patent No. 4,880,592, or by compression molding as described, for example, in U.S. Patent No. 4,427,614, or by any other suitable method. For example, films may be produced by the well known cast film, blown film and extrusion coating techniques, the latter including extrusion onto a substrate. Such a substrate may also include a tie-layer. Films produced by melt casting or blowing can be thermally bonded or sealed to a substrate using an adhesive. The compositions may be fabricated into monolayer or multilayer films by any technique known in the art. For example, monolayer, or multilayer films may be produced by the well known cast film, blown film and extrusion coating techniques, the latter including extrusion onto a substrate. Representative substrates include films, sheets, and woven and nonwoven fabrics. Monolayer, or multilayer films produced by melt casting or blowing can be thermally bonded or sealed to a substrate using an adhesive. [0104] For example, the composition may be formed into a film using a conventional blown film apparatus. The film forming apparatus may be one which is referred to in the art as a "blown film" apparatus and includes a circular die head for bubble blown film through which the composition is forced and formed into a film "bubble". The "bubble" is ultimately collapsed and formed into a film.
[0105] The compositions also may be used to form shaped articles through extrusion blow molding and injection stretch-blow molding. An injection molding process softens the copolyamide or homogeneous polyamide blend in a heated cylinder, injecting it while molten under high pressure into a closed mold, cooling the mold to induce solidification, and ejecting the molded preform from the mold. Molding compositions are well suited for the production of preforms and subsequent reheat stretch-blow molding of these preforms into the final bottle shapes having the desired properties. The injection molded preform is heated to suitable orientation temperature in the 1000C to 15O0C range and then stretch-blow molded. The latter process consists of first stretching the hot preform in the axial direction by mechanical means such as by pushing with a core rod insert followed by blowing high pressure air (up to 500 psi) to stretch in the hoop direction. In this manner, a biaxially oriented blown bottle is made. Typical blow-up ratios range from 5/1 to 15/1. [0106] The excellent transparency and low haze of the compositions of the invention enable the preparation of transparent, shaped articles with the incorporation of substantial amounts of scrap polymer or "regrind". The term "regrind", as used herein, is understood to have its commonly accepted meaning in art, that is, scrap polymer that recovered from an article forming process and ground into smaller particles. Often, regrind is sold as scrap for incorporation into shaped articles in which the transparency of the article is immaterial to its application. For certain shaped articles such as, for example, bottles and films used in packaging applications, low haze and high transparency are important features. The manufacture of these articles, in particular, multilayered articles, inherently produces large quantities of scrap polymer which frequently cannot -be returned to the article-forming process because of the formation of unacceptable levels of haze. Because of the close match in the refractive indices of the first and second components, low haze, transparent, shaped articles may be produced from the compositions of the invention with the inclusion of regrind.
[0107] Another aspect of our invention, therefore, is a process for forming a shaped article, comprising: (A) melt blending
(i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein the first component (i) and second component (ii) form an immiscible blend, the second component and the first component have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
(B) forming a shaped article;
(C) recovering a scrap polymer composition comprising the blended first and second components (i) and (ii) ;
(D) grinding the scrap polymer composition to produce a polymer regrind;
(E) optionally, drying the scrap polymer composition;and
(F) combining the polymer regrind with the first and second components (i) and (ii) of step (A).
Our process, thus, permits the incorporation of scrap polymer regrind into the shaped article with retention of low haze and high transparency. It should be further understood the above process includes the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, and any combination thereof described hereinabove. [01 08] For example, as described previously, the immiscible blend formed from the first and second components may further comprise at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements. Examples of metals include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 1 0 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article. The preferred metal is cobalt.
[01 09] The shaped article of our inventive process may be formed by any methods known in the art and described hereinabove. For example, the shaped article may be formed by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing.
[01 10] Although the process of the invention may be used to prepare any shaped article, representative articles that may be produced are sheets, films, preforms, tubes, and bottles. These article may have a single layer or contain from 2 to about 7 layers. The regrind may be incorporated into one or more of these layers which may comprise from about 50 to 100 weight percent regrind based on the weight of the one or more layers. Other examples of regrind levels that can be present in the shaped article are 5 to about 95 weight percent, about 10 to about 60 weight percent, about 1 5 to about 50 weight, and about 20 to about 30 weight percent.
[01 1 1] The shaped article may comprise multiple layers in which one or more of the layers comprise the first and second component as an immiscible blend or in which the first component and the second component are present in separate layers. Thus, another aspect of the instant invention, is a multilayered, shaped article, comprising: (i) a first layer comprising at least one thermoplastic polymer selected from polyester, polycarbonate, polyarylate, and homogeneous blends thereof; and (ii) a second layer comprising a transamidized homogeneous blend of at least two polyamides; wherein the second layer (ii) and the first layer (i) have a difference in refractive index, Rl(second layer) - RKfirst layer), of about 0.006 to about
-0.0006, and the shaped article has a percent transmittance of at least
75%, and a haze of 10% or less. The shaped article may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, and any combination thereof described hereinabove. [01 12] The multilayered shaped article may be produced by extrusion, calendering, thermoforming, blow-molding, extrusion blow-molding, injection molding, compression molding, casting, drafting, tentering, or blowing. Because of the close match between the refractive indices of the first and second layers, the multilayered article may further comprise a regrind comprising a mixture of the first and second layers, which may be incorporated into first layer, second layer, or a combination of the first and second layer. Typically, the regrind is about 5 weight percent to about 60 weight percent of the multilayered article, based on the total weight of the article. Other examples of weight percentages of regrind in the shaped article are about 10 weight percent to about 40 weight percent and about 20 weight percent to about 30 weight percent of the total weight of the article.
[01 13] The multilayered article can have from 2 to about 7 layers depending on its intended application. For example, as described above, the shaped article may be a sheet, film, tube, bottle, or preform. Complex layered structures are possible also. For example, the shaped article can have a layered structure represented by ABA, ABABA, ABCBA, or ACBCA in which layer A comprises the first layer (i), layer B comprises the second layer (ii), and layer C comprises a regrind comprising a mixture of scrap first and second layers (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof. Depending on the composition of the regrind, it can be advantageous that layer B and layer C have a difference in refractive index, RKlayer B) - R(layer C), of about 0.006 to about -0.0006 to maintain the transparency of the article and the ability to incorporate regrind. [01 14] In another embodiment, layer A can comprise the second layer (ii), layer B comprises the first layer (i) and layer C comprises a a mixture of scrap first and second layers (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
[0115] In addition, the second layer (ii) of our novel multilayered article can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements. Examples of metals include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article. The preferred metal is cobalt.
[0116] In yet another embodiment, the multilayered, shaped article of the invention can further comprise at least one additional layer comprising about 50 to about 100 weight percent of regrind, based on the total weight of the layer. The additional layer containing the regrind can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements. Examples of metals include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 10 to about 500 parts per million by weight of said metal, based on the total weight of said shaped article. The preferred metal is cobalt. [0117] As noted above, the multilayered, shaped article may comprise the various embodiments of the shaped articles, thermoplastic polymers, polyamides, immiscible blends, homogeneous blends, and oxygen scavenging compositions as described earlier. For example, the at least one thermoplastic polymer may comprise a linear or branched polyester comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l ,3-cydobutanediol; and from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons; and the one or more barrier polymers comprise a homogeneous blend of a first polyamide comprising the residues of m-xylylenediamine and adipic acid, and a second polyamide comprising nylon 6, nylon 6,6, or blends thereof. For example, the thermoplastic polymer may comprise a branched polyester. In a further example, the thermoplastic polymer further comprise a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A.
[0118] The multilayered, shaped articles of the present invention may be prepared by any method known to persons of ordinary skill in the art. For example, the shaped articles can be formed by any conventional technique for forming films, including lamination, extrusion lamination, coinjection, stretch- blow molding and coextrusion blowmolding, and may be illustrated with particular reference to a typical method for making multilayer film by coextrusion. For example, the first and second components, as well as any optional layers, are fed into infeed hoppers of the extruders of like number, each extruder handling the material for one or more of the layers. Typically, for compositions of the present invention, the first and second components each will be heated to a temperature of about Tg + 1000C to about Tg + 3000C before and during extrusion, wherein Tg is the glass transition temperature of the first or second component as measured by differential scanning calorimetry. The melted streams from the individual extruders are fed into a single manifold co-extrusion die. While in the die, the layers are juxtaposed and combined, then emerge from the die as a single multiple layer film of polymeric material. After exiting the die, the film is cast onto a first controlled temperature casting roll, passes around the first roll, and then onto a second controlled temperature roll, which is normally cooler than the first roll. The controlled temperature rolls largely control the rate of cooling of the film after it exits the die. In another method, the film forming apparatus may be one which is referred to in the art as a blown film apparatus and includes a multi-manifold circular die head for bubble blown film through which the film composition is forced and formed into a film bubble which may ultimately be collapsed and formed into a film. Processes of coextrusion to form film and sheet laminates are generally known. Alternatively the individual layers may first be formed into sheets and then laminated together under heat and pressure with or without intermediate adhesive layers.
[01 19] The transparency and low haze of the compositions of the invention also enable the preparation of multilayered, transparent, shaped articles with the incorporation of substantial amounts of scrap polymer or "regrind". Our invention, therefore, also provides a process for forming a multilayered, shaped article, comprising: (i) heating a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof to a temperature of about Tg +1000C to about Tg + 3000C of the first component; (ii) heating a second component comprising a copolyamide or a transamidized, homogeneous blend of at least two polyamides to a temperature of about Tg +1000C to about Tg + 3000C of the second component; (iii) forming a shaped article having the first and second components in separate layers;
(iv) recovering scrap first and second components; (v) grinding the scrap first and second components to produce a regrind; (vi) optionally, drying the regrind; and (vii) combining the regrind with the first component, second component, or a combination thereof, of steps (i) and (ii); wherein the second component of step (ii) and the first component of step (i) of have a difference in refractive index, RKsecond component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 10% or less. The process may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, article-forming processes, and any combination thereof described hereinabove. [0120] Our process enables the incorporation of substantial amounts of regrind into shaped article while maintaining low haze and high transparency. The regrind will typically comprise a mixture of the first and second components of steps (i) and (ii) that are produced as scrap during the article-forming process, but any polymer material can be used as long as its refractive index differs from the that second component by about 0.006 to about -0.0006. The regrind material of the process can be combined with the first component of step (i), the second component of step (ii) or a combination of the first and second components. The regrind can be from about 5 weight percent to about 60 weight percent of the shaped article, based on the total weight of the shaped article. Other representative examples of regrind content for the shaped artice of the process of the invention are about 10 weight percent to about 40 weight percent of the shaped article and about 20 weight percent to about 30 weight percent of the shaped article.
[0121] The multilayered article of our process can have from 2 to about 7 layers depending on its intended application. For example, as described above, the multilayered, shaped article may be a sheet, film, tube, bottle, or preform. Complex layered structures are possible also. For example, the shaped article can have a layered structure represented by ABA, ABABA, ABCBA, or ACBCA in which layer A comprises the first component of step (i), layer B comprises the second component of step (ii), and layer C comprises a regrind comprising a mixture of scrap first and second components from steps (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof. Depending on the composition of the regrind, it can be advantageous that layer B and layer C have a difference in refractive index, Rl(layer B) - R(layer C), of about 0.006 to about -0.0006 to maintain the transparency of the article and the ability to incorporate regrind.
[0122] In another embodiment, layer A can comprise the second component of step (ii), layer B comprises the first component of step (i) and layer C comprises a a mixture of scrap first and second components of steps (i) and (ii), polyester or polycarbonate obtained from post consumer recycle, or a combination thereof.
[0123] In addition, the second component of step (ii) of our novel multilayered article can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements. Examples of metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article. The preferred metal is cobalt.
[0124] In yet another embodiment, step (iii) of the process of the invention can further comprise forming at least one additional layer comprising about 50 to about 1 00 weight percent of regrind, based on the total weight of the layer. The additional layer containing the regrind can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements. Examples of metals include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 10 to about 500 parts per million by weight of said metal, based on the total weight of said shaped article. The preferred metal is cobalt. [0125] As noted above, the multilayered, shaped article may comprise the various embodiments of the shaped articles, thermoplastic polymers, polyamides, immiscible blends, homogeneous blends, and oxygen scavenging compositions as described earlier. For example, the at least one thermoplastic polymer may comprise a polyester comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l ,3-cyclobutanediol; and from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons; and the one or more barrier polymers comprise a homogeneous blend of a first polyamide comprising the residues of m-xylylenediamine and adipic acid, and a second polyamide comprising nylon 6, nylon 6,6, or blends thereof. For example, the thermoplastic polymer may comprise a branched polyester. In a further example, the thermoplastic polymer further comprise a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A.
[0126] Another embodiment of our invention further is a process for forming a multilayered shaped article, comprising: (A) heating a first component comprising (i) at least one polyester comprising: (a) diacid residues comprising at least about 95 mole percent, based on the total diacid residues, of the residues of terephthalic acid; and (b) diol residues comprising at least 95 mole percent, based on the total moles of dio! residues, of the residues of at least one diol selected from ethylene glycol and 1 ,4-cyclohexanedimethanol; (ii) at least one polycarbonate comprising the residues of bisphenol A; or (iii) a homogeneous blend thereof to a temperature of about Tg +1 000C to about Tg + 300°C of the polyester or polycarbonate;
(B) heating a second component comprising a transamidized, homogeneous blend of a polyamide comprising diamine and diacid residues, the polyamide comprising about 1 00 mole percent, based on the total diamine residues, of the residues of m-xylylenediame and about T OO mole percent, based on the total diacid residues, of the residues of adipic acid, and at least one polyamide selected from nylon 6 and nylon 6,6 to a temperature of about 29O0C;
(C) forming a shaped article having the first and second polymer compositions in separate layers;
(D) recovering scrap first and second components;
(E) grinding the scrap first and second components to produce a regrind;
(F) optionally, drying the regrind; and
(G) combining the regrind with the first component, second component, or a combination thereof, of steps (A) and (B); wherein the second component of step (B) and the first component of step (B) have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about -0.0006, and the blend has a percent transmittance of at least 75%, and a haze of 1 0% or less. The process may include the various embodiments of the first and second components, polyesters, polycarbonates, polyarylates, homogeneous blends, copolyamides, polyamides, oxygen-scavenging compositions, shaped articles, article-forming processes, and any combination thereof described hereinabove. [0127] As described previously, the regrind may comprise a mixture of the first and second components (i) and (ii) and can be combined with the first component (i), second component (ii), or a combination thereof. The regrind can be from about 5 weight percent to about 60 weight percent of the shaped article, based on the total weight of the shaped article. Other representative examples of regrind content for the shaped artice of the process of the invention are about 1 0 weight percent to about 40 weight percent of the shaped article and about 20 weight percent to about 30 weight percent of the shaped article.
[0128] The polyester of the process can comprises diacid residues comprising at least about 95 mole percent of the residues of terephthalic acid and can have a range of diol compositions. For example, the polyester can comprise diol residues comprising about 1 to about 5 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 99 to about 95 mole percent of the residues of ethylene glycol. Other examples of diol compositions for the polyester of our process include, but are not limited to: (i) diol residues comprising about 29 to about 33 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 71 to about 67 mole percent of the residues of ethylene glycol; (b) diol residues comprising about 45 to about 55 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 55 to about 45 mole percent of the residues of ethylene glycol; (iii) residues comprising about 60 to about 65 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 40 to about 35 mole percent of the residues of ethylene glycol; (iv) diol residues comprising about 79 to about 83 mole percent of the residues of 1 ,4-cyclohexanedimethanol and about 21 to about 17 mole percent of the residues of ethylene glycol; and (v) diol residues comprising about 100 mole percent of the residues of 1 ,4- cyclohexanedimethanol. The polyester may further comprise about 0.1 to 2 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride.
[0129] In a further example, the thermoplastic polymer may further comprise a homogeneous blend of the polyester and a polycarbonate comprising the residues of bisphenol A. Each of the polyester and polycarbonate may be linear or branched.
[0130] In addition, the second component of step (ii) of our novel process can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements. Examples of metals which can be used include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 10 to about 500 parts per million by weight of the metal, based on the total weight of the shaped article. The preferred metal is cobalt.
[0131 ] In yet another embodiment, step (C) of the process of the invention can further comprise forming at least one additional layer comprising about 50 to about 1 00 weight percent regrind, based on the total weight of the layer. The additional layer containing the regrind can further comprise at least one metal selected from Groups 3-12, Rows 4-6 of the Periodic Table of the Elements. Examples of metals include copper, nickel, cobalt, iron, manganese, and combinations thereof. Typically, the metal is present in amounts of about 10 to about 500 parts per million by weight of said metal, based on the total weight of said shaped article. The preferred metal is cobalt.
[0132] The shaped articles of the invention may be further oriented by stretching which may improve the barrier properties of the article. As described earliner, it may be desirable to incorporate other conventional additives or modifying polymers with the polymeric compositions of the present invention. For example, there may be added antioxidants, heat and light stabilizers, dyes, antistatic agents, lubricants, preservatives, processing aids, slip agents, antiblocking agents, pigments, flame retardants, blowing agents, and the like. More than one additive may be used. The additive may be present in any desired amount, but typically are not present at more than about 20 weight percent, preferably not more than 10 weight percent, of the total weight of the shaped article.
[0133] The polymer compositions, oxygen-scavenging compositions, and shaped articles prepared therefrom also may comprise up to about 30 weight percent, preferably less than about 20 weight percent, of certain platelet particles derived from at least one layered silicate material to improve their barrier properties. The platelet particles can be modified with at least one ammonium compound. The amount of platelet particles may be determined by . measuring the residual ash of the polymer-platelet particle compositions when treated in accordance with ASTM D5630-94. The gas barrier improvement typically increases with increasing concentration of platelet particles in the composite. While amounts of platelet particles as low as about 0.01 percent provide improved barrier (especially when well dispersed and ordered), compositions having at least about 0.5 weight percent of the platelet particles are preferred because they display desirable improvements in gas permeability. [0134] Generally layered silicate materials are a dense agglomeration of platelet particles which are closely stacked together like cards. The platelet particles of the present invention have a thickness of less than about 2 nm and a diameter in the range of about 10 to about 5000 nm. For the purposes of this invention, measurements refer only to the platelet particle and not to the ammonium compounds or any additional dispersing aids and treatment compounds which might be used. Suitable platelet particles are derived from layered silicate materials that are typically free flowing powders having a cation exchange capacity between about 0.3 and about 3 meq/g and preferably between about 0.8 and about 1.5 meq/g. Examples of suitable layered silicate materials include mica-type layered phyllosilicates, including clays, smectite clays, sodium montmorillonite, sodium hectorite, bentonites, nontronite, beidelite, volonsloite, saponite, sauconite, magadite, kenyaite, synthetic sodium hectorites, and the like. Clays of this nature are available from various companies including Southern Clay Products and Nanocor, Inc. The most preferred platelet particles are derived for sodium bentonite or sodium montmorillonite. Such clays are readily available in the U.S., known as Wyoming type montmorillonite, and other parts of the world, including the Kunipia clays available from Kunimine Industries, Inc.
[0135] The layered silicate materials are typically treated to improve dispersion into the polymer composition. Many useful clay treatments are known in the art, and these treatments may also be used before, after, or during incorporation of the layered silicate materials into the composites of this invention without deviating from the scope of this invention. Examples of useful treatments include, but are not limited to treatments with silane compounds, expanding agents, polymers and oligomers, dispersing aids, organic cation salts, and their combinations.
[01 36] Examples of useful treatment with silane compounds include those treatments disclosed in International Publication No. WO 93/1 1 1 90. Examples of useful silane compounds includes (3-glycidoxypropyl)trimethoxysilane, 2- methoxy (polyethyleneoxy)propyl heptamethyl trisiloxane, octadecyl dimethyl (3-trimethoxysilylpropyl) ammonium chloride and the like. [01 37] Examples of useful treatment with expanding agents include oligomeric polymers well known in the art. Representative polymers and oligomers for treating clays include those disclosed in U.S. Patent No.'s 5,552,469 and 5,578,672. Many dispersing aids are known, covering a wide range of materials including water, alcohols, ketones, aldehydes, chlorinated solvents, hydrocarbon solvents, aromatic solvents, and the like or combinations thereof.
EXAMPLES
[01 38] General: The invention is further illustrated by the following examples. The glass transition temperatures (Tg's) of the polyesters, polyamides, and blends were determined by ASTM Method D341 8 using a TA Instruments 2920 differential scanning calorimeter (DSC) at a scan rate of 20°C/min. Heat Deflection Temperature was determined by ASTM Method D648, and Notched Izod Impact Strength was performed according to ASTM Method D256. Flexural properties were determined according to ASTM Method D790. The tensile properties of the blends were determined according to ASTM Method D638 at 23°C. The inherent viscosity of the polyesters was determined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100 mL at 250C. The diol content of the polyester portion of these blends was determined by proton nuclear magnetic resonance spectroscopy (1H NMR). The miscibility of the blends was determined by differential scanning calorimetry of pressed films and molded objects.
[0139] Haze values were determined by ASTM Method Dl 003 ( %Haze = 100 * Diffuse Transmission / Total Transmission) using a HunterLab UltraScan Sphere 8000 Colorimeter manufactured by Hunter Associates Laboratory, Inc., Reston, VA., using Hunter's Universal Software (version 3.8). Calibration and operation of the instrument was carried out according to the HunterLab User Manual. Diffuse transmission (% transmission) was obtained by placing a light trap on the other side of the integrating sphere from the sample port, thus eliminating the straight-thru light path. Only light scattered by greater than 2.5 degrees was measured. Total transmission includes measurement of light passing straight-through the sample and also off-axis light scattered to the sensor by the sample. The sample was placed at the exit port of the sphere so that off-axis light from the full sphere interior is available for scattering. Clarity was determined visually and with haze measurements. For blends and the various compositions of the invention, haze was determined by forming the composition into a sheet, film, or plaque having a thickness of 1 /8 inch or less and measuring the haze according to the above procedure. For shaped articles, including multilayer shaped articles, the haze was determined by cutting out a small (i.e., 1 X 1 cm) section of the article, having a thickness of 1 /8 inch or less, and measuring the haze according the procedure described above. [0140] Refractive index was measured at 633 nm with a Metricon Prism Coupler™ model 2010 refractometer (available from Metricon Inc.) and is reported as the average of the refractive indices measured in 3 orthogonal directions (extrusion or stretch, transverse, and thickness directions). Oriented films were produced on a TM Long film stretcher (named for the producer) which uniaxially or biaxially stretches samples of pressed, blown, or extruded film. The operation of the film stretcher was based upon the movement of two drawbars at right angles to each other upon hydraulically driven rods. There was a fixed draw bar opposed to each moving draw bar. These pairs of opposed moving and fixed draw bars, to which the four edges of the film specimen are attached, form the two axes at right angles to each other along which the specimen is stretched in any stretch ratio up to four or seven times original size, depending on the machine being used. Samples were placed in grips on the machine and heated prior to stretching if desired. The outputs from the device are stress versus elongation data (if desired) at the temperature of the experiment and the stretched film.
[0141] Oxygen permeabilities of films were determined using Ox-Tran Oxygen Permeation instruments manufactured by MOCON, Inc. Minneapolis, MN. Oxygen permeabilities were calculated from the known area of the films in test, thickness of the film, partial pressure differential of oxygen across the film, and the measured steady state transmission rate. In the case of samples which exhibit active oxygen scavenging, the measured flux is not truly at steady state, since the transmission rate can slowly change as the efficiency of the oxygen scavenging reaction changes with time. However, in these instances, the oxygen transmission can often be considered to be at pseudo-steady state during the duration of permeation measurement. In the active oxygen scavenger samples included in the examples which follow, little to no change in scavenger efficiency was evident during the course of the measurements and permeabilities were calculated from the measured pseudo-steady state transmission rates. [0142] Comparative Examples 1-12: The copolyesters listed in Table 1 were prepared from terephthalic acid, ethylene glycol, and 1 ,4-cyclohexane- dimethanol (CHDM). The amount of CHDM in the polyesters is shown in Table 1 . Example F contains 1 00% CHDM (0% ethylene glycol) but 26 mole% of the acid portion is isophthalic acid instead of terephthalic acid
Table 1
Figure imgf000086_0001
[0143] The copolyesters and MXD6 6121 polyamide (containing 1 00 mole% m-xylylene and 100 mole% adipic acid, available from Mitsubishi Corporation) were dried overnight at 700C. Each of these copolyesters were bag blended with a MXD6 at 1 , 3, and 5 wt% and fed to a Sterling 1 .5 inch single screw extruder at 90 rpm under the following temperature settings (degrees C) to form a blend:
Figure imgf000087_0001
[0144] The blends were dried overnight at 700C and then injection molded into 1 /8 inch thick 4 square plaques at 270°C on a Toyo 90 injection molding machine. The refractive index of the MXD6 was measured to be 1 .5824. The resulting haze values and the result of the subtraction of the refractive index of the polyester from the refractive index of the nylon are shown in Table 2:
Table 2
Figure imgf000087_0002
[0145] Examples 13-24, 27-29, 37 -32, 34-36, 38 and Comparative Examples 25-26, 30, 33, 36-37, and 39 : Nylon 6 (availabe as Zytel® 7335F from DuPont) and MXD6 (grade 61 21 ) were dried at 1 2O0C for 48 hours and bag blended in various ratios. Polyamide bag blends were then fed to a Sterling 1 .5 inch single screw extruder at 90 rpm under the following conditions (0C) to form a homogeneous, transamidized blends as indicated by the presence of a single, composition dependent Tg value for each blend. The Tg values are shown in Table 3.
Figure imgf000088_0001
[0146] Portions of the transamidized nylon blends or MXD6 were dried overnight at 1 20°C and then either injection molded into 1 /8 inch thick samples at 240°C on a Toyo 90 injection molding machine or extruded into 1 5 mil thick film at 2400C. The films were prepared by the following extrusion process: The extruder used was a conventional 2.54 cm diameter Killian extruder, 24:1 LD (length:diameter) ratio, fitted with a feed screw with 3:1 compression ratio and twisted maddock mixing section. The conventional feedblock was used to convey the melt to a conventional 1 5.24 cm coathanger die. A 2— roll cast film downstack configuration was used for quenching the melt. These films were then stretched on the TM-Long 4x in each direction at 95 0C. The properties of these films before stretching are shown in Table 3 and after stretching are shown in Table 3A. It should be noted that oxygen permeabilities in Tables 3A were measured at 30°C and 50% relative humidity with 100% O2 as the test gas. Table 3 - Film Properties Before Stretching
Figure imgf000088_0002
Figure imgf000089_0001
Table 3 A - Film Properties After Stretching
Figure imgf000089_0002
[0147] To generate examples and comparative examples shown in Table 4, portions of the transamidized blends or MXD6 were dried overnight between 70 and 120°C and then compounded with the polyesters of Table 1 . The polyesters were dried overnight between 70 and 1 20°C. Each of these polyesters of Table 1 were bag blended with 1 0 wt% of selected transamidized blends of Table 3 or MXD6 and fed to a Sterling 1 .5 inch single screw extruder at 90 rpm under the following temperature settings (0C) to form an immiscible blend:
Figure imgf000090_0001
The blends were dried overnight at 70°C and then injection molded into 1 /8 inch thick 4 square plaques at 2700C on a Toyo 90 injection molding machine. The resulting haze values and the result of the subtraction of the refractive index of the polyester from the refractive index of the nylon are shown in Table 4. [0148] To generate example 38 and comparative example C-39, the transamidized blend from example 20 of Table 3 was dried overnight at 70°C and then bag blended with either polyester A or C of Table 1 . The polyesters were also dried overnight between 70 and 1200C. The bag blends were then injection molded into 1 /8 inch thick 4 square plaques at 27O0C on a Toyo 90 injection molding machine. The resulting haze values and the results of the subtraction of the refractive index of the polyester from the refractive index of MXD6 or the nylon blends are shown in Table 4.
Table 4 - Polyester blends with homogeneous MXD6/Nylon 6 blends
Figure imgf000090_0002
Figure imgf000091_0001
[0149] Example 40: In this prophetic example, a synthetic route to a polyamide with the appropriate refractive index is employed instead of blending two polyamides as in the above Examples 1 3-24. Any method known in the art can be used to produce these directly synthetic polyamides. The polyamides are generally prepared by melt phase polymerization from a diacid-diamine complex which may be prepared either in situ or in a separate step. In either method, the diacid and diamine are used as starting materials. Alternatively, an ester form of the diacid may be used, preferably the dimethyl ester. If the ester is used, the reaction must be carried out at a relatively low temperature, generally 80 to 12O0C, until the ester is converted to an amide. The mixture is then heated to the polymerization temperature. For this prophetic example, the polyamide synthesized is poly(m-xylylene pimelamide) which is synthesized from the diamine m-xylylenediamine and the diacid pimelic acid. This polyamide is then blended with 90 wt% of the copolyester A in Table 1 , in accordance with methods disclosed in Examples 25-39. The difference in refractive index between these the copolyester A and poly(m-xylylene pimelamide) is predicted to be 0.0034 and is predicted to be transparent. The resulting blend is predicted to have a haze value of less 10% and a transmittance of greater than 75%. [0150] Examples 42-43 and 47-49 and Comparative Examples 41, 44-46, and 50-53. Monolayer Films of blends and Oxygen-Scavenging Compositions: Several MXD6/N6 transamidized blends were prepared in the manner discussed above for examples 1 3-24 and are given in Table 5. The refractive index values listed in Table 5 were measured on 1 5mil films of these transamidized blends in the manner discussed above for examples 13-24. Three wt% or 5 wt% of either these transamidized MXD6/N6 preblends or MXD6 were bag blended with several of the copolyesters from Table 1 as per Table 6. These pellet blends were then dried overnight at 600C - 70°C and then fed to a Killian 1.0 inch single screw extruder at 95 rpm at the temperatures indicated in table 7 to form nominally 30 mil thick films from the immiscible blend. All films containing pure MXD6 had haze values greater than 10%. The films where the refractive index of nylon blend was matched to the refractive index of corresponding polyester within a range of 0.006 to -0.0006 were clear (haze ≤ 10%).
Table 5 - Homogeneous MXD6 - Nylon 6 Blends
Figure imgf000092_0001
[0151] To produce oxygen-scavenging compositions, a concentrate containing cobalt neodecanoate was added to two of the films. This concentrate was prepared as follows. Separate feeds of polyester type C and cobalt neodecanoate, in the form of a pastille and supplied as Cobalt Ten-Cem™ 22.5% (available from OMG Corp.) were fed into a 57mm twin-screw extruder and melt blended at barrel set points of approximately 2350C. Molten polymer exited the extruder in the form of approximate 0.08" diameter strands which were water quenched and cut into approximate 0.125" length pellets. The ratio (by weight) of polyester to polyamide to concentrate was 93:5 to 5 to 1 .5 and the concentration of cobalt metal in the concentrate was such that this ratio resulted in about 140 to 150 ppm cobalt in the final blended film. The samples which contained cobalt exhibited excellent oxygen scavenging capacity. These samples, which were mounted on the Ox-T ran permeation instrument 1 week after extrusion, had average apparent permeabilities under these conditions of less than 0.1 5 cc(STP)*mil/100 in2/day/atm for over 6 months. Table 6 - 30 mil Monolayer Film Results
Figure imgf000093_0001
* apparent permeabilities (average of 2 films per composition and 3 permeability measures per film) fifteen days after mounting on the instrument measured at 23°C and about 60 to 80% relative humidity using air as the upstream test gas. [01 52] Example 56 and Comparative Examples 54-55 - Regrind of Multilayer Films: Multilayer films were prepared by co-extruding two 1 5 mil layers of polyester C around a 4 mil thick layer of either MXD6 or transamidized MXD6/30wt% N6 blend "X". This is referred to as an "ABA" structure where the "A" layers are the outer layers and the "B" layer is the interior layer. A Killian 1 extruder was used to extrude the outer layers from polyester C at a temperature of 265 0C. A 0.75 Killian extruder was used to extrude the inner layers at a temperature of 2850C for the MXD6 and 2750C for the transamidized MXD6/30wt% Nylon 6 blend "X". In order to simulate the reuse of these multilayer films as regrind in a monolayer structure, these multilayer films were then ground up and dry blended with additional polyester C pellets at a 50/50 ratio. This dry blend was then dried at 7OC and extruded on a Killian 1 " extruder at a temperature of 2400C into 20 mil films. Haze values are shown in table 7. The coextruded films all have haze values less then 2%. However, when these films are reground and blended with neat polyester "C", the film containing the C/MXD6 regrind blend the values increase above 1 0%. The film containing the "C/X" regrind remains clear.
Table 7
20 mil Monolayer films in mARA o«QV*r..ri«,ri produced from a mixture p FϊMmis fS (4 m mnil l B^ lavyperrf) 5 o 0 f % 50 g % rQ "m c"d P c e o ll e e χ t t s ru w d«e h d film xamp e Totø) ^^ Ri(nylon) -
Materials /0/ . Transmittance Haze (%) Transmittance Rl(polyester)
( Zo)
C-54 C 0.12 91.5 0.09 91.5 n/a
C-55 C/MXD6/C 1.49 91.1 16.44 87.3 0.0231
56 C/X/C 0.62 91.2 0.37 91.5 0.0022 [01 53] Example and Comparative Examples 57 and 58. Adhesion of multilayer films: ABA films were prepared by co-extruding two 1 5 mil layers of polyester C around a 4 mil thick layer of either MXD6 or transamidized MXD6/30wt% N6 blend "X". The Nylon 6 used in the transamidized blend in this example was Zytel 7301 . A Killian 1 extruder was used to extrude the outer polyester C layers at a temperature of 2650C. A 0.75 Killian extruder was used to extrude the inner layers at the temperatures indicated in Table 8. The transamidized MXD6/3Owt% N6 blend "X" shows superior adhesion over MXD6 to polyester C. Furthermore, improved adhesion of the transamidized MXD6/30wt% N6 blend to polyester C was obtained when the inner layer melt, temperature was increased from 28O0C tO 285°C. MXD6 adhesion did not show any temperature dependency.
Table 8
Example Materials "B" layer Average Peel melt Strength temperature g/mm
C-57 C/MXD6/C 2700C 1.74
2800C 1.7
285°C 1.88
58 C/X/C 270°C 4.33
2800C 4.42
285°C 7.14

Claims

CLAIMS What is claimed:
1 . A process for forming a shaped article, comprising:
(A) melt blending
(i) a first component comprising at least one thermoplastic polymer selected from polyesters, polycarbonates, polyarylates, and homogeneous blends thereof; and (ii) a second component comprising a copolyamide or a homogeneous, transamidized blend of at least 2 polyamides; wherein said first component (i) and second component (ii) form an immiscible blend, said second component and said first component have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.006 to about - 0.0006, and said blend has a percent transmittance of at least 75%, and a haze of 1 0% or less;
(B) forming a shaped article;
(C) recovering a scrap polymer composition comprising said blended first and second components (i) and (ii) ;
(D) grinding said scrap polymer composition to produce a polymer regrind;
(E) optionally, drying said scrap polymer composition;and
(F) combining said polymer regrind with said first and second components (i) and (ii) of step (A).
2. The process of claim 1 where said melt blending is at about 29O0C to about 340°C.
3. The process of claim 2 wherein said blended first and second components (i) and (ii) comprise about 5 to about 99 weight percent of said first component and about 95 to about 1 weight percent of said second component, based on the total weight of said blended components.
4. The process of claim 3 wherein said blended first and second components (i) and (ii) comprise about 50 to about 99 weight percent of said first component and about 50 to about 1 weight percent of said second component.
5. The process of claim 4 wherein said blended first and second components (i) and (ii) comprise about 70 to about 99 weight percent of said first component and about 30 to about 1 weight percent of said second component.
6. The process of claim 1 wherein said second component (ii) and said first component (i) have have a difference in refractive index, Rl(second component) - Rl(first component), of about 0.005 to about -0.0006.
7. The process of claim 1 wherein said at least one thermoplastic polymer comprises a polyester comprising: (a) diacid residues comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4-tetramethyl-l ,3-cyclo- butanediol; and from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons.
8. The process of claim 7 wherein said modifying dicarboxylic acid is selected from 4,4'-biphenyldicarboxylic acid, 1 ,4- naphthalenedicarboxylic acid, 1 ,5- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'- oxybenzoic acid, trans-4,4'-stilbenedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; and said modifying diol is selected from 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,4-cyclohexanedimethanol, p-xylene glycol, neopentyl glycol, polyethylene glycol, diethylene glycol, polytetramethylene glycol, and 2,2,4,4-tetramethyl-l ,3-cyclobutanediol.
9. The process of claim 7 wherein said diacid residues comprise the residues of one or more dicarboxylic acids selected from terephthalic acid, isophthalic acid, or combinations thereof, and said diol residues comprise the residues of one or more diols selected from 1 ,4-cyclohexane- dimethanol, neopentyl glycol, ethylene glycol, and combinations thereof.
10. The process of claim 7 wherein said polyester further comprises about 0.1 to 2 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride.
1 1 . The process of claim 7 wherein said diacid residues comprise about 60 to 100 mole percent of the residues of terephthalic acid and 0 to about 40 mole percent of the residues of isophthalic acid and said diol residue comprises about 100 mole percent of the residues of 1 ,4- cyclohexanedimethanol.
12. The process of claim 7 wherein said diacid residues comprise 100 mole percent of the residues of terephthalic acid.
13. The process of claim 7 wherein said diacid residues comprise 80 to 100 mole percent of the residues of terephthalic acid and said diol residues comprise about 50 to about 90 mole percent of the residues of 1 ,4- cyclohexanedimethanol and about 10 to about 50 mole percent of the residues of neopentyl glycol.
14. The process of claim 7 wherein said diacid residues comprise 100 mole percent of the residues of terephthalic acid and said diol residues comprise about 10 to about 40 mole percent of the residues of
1 ,4-cyclohexanedimethanol and 60 to about 90 mole percent of the residues of ethylene glycol.
15. The process of claim 12 wherein said diol residues comprise about 10 to about 99 mole percent of the residues of 1 ,4-cyclohexanedimethanol, 0 to about 90 mole percent of the residues of ethylene glycol, and about 1 to about 25 mole percent of the residues of diethylene glycol.
16. The process of claim 12 wherein said diol residues comprise about 50 to about 90 mole percent 1 ,4-cyclohexanedimethanol and about 1 0 to about 50 mole percent ethylene glycol.
17. The process of claim 1 wherein said second component comprises a copolyamide comprising the residues of m-xylylenediamine, p- xylylenediamine, or a combination thereof; and the residues of at least one monomer selected from terephthalic acid, isophthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioc acid, dodecanedioc acid, caprolactam, butyrolactam, 1 1 -amino- undecanedioc acid, isophthalic acid, and 1 ,6-hexamethylenediamine.
1 8. The shaped article of claim 1 7 wherein said copolyamide comprises about 1 5 to about 1 00 mole percent of the residues of m-xylylenediamine, based on a total diamine residue content of 1 00 mole%; and about 1 5 to about 85 mole percent of the residues adipic acid and about 85 to about 1 5 mole percent of the residues of one or more aliphatic or cycloaliphatic dicarboxylic acids selected from pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and 1 ,4-cyclohexane- dicarboxylic acid, based on a total diacid residue content of 1 00 mole%.
1 9. The process of claim 1 wherein said second component (ii) comprises a homogeneous blend comprising a first polyamide, comprising aromatic residues, and a second polyamide comprising aliphatic residues.
20. The process of claim 1 9 wherein said homogeneous blend comprises a first polyamide comprising the residues of m-xylylenediamine and adipic acid, and said second polyamide comprises the residues of at least one aliphatic or cycloaliphatic monomer selected from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioc acid, dodecanedioc acid, caprolactam, butyrolactam, 1 1 -aminoundecanedioc acid, isophthalic acid, and hexamethylene diamine.
1 . The process of claim 19 wherein said second polyamide comprises at least one polyamide selected from from nylon 4; nylon 6; nylon 9; nylon 1 1 ; nylon 12; nylon 6,6; nylon 5,10; nylon 6,12; nylon 6,1 1 ; nylon 10,12; and combinations thereof.
22. The process of claim 21 wherein said second polyamide comprises nylon 6, nylon 6,6, or blends thereof.
23. The process of claim 1 wherein said regrind is about 5 weight percent to about 60 weight percent of said composition, based on the total weight of said composition.
24. The process of claim 23 wherein said regrind is about 1 0 weight percent to about 40 weight percent of said composition, based on the total weight of said composition.
25. The process of claim 24 wherein said regrind is about 20 weight percent to about 30 weight percent of said composition, based on the total weight of said composition.
26. The process of claim 22 wherein said at least one thermoplastic polymer comprises a polyester comprising: (a) diacid residues comprising at least 80 mole percent, based on the total diacid residues, of the residues of at least one dicarboxylic acid selected from terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and 1 ,4-cyclohexanedicarboxylic acid, and 0 to about 20 mole percent of the residues of at least one modifying dicarboxylic acid having 2 to 20 carbon atoms; and (b) diol residues comprising at least 80 mole percent, based on the total moles of diol residues, of the residues of at least one diol selected from ethylene glycol, 1 ,4-cyclohexanedimethanol; neopentyl glycol, diethylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, and, 2,2,4,4~tetramethyl-1 ,3-cyclo- butanediol; and from 0 to about 20 mole percent of the residues of at least one modifying diol having from 3 to 16 carbons.
27. The process of claim 26 wherein said diacid residues comprise the residues of one or more dicarboxylic acids selected from terephthalic acid, isophthalic acid, or combinations thereof, and said diol residues comprise the residues of one or more diols selected from 1 ,4- cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and combinations thereof.
28. The process of claim 26 wherein said diacid residues comprise about 60 to 100 mole percent of the residues of terephthalic acid and 0 to about 40 mole percent of the residues of isophthalic acid and said diol residues comprise about 100 mole percent of the residues of 1 ,4- cyclohexanedimethanol.
29. The process of claim 26 wherein said diacid residues comprise 100 mole percent terephthalic acid.
30. The process of claim 26 wherein said diacid residues comprise 80 to 100 mole percent terephthalic acid and said diol residues comprise about 50 to about 90 mole percent 1 ,4-cyclohexanedimethanol and about 10 to about 50 mole percent neopentyl glycol.
31. The process of claim 26 wherein said diacid residues comprise 100 mole percent terephthalic acid and said diol residues comprise about 10 to about 40 mole percent 1 ,4-cyclohexanedimethanol and 60 to about 90 mole percent ethylene glycol.
32. The process of claim 26 wherein said diol residues comprise about 10 to about 99 mole percent of of 1 ,4-cyclohexanedimethanol, 0 to about 90 mole percent of ethylene glycol, and about 1 to about 25 mole percent of diethylene glycol.
33. The process of claim 26 wherein said diol residues comprise about 50 to about 90 mole percent 1 ,4-cyclohexanedimethanol and about 10 to about 50 mole percent ethylene glycol.
34. The process of claim 33 wherein said polyester further comprises about 0.1 to 2 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride.
35. The process of claim 26 wherein said at least one thermoplastic polymer further comprises a homogeneous blend of said polyester and a polycarbonate comprising the residues of bisphenol A.
36. The process of claim 35 wherein said polyester and said polycarbonate are branched.
37. The process of claim 35 wherein said polyester further comprises about 0.1 to 2 mole%, based on the total diacid residues, of the residues of at least one branching agent selected from trimellitic acid, trimellitic anhydride, and pyromellitic dianhydride.
38. The process of claim 35 wherein said diacid residues comprise the residues of one or more dicarboxylic acids selected from terephthalic acid, isophthalic acid, or combinations thereof, and said diol residues comprise the residues of one or more diols selected from 1 ,4- cyclohexanedimethanol, neopentyl glycol, ethylene glycol, and combinations thereof.
39. The process of claim 35 wherein said diacid residues comprise about 60 to 1 00 mole percent of the residues of terephthalic acid and 0 to about 40 mole percent of the residues of isophthalic acid and said diol residue comprises about 1 00 mole percent of the residues of 1 ,4- cyclohexanedimethanol.
40. The process of claim 35 wherein said diacid residues comprise 1 00 mole percent terephthalic acid.
41 . The process of claim 35 wherein said diacid residues comprise 80 to 1 00 mole percent terephthalic acid and said diol residues comprise about 50 to about 90 mole percent 1 ,4-cyclohexanedimethanol and about 1 0 to about 50 mole percent neopentyl glycol.
42. The process of claim 35 wherein said diacid residues comprise 1 00 mole percent terephthalic acid and said diol residues comprise about 1 0 to about 40 mole percent 1 ,4-cyclohexanedimethanol and 60 to about 90 mole percent ethylene glycol.
43. The process of claim 35 wherein said diol residues comprise about 1 0 to about 99 mole percent of of 1 ,4-cyclohexanedimethanol, 0 to about 90 mole percent of ethylene glycol, and about 1 to about 25 mole percent of diethylene glycol.
44. The process of claim 35 wherein said diol residues comprise about 50 to about 90 mole percent 1 ,4-cyclohexanedimethanol and about 1 0 to about 50 mole percent ethylene glycol.
45. The process of claim 20 wherein said immiscible blend further comprises at least one metal selected from Groups 3-1 2, Rows 4-6 of the Periodic Table of the Elements.
46. The process of claim 45 wherein said metal is selected from copper, nickel, cobalt, iron, manganese, and combinations thereof.
47. The process of claim 46 which contains from about 10 to about 500 parts per million by weight of said metal, based on the total weight of said shaped article.
48. The process of claim 47 wherein said metal is cobalt.
49. The process of claim 1 wherein said shaped article is formed by extrusion, calendering, thermoforming, blow-molding, injection molding, compression molding, extrusion blow-molding, casting, drafting, tentering, or blowing.
50. The process of claim 49 wherein said shaped article is a sheet, film, preform, tube, or bottle.
51 . The process of claim 50 wherein said shaped article has from 2 to 7 layers.
52. The process of claim 51 wherein one or more of said 2 to 7 layers comprises 50 to 100 weight percent said regrind, based on the total weight of said layers.
PCT/US2006/007489 2005-03-02 2006-03-02 Process for the preparation of transparent, shaped articles WO2006094148A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AT06736755T ATE527315T1 (en) 2005-03-02 2006-03-02 METHOD FOR PRODUCING TRANSPARENT MOLDED BODY
JP2007558234A JP5243047B2 (en) 2005-03-02 2006-03-02 Manufacturing method for transparent shaped products
CA 2598563 CA2598563C (en) 2005-03-02 2006-03-02 Process for the preparation of transparent shaped articles
EP20060736755 EP1871837B1 (en) 2005-03-02 2006-03-02 Process for the preparation of transparent, shaped articles

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US65774705P 2005-03-02 2005-03-02
US65774605P 2005-03-02 2005-03-02
US60/657,747 2005-03-02
US60/657,746 2005-03-02
US11/363,417 US7955533B2 (en) 2005-03-02 2006-02-27 Process for the preparation of transparent shaped articles
US11/363,417 2006-02-27

Publications (1)

Publication Number Publication Date
WO2006094148A1 true WO2006094148A1 (en) 2006-09-08

Family

ID=36943381

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/007489 WO2006094148A1 (en) 2005-03-02 2006-03-02 Process for the preparation of transparent, shaped articles

Country Status (6)

Country Link
US (2) US7955533B2 (en)
EP (1) EP1871837B1 (en)
JP (2) JP5243047B2 (en)
AT (1) ATE527315T1 (en)
CA (2) CA2598563C (en)
WO (1) WO2006094148A1 (en)

Families Citing this family (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7462684B2 (en) * 2005-03-02 2008-12-09 Eastman Chemical Company Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends
US7955533B2 (en) * 2005-03-02 2011-06-07 Eastman Chemical Company Process for the preparation of transparent shaped articles
US7959998B2 (en) 2005-03-02 2011-06-14 Eastman Chemical Company Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7968164B2 (en) * 2005-03-02 2011-06-28 Eastman Chemical Company Transparent polymer blends and articles prepared therefrom
US7959836B2 (en) 2005-03-02 2011-06-14 Eastman Chemical Company Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
US20060199871A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Multilayered, transparent articles and a process for their preparation
US7786252B2 (en) * 2005-03-02 2010-08-31 Eastman Chemical Company Preparation of transparent multilayered articles
US7842776B2 (en) 2005-06-17 2010-11-30 Eastman Chemical Company Appliance parts comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US7955674B2 (en) 2005-03-02 2011-06-07 Eastman Chemical Company Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7704605B2 (en) 2006-03-28 2010-04-27 Eastman Chemical Company Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein
US20070037960A1 (en) * 2005-08-15 2007-02-15 General Electric Company Copolyester stilbene embossed film and methods of making the same
US8193302B2 (en) 2005-10-28 2012-06-05 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof
ATE505500T1 (en) 2005-10-28 2011-04-15 Eastman Chem Co HIGH GLASS TRANSITION TEMPERATURE POLYESTER COMPOSITIONS CONTAINING CYCLOBUTANEDIOL AND ARTICLES MADE THEREFROM
US20070106054A1 (en) * 2005-10-28 2007-05-10 Crawford Emmett D Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and high glass transition temperature and articles made therefrom
US8586701B2 (en) 2005-10-28 2013-11-19 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
US9598533B2 (en) 2005-11-22 2017-03-21 Eastman Chemical Company Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom
US7737246B2 (en) 2005-12-15 2010-06-15 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor
JP4683289B2 (en) * 2006-01-13 2011-05-18 富士フイルム株式会社 Method for producing thermoplastic resin film
US9169388B2 (en) 2006-03-28 2015-10-27 Eastman Chemical Company Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof
AT505462B1 (en) * 2006-11-13 2010-10-15 Erema PROCESSING FOR PRE-TREATMENT, UPGRADING BZW. RECYCLING OF THERMOPLASTIC PLASTIC MATERIAL
US8501287B2 (en) 2007-11-21 2013-08-06 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
CN101868340B (en) 2007-11-21 2016-04-20 伊士曼化工公司 Plastic baby bottles, other blow molded articles and preparation method thereof
EP2247649B1 (en) * 2008-01-31 2013-04-10 Basf Se Fiber-reinforced polyamide[5,10] molding compositions
US8198371B2 (en) 2008-06-27 2012-06-12 Eastman Chemical Company Blends of polyesters and ABS copolymers
US8895654B2 (en) 2008-12-18 2014-11-25 Eastman Chemical Company Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid
US8420869B2 (en) 2010-12-09 2013-04-16 Eastman Chemical Company Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8420868B2 (en) 2010-12-09 2013-04-16 Eastman Chemical Company Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US8394997B2 (en) 2010-12-09 2013-03-12 Eastman Chemical Company Process for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
US20120184668A1 (en) * 2011-01-17 2012-07-19 Eastman Chemical Company Clear Ternary Blends of Polycarbonate with an Aliphatic Polyester and an Aromatic-Aliphatic Polyester
WO2012165258A1 (en) * 2011-05-27 2012-12-06 旭化成ケミカルズ株式会社 Reinforced polyamide resin pellets
US20130217830A1 (en) 2012-02-16 2013-08-22 Eastman Chemical Company Clear Semi-Crystalline Articles with Improved Heat Resistance
US8691915B2 (en) 2012-04-23 2014-04-08 Sabic Innovative Plastics Ip B.V. Copolymers and polymer blends having improved refractive indices
JP6305182B2 (en) * 2014-04-16 2018-04-04 三笠産業株式会社 Multi-layer container
KR20210005865A (en) * 2018-04-24 2021-01-15 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 Multilayer and Multilayer Container
EP3785907B1 (en) 2018-04-24 2023-06-07 Mitsubishi Gas Chemical Company, Inc. Multilayered article and multilayered container
JP7327386B2 (en) 2018-04-26 2023-08-16 三菱瓦斯化学株式会社 Stretched film, packaging material and method for producing stretched film
CN113498421B (en) * 2018-08-20 2023-08-01 英威达纺织(英国)有限公司 Method for recycling nylon with high relative viscosity
JP7260855B2 (en) * 2019-10-30 2023-04-19 株式会社豊田中央研究所 Method for producing transparent reinforced polyamide resin composition
CN111138605A (en) * 2020-01-13 2020-05-12 淮北师范大学 Low-temperature-resistant chemical-resistant composite material and preparation method thereof
JP2023131810A (en) * 2022-03-10 2023-09-22 三菱瓦斯化学株式会社 Resin composition, molded body and multilayer body

Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999835A (en) 1959-01-02 1961-09-12 Gen Electric Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same
US3028365A (en) 1953-10-16 1962-04-03 Bayer Ag Thermoplastic aromatic polycarbonates and their manufacture
US3030335A (en) 1959-01-02 1962-04-17 Gen Electric Aromatic polycarbonate reaction products
US3153008A (en) 1955-07-05 1964-10-13 Gen Electric Aromatic carbonate resins and preparation thereof
US3317466A (en) 1961-09-14 1967-05-02 Eastman Kodak Co Three-dimensional polycyclic bisphenol polycarbonates and polyesters
US4286083A (en) 1976-12-29 1981-08-25 General Electric Company Method of preparing polyester carbonates
US4321355A (en) 1980-09-23 1982-03-23 Union Carbide Corporation Process for preparing polyarylates
US4374239A (en) 1980-03-03 1983-02-15 Union Carbide Corporation Process for preparing polyarylates
US4427614A (en) 1980-04-30 1984-01-24 Imperial Chemical Industries Plc 3-Hydroxybutyric acid polymers
US4474999A (en) 1982-03-19 1984-10-02 General Electric Company Phenol compounds, process and polymers
US4880592A (en) 1985-12-09 1989-11-14 W. R. Grace & Co.-Conn. Manufacture of polymeric products
EP0404463A2 (en) * 1989-06-20 1990-12-27 The Dow Chemical Company Reflective polymeric body
EP0426636A2 (en) * 1989-10-31 1991-05-08 The Mearl Corporation Iridescent film with thermoplastic elastomeric components
US5034502A (en) 1987-07-22 1991-07-23 Unitika Ltd. Process for producing a polyarylate
WO1993011190A1 (en) 1991-11-26 1993-06-10 Allied-Signal Inc. Polymer nanocomposites formed by melt processing of a polymer and an exfoliated layered material derivatized with reactive organo silanes
US5262511A (en) 1992-03-03 1993-11-16 General Electric Co. Branched aromatic carbonate polymer
US5290631A (en) 1991-10-29 1994-03-01 Rhone-Poulenc Chimie Hydrosoluble/hydrodispersible polyesters and sizing of textile threads therewith
US5489665A (en) 1991-05-08 1996-02-06 Daicel Chemical Industries, Ltd. Process for producing polycarbonate
US5494992A (en) 1993-01-29 1996-02-27 Daicel Chemical Industries, Ltd. (Co)polycarbonate and process for producing the same
US5498688A (en) 1993-04-16 1996-03-12 Daicel Chemical Industries, Ltd. Two-step process for the preparation of a (co)polycarbonate by transesterification
US5552469A (en) 1995-06-07 1996-09-03 Amcol International Corporation Intercalates and exfoliates formed with oligomers and polymers and composite materials containing same
US5578672A (en) 1995-06-07 1996-11-26 Amcol International Corporation Intercalates; exfoliates; process for manufacturing intercalates and exfoliates and composite materials containing same
US6022941A (en) 1998-04-01 2000-02-08 General Electric Company Branched polycarbonate produced by reactive extrusion
US6160082A (en) 1997-11-05 2000-12-12 General Electric Company Process for branching thermoplastic linear polycarbonate resins
US6211309B1 (en) 1998-06-29 2001-04-03 Basf Corporation Water-dispersable materials
EP1239008A1 (en) * 2001-03-05 2002-09-11 Mitsubishi Gas Chemical Company, Inc. Polyester-based resin composition and shaped articles
EP1262524A2 (en) * 2001-05-24 2002-12-04 Mitsubishi Gas Chemical Company, Inc. Polyester based resin composition and molded product therefrom

Family Cites Families (94)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3313777A (en) 1959-12-18 1967-04-11 Eastman Kodak Co Linear polyesters and polyester-amides from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols
US3360547A (en) 1961-05-01 1967-12-26 Eastman Kodak Co Polyesters of tetraalkylcyclobutanediol
FR1456345A (en) 1964-12-07 1966-10-21 Eastman Kodak Co New process for the preparation of polyesters and new products obtained
GB1141981A (en) 1966-01-21 1969-02-05 Dow Chemical Co Iridescent bodies and coating compositions and composite structures comprising them
GB1380918A (en) 1970-12-29 1975-01-15 Toyo Boseki Film manufacture
US4133802A (en) 1974-03-26 1979-01-09 Toyo Boseki Kabushiki Kaisha Meta-xylylene diamine/aliphatic dicarboxylic acid polyamide film
US4430484A (en) 1981-01-14 1984-02-07 General Electric Company Polyester-carbonate resin blends
JPS58183243A (en) 1982-04-22 1983-10-26 株式会社吉野工業所 Biaxial stretched blow molded bottle body made of synthetic resin
US4598130A (en) 1983-02-18 1986-07-01 Union Carbide Corporation Blends of a polyarylate and a poly(ester carbonate)
US4581288A (en) 1983-10-20 1986-04-08 Corning Glass Works Composite photochromic lenses
US5239020A (en) 1985-08-21 1993-08-24 Eastman Kodak Company Polyester/polycarbonate blends
JPS62119256A (en) 1985-11-20 1987-05-30 Toray Ind Inc Thermoplastic resin composition
US4837115A (en) 1986-07-30 1989-06-06 Toyo Seikan Kaisha, Ltd. Thermoplastic polyester composition having improved flavor-retaining property and vessel formed therefrom
JPH0741907B2 (en) 1986-12-27 1995-05-10 三菱瓦斯化学株式会社 Multi-layer container
SE8702840D0 (en) 1987-07-10 1987-07-10 Plm Ab BARRIERFORSTERKNING
AU611181B2 (en) 1987-07-27 1991-06-06 Constar International Inc. Improvements in and relating to packaging
JP2543544B2 (en) 1987-11-30 1996-10-16 三菱瓦斯化学株式会社 Gas barrier multi-layer structure
US4983431A (en) 1989-05-22 1991-01-08 International Paper Company Oxygen impermeable leak free container
US4929476A (en) 1989-05-22 1990-05-29 International Paper Company Oxygen impermeable leak free container
US4981739A (en) 1989-05-22 1991-01-01 International Paper Company Oxygen impermeable leak free container
US4937130A (en) 1989-01-18 1990-06-26 General Electric Company Polycarbonate container having internal layers of amorphous polyamide
US4937134A (en) 1989-04-17 1990-06-26 The Dow Chemical Company Elastomeric optical interference films
GB8914466D0 (en) 1989-06-23 1989-08-09 Orbitel Mobile Communications Apparatus for and method of digitizing fsk demodulated data
US6288161B1 (en) 1990-01-31 2001-09-11 Pechiney Emballage Flexible Europe Barrier compositions and articles made therefrom
AU649710B2 (en) 1990-09-11 1994-06-02 Mitsubishi Gas Chemical Company, Inc. Polyamide resin composition and film therefrom
JPH04197634A (en) 1990-11-28 1992-07-17 Kao Corp Multi-layer plastic vessel and its manufacture
US6495656B1 (en) 1990-11-30 2002-12-17 Eastman Chemical Company Copolyesters and fibrous materials formed therefrom
WO1992022837A1 (en) 1991-06-17 1992-12-23 Seiko Epson Corporation Phase difference elemental film, phase difference plate and liquid crystal display using same
US5258233A (en) 1992-04-02 1993-11-02 Eastman Kodak Company Polyester/polyamide blend having improved flavor retaining property and clarity
US5628957A (en) 1992-07-07 1997-05-13 Continental Pet Technologies, Inc. Method of forming multilayer container with polyethylene naphthalalte (pen)
CA2097655A1 (en) 1992-07-20 1994-01-20 Thomas Maria Klerks Multilayer container of polycarbonate and amorphous polyamide of improved barrier and stress crack resistant
JP3153437B2 (en) * 1995-05-11 2001-04-09 電気化学工業株式会社 Polyester-based multilayer sheet, container, and method for producing the same
US5650469A (en) 1995-10-25 1997-07-22 Eastman Chemical Company Polyester/polyamide blend having improved flavor retaining property and clarity
US6005059A (en) 1996-12-28 1999-12-21 Eastman Chemical Company Clear polycarbonate and polyester blends
US5942585A (en) 1996-12-28 1999-08-24 Eastman Chemical Company Polycarbonate and polyester blends
US6037424A (en) 1996-12-28 2000-03-14 Eastman Chemical Company Clear blends of polycarbonates and polyesters
US6011124A (en) 1996-12-28 2000-01-04 Eastman Chemical Company Blends of bisphenol a polycarbonate and polyesters
US6043322A (en) 1996-12-28 2000-03-28 Eastman Chemical Company Clear polycarbonate and polyester blends
US5989663A (en) 1996-12-30 1999-11-23 Eastman Chemical Company Blow-molding polyesters from terephthalic acid, 2, 2, 4, 4-tetramethyl-1,3-cyclobutanediol, and ethylene glycol
US6044124A (en) * 1997-08-22 2000-03-28 Silicon Systems Design Ltd. Delta sigma PLL with low jitter
JP4495264B2 (en) 1998-04-24 2010-06-30 株式会社クレハ Heat shrinkable multilayer film
IT1301690B1 (en) 1998-06-11 2000-07-07 Sinco Ricerche Spa MIXTURES OF POLYESTER RESINS WITH HIGH PROPERTIES OF AIGAS BARRIER.
US6239233B1 (en) 1998-10-09 2001-05-29 Eastman Chemical Company Polyester/polyamide blends with improved color
AU1836600A (en) 1998-12-07 2000-06-26 Eastman Chemical Company A polymer/clay nanocomposite having improved gas barrier comprising a clay material with a mixture of two or more organic cations and a process for preparing same
WO2000058404A1 (en) 1999-03-31 2000-10-05 Toyo Boseki Kabusiki Kaisya Oxygen-absorbing material and molded object obtained therefrom
CN1505661A (en) 1999-07-30 2004-06-16 伊斯曼化学公司 Polyester-polyamide blends with reduced gas permeability and low haze
DE10009756B4 (en) 2000-03-01 2004-03-25 Ems-Chemie Ag Colorless, highly transparent polyamide blends with improved stress crack resistance
US6423776B1 (en) 2000-05-02 2002-07-23 Honeywell International Inc. Oxygen scavenging high barrier polyamide compositions for packaging applications
US7186464B2 (en) 2000-05-19 2007-03-06 Chevron Phillips Chemical Co. Lp Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers
JP2002069276A (en) 2000-08-30 2002-03-08 Unitika Ltd Gas barrier polyester film and its manufacturing method
JP2002088174A (en) 2000-09-12 2002-03-27 Toyobo Co Ltd Biaxially oriented polyamide film
US20020111428A1 (en) 2000-12-14 2002-08-15 General Electric Company Transparent polycarbonate polyester composition and process
US6933055B2 (en) 2000-11-08 2005-08-23 Valspar Sourcing, Inc. Multilayered package with barrier properties
US6410156B1 (en) 2001-03-06 2002-06-25 Honeywell International Inc. Oxygen scavenging polyamide compositions suitable for pet bottle applications
JP2002348482A (en) * 2001-05-25 2002-12-04 Mitsubishi Rayon Co Ltd Thermoplastic resin composition
JP3741095B2 (en) 2001-10-19 2006-02-01 東洋紡績株式会社 Polyester composition and polyester molded body comprising the same
US7037576B2 (en) 2002-02-06 2006-05-02 Eastman Chemical Company Polyester or copolyester/polyolefin laminate structures and methods of making the same
WO2003102079A1 (en) * 2002-06-03 2003-12-11 Toyo Boseki Kabushiki Kaisha Polyester composition and packaging material comprising the same
US6964816B2 (en) 2002-09-09 2005-11-15 Curwood, Inc. Packaging films containing coextruded polyester and nylon layers
EP1400568B1 (en) * 2002-09-17 2007-11-07 Mitsubishi Gas Chemical Company, Inc. Polyester-based resin composition
US6896966B2 (en) 2002-11-22 2005-05-24 Eastman Chemical Company Articles of manufacture incorporating polyester/polycarbonate blends
JP4164653B2 (en) 2002-11-29 2008-10-15 三菱瓦斯化学株式会社 Method for producing polyamide resin composition and resin molded body
US7022764B2 (en) 2002-12-18 2006-04-04 General Electric Company Static dissipating resin composition and methods for manufacture thereof
DE10302036A1 (en) 2003-01-21 2004-07-29 Mitsubishi Polyester Film Gmbh Biaxially-oriented polyester film for use in food and other packaging has a base layer containing poly(m-xylene-adipamide) and a barrier layer containing a maleic acid/acrylic acid copolymer
JP2004285194A (en) 2003-03-20 2004-10-14 Mitsubishi Gas Chem Co Inc Polyester resin composition and molded form
US7087682B2 (en) 2003-05-02 2006-08-08 General Electric Polymeric blends for optical devices and method of manufacture thereof
CN1550326B (en) 2003-05-06 2010-08-25 三菱瓦斯化学株式会社 Multilayer container
AU2004202264B2 (en) 2003-05-29 2008-12-18 Mitsubishi Gas Chemical Company, Inc. Masterbatch and production method of oxygen-absorbing molded article
JP2005015791A (en) 2003-06-05 2005-01-20 Toyobo Co Ltd Polyester composition and polyester molded product thereof
JP2005008809A (en) * 2003-06-20 2005-01-13 Mitsubishi Gas Chem Co Inc Method for producing recycled polyester resin composition
US20050009976A1 (en) 2003-07-10 2005-01-13 Honeywell International, Inc. Delamination-resistant, barrier polyamide compositions for 3-layer pet beverage bottles
EP1504999A1 (en) 2003-08-05 2005-02-09 Amcor Limited Rigid plastic container having gas-barrier properties and high transparency
US20050159526A1 (en) * 2004-01-15 2005-07-21 Bernard Linda G. Polymamide nanocomposites with oxygen scavenging capability
ATE375860T1 (en) 2004-02-03 2007-11-15 Ems Chemie Ag MATERIAL COMPOSITES FROM A MOLDED PART MADE OF TRANSPARENT OR TRANSLUCENT, COLORABLE PLASTIC MOLDING COMPOUNDS
US8192676B2 (en) * 2004-02-12 2012-06-05 Valspar Sourcing, Inc. Container having barrier properties and method of manufacturing the same
KR100725311B1 (en) 2004-05-07 2007-06-07 주식회사 새 한 Multilayer laminate with excellent heat resistance and gas barrier properties
US20060004151A1 (en) 2004-06-30 2006-01-05 General Electric Company Copolymers containing indan moieties and blends thereof
EP1784300B1 (en) 2004-08-31 2012-05-23 INVISTA Technologies S.à.r.l. Polyester-polyamide blends having low haze
RU2007125260A (en) * 2004-12-06 2009-01-20 Констар Интернэшнл Инк. (Us) MIXTURES OF OXYGEN-BARRIER POLYAMIDES WITH COMPLEX POLYESTERS AND THEIR APPLICATION
US7375154B2 (en) * 2004-12-06 2008-05-20 Eastman Chemical Company Polyester/polyamide blend having improved flavor retaining property and clarity
BRPI0518849A2 (en) * 2004-12-06 2008-12-09 Eastman Chem Co solid concentrate, processes for producing a preform, and for drying particles, and polyester polymer concentrate
US20080009574A1 (en) 2005-01-24 2008-01-10 Wellman, Inc. Polyamide-Polyester Polymer Blends and Methods of Making the Same
US7959998B2 (en) * 2005-03-02 2011-06-14 Eastman Chemical Company Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7964258B2 (en) * 2005-03-02 2011-06-21 Eastman Chemical Company Transparent, oxygen-scavenging compositions and articles prepared therefrom
US7968164B2 (en) * 2005-03-02 2011-06-28 Eastman Chemical Company Transparent polymer blends and articles prepared therefrom
US20060199871A1 (en) * 2005-03-02 2006-09-07 Hale Wesley R Multilayered, transparent articles and a process for their preparation
US7786252B2 (en) * 2005-03-02 2010-08-31 Eastman Chemical Company Preparation of transparent multilayered articles
US7955674B2 (en) * 2005-03-02 2011-06-07 Eastman Chemical Company Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7959836B2 (en) * 2005-03-02 2011-06-14 Eastman Chemical Company Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
US7462684B2 (en) * 2005-03-02 2008-12-09 Eastman Chemical Company Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends
US7955533B2 (en) * 2005-03-02 2011-06-07 Eastman Chemical Company Process for the preparation of transparent shaped articles
US7427430B2 (en) * 2005-12-29 2008-09-23 Honeywell International Inc. Polyamide blend composition having excellent gas barrier performance
JP5010196B2 (en) 2006-07-18 2012-08-29 株式会社神戸製鋼所 Heat-resistant aluminum alloy shape manufacturing method, heat-resistant aluminum alloy shape material and heat-resistant aluminum alloy shape forming apparatus
US20080255280A1 (en) * 2007-04-11 2008-10-16 Susan Sims Oxygen-scavenging polymer blends suitable for use in packaging

Patent Citations (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3028365A (en) 1953-10-16 1962-04-03 Bayer Ag Thermoplastic aromatic polycarbonates and their manufacture
US3153008A (en) 1955-07-05 1964-10-13 Gen Electric Aromatic carbonate resins and preparation thereof
US3030335A (en) 1959-01-02 1962-04-17 Gen Electric Aromatic polycarbonate reaction products
US2999835A (en) 1959-01-02 1961-09-12 Gen Electric Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same
US3317466A (en) 1961-09-14 1967-05-02 Eastman Kodak Co Three-dimensional polycyclic bisphenol polycarbonates and polyesters
US4286083A (en) 1976-12-29 1981-08-25 General Electric Company Method of preparing polyester carbonates
US4374239A (en) 1980-03-03 1983-02-15 Union Carbide Corporation Process for preparing polyarylates
US4427614A (en) 1980-04-30 1984-01-24 Imperial Chemical Industries Plc 3-Hydroxybutyric acid polymers
US4321355A (en) 1980-09-23 1982-03-23 Union Carbide Corporation Process for preparing polyarylates
US4474999A (en) 1982-03-19 1984-10-02 General Electric Company Phenol compounds, process and polymers
US4880592A (en) 1985-12-09 1989-11-14 W. R. Grace & Co.-Conn. Manufacture of polymeric products
US5034502A (en) 1987-07-22 1991-07-23 Unitika Ltd. Process for producing a polyarylate
EP0404463A2 (en) * 1989-06-20 1990-12-27 The Dow Chemical Company Reflective polymeric body
EP0426636A2 (en) * 1989-10-31 1991-05-08 The Mearl Corporation Iridescent film with thermoplastic elastomeric components
US5489665A (en) 1991-05-08 1996-02-06 Daicel Chemical Industries, Ltd. Process for producing polycarbonate
US5290631A (en) 1991-10-29 1994-03-01 Rhone-Poulenc Chimie Hydrosoluble/hydrodispersible polyesters and sizing of textile threads therewith
WO1993011190A1 (en) 1991-11-26 1993-06-10 Allied-Signal Inc. Polymer nanocomposites formed by melt processing of a polymer and an exfoliated layered material derivatized with reactive organo silanes
US5262511A (en) 1992-03-03 1993-11-16 General Electric Co. Branched aromatic carbonate polymer
US5494992A (en) 1993-01-29 1996-02-27 Daicel Chemical Industries, Ltd. (Co)polycarbonate and process for producing the same
US5498688A (en) 1993-04-16 1996-03-12 Daicel Chemical Industries, Ltd. Two-step process for the preparation of a (co)polycarbonate by transesterification
US5552469A (en) 1995-06-07 1996-09-03 Amcol International Corporation Intercalates and exfoliates formed with oligomers and polymers and composite materials containing same
US5578672A (en) 1995-06-07 1996-11-26 Amcol International Corporation Intercalates; exfoliates; process for manufacturing intercalates and exfoliates and composite materials containing same
US6160082A (en) 1997-11-05 2000-12-12 General Electric Company Process for branching thermoplastic linear polycarbonate resins
US6022941A (en) 1998-04-01 2000-02-08 General Electric Company Branched polycarbonate produced by reactive extrusion
US6211309B1 (en) 1998-06-29 2001-04-03 Basf Corporation Water-dispersable materials
EP1239008A1 (en) * 2001-03-05 2002-09-11 Mitsubishi Gas Chemical Company, Inc. Polyester-based resin composition and shaped articles
EP1262524A2 (en) * 2001-05-24 2002-12-04 Mitsubishi Gas Chemical Company, Inc. Polyester based resin composition and molded product therefrom

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Mixing and Compounding of Polymers", 1994, CARL HANSER VERLAG
"Polymer Blends", vol. 1-2, 2000, JOHN WILEY & SONS, INC.
BIANGARDI ET AL., DIE ANGEW. MAKROMOLE. CHEMIE, 1990, pages 183
TAKEDA, POLYMER, vol. 33, 1992, pages 3394

Also Published As

Publication number Publication date
JP2012207235A (en) 2012-10-25
EP1871837A1 (en) 2008-01-02
JP5744802B2 (en) 2015-07-08
US20060197246A1 (en) 2006-09-07
ATE527315T1 (en) 2011-10-15
US20110201703A1 (en) 2011-08-18
US8133417B2 (en) 2012-03-13
CA2601928A1 (en) 2006-09-08
CA2601928C (en) 2010-11-02
JP5243047B2 (en) 2013-07-24
JP2008531827A (en) 2008-08-14
CA2598563A1 (en) 2006-09-08
CA2598563C (en) 2011-05-10
EP1871837B1 (en) 2011-10-05
US7955533B2 (en) 2011-06-07

Similar Documents

Publication Publication Date Title
CA2601928C (en) Transparent, oxygen-scavenging compositions and articles prepared therefrom
US8304499B2 (en) Transparent polymer blends and articles prepared therefrom
CA2601925C (en) Multilayered, transparent articles and a process for their preparation
US7964258B2 (en) Transparent, oxygen-scavenging compositions and articles prepared therefrom
US7959998B2 (en) Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom
US7959836B2 (en) Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol
US7955674B2 (en) Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom
CA2598196C (en) Preparation of transparent multilayered articles
US7462684B2 (en) Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends
WO2007001574A1 (en) Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680006970.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2598563

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2007558234

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2006736755

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: RU