WO1992016582A1 - Glass-reinforced grafted branched higher alpha-olefins - Google Patents

Glass-reinforced grafted branched higher alpha-olefins Download PDF

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Publication number
WO1992016582A1
WO1992016582A1 PCT/US1992/002210 US9202210W WO9216582A1 WO 1992016582 A1 WO1992016582 A1 WO 1992016582A1 US 9202210 W US9202210 W US 9202210W WO 9216582 A1 WO9216582 A1 WO 9216582A1
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WIPO (PCT)
Prior art keywords
polymer
parts
weight
tert
composition
Prior art date
Application number
PCT/US1992/002210
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French (fr)
Inventor
Edwin Boudreaux, Jr.
Mary Jane Hagenson
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Phillips Petroleum Company
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Publication date
Application filed by Phillips Petroleum Company filed Critical Phillips Petroleum Company
Priority to EP92909523A priority Critical patent/EP0530360B1/en
Priority to JP4508825A priority patent/JP2837953B2/en
Priority to CA002081210A priority patent/CA2081210C/en
Priority to DE69228159T priority patent/DE69228159T2/en
Publication of WO1992016582A1 publication Critical patent/WO1992016582A1/en
Priority to KR1019920702785A priority patent/KR100205080B1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/23907—Pile or nap type surface or component
    • Y10T428/23957—Particular shape or structure of pile
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249948—Fiber is precoated
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31859—Next to an aldehyde or ketone condensation product
    • Y10T428/31877—Phenol-aldehyde

Definitions

  • This invention relates to glass-reinforced thermoplastics.
  • Polyolefins tend to have excellent physical and chemical properties. Improvement of polymer properties is a dominant factor in the development and production of olefin polymers. Several methods have been employed to improve various polymer
  • reinforcing agents such as glass fibers
  • glass fibers can be incorporated into the polymer to improve the mechanical properties and/or the heat resistance of the polymer.
  • merely mixing the glass fibers and the polyolefins together can result in weak bonding between the glass fibers and the polyolefin.
  • One solution is to have a more bondable component grafted onto the polymers to facilitate reinforcement with glass fibers and other generally infusible reinforcing agents.
  • Polymers with relatively high melting points such as stereoregular polymers of branched, higher alpha-olefins, have been developed. These polymers are useful in high temperature applications, such as microwave packaging. Improving the
  • a coupling agent that provides better adhesion between the glass fiber strand and the polymeric materials that are reinforced with the glass fiber strand
  • other additives such as emulsifiers, wetting agents, nucleating agents, and the like.
  • Various sizing compositions have been developed for glass fiber reinforcements to provide improved adhesion between various polymeric materials and the glass fiber. Sizing compositions are known for treating glass fibers for improved adhesion between the glass fiber strand and relatively low melting point polyolefins, such as polyethylene and polypropylene. The polyolefin may be modified partially or entirely with an unsaturated carboxylic acid or derivative thereof.
  • the prior art does not teach sizing compositions for treating glass fibers for improved adhesion between glass fibers and stereoregular polymers of branched, higher alpha-olefins or stereoregular polymers of branched, higher alpha-olefins which have been modified with
  • thermoplastic materials from which products with improved properties can be made.
  • a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids;
  • Exemplary monomers include, but are not limited to, 3-methyl-1-butene (3MB1), 3-methyl-1-pentene (3NP1), 4-methyl-1-pentene (4MP1), 4-methyl-1-hexene (4MH1), 3,3-dimethyl-1-butene (3,3DHB1), 4,4-dimethyl-1-hexene (4,4DHH1), 3-ethyl-1-hexene (3EH1) and other similar monomers.
  • polymers of 4NP1, also called polymethylpentene (PMP), and 3MB1, also called polymethylbutene (PMB), are utilized in this invention. Table I gives the approximate melting point of each homopolymer listed above. TABLE I
  • the polymer in general, it is preferred for the polymer to comprise at least about 85 mole percent moieties derived from higher, branched alpha-olefins, and more preferably, at least about 90 mole percent moieties derived from higher, branched alpha-olefins. Most preferably, the polymer comprises at least about 95 mole percent moieties derived from higher, branched alpha-olefins, which results in a polymer of superior strength and a high melting point.
  • the polymer After the polymer has been produced, it is essential, according to this invention, that the polymer be given a prophylactic charge with a
  • the hindered phenol antioxidant used for the prophylactic charge is selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol; tetrakis(methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane;
  • any additive can be combined with the polymer according to any method known in the art.
  • incorporation methods include, but are not limited to, dry mixing in the form of a powder and wet mixing in the form of a solution or slurry.
  • the polymer can be in any form, such as, for example, fluff, powder, granulate, pellet, solution, slurry, and/or emulsion.
  • the initial prophylactic charge of hindered phenol is usually solution or slurry mixed with the polymer prior to drying and handling of the polymer.
  • Any additional stabilizers or additives can be blended with the polymer prior to grafting, added to the polymer melt during the grafting or glass reinforcing process, and/or added during reprocessing of the grafted, glass reinforced polymer.
  • Suitable silanes of this type include those represented by the formula:
  • inventions include, but are not limited to, 3-acryloxypropyltriethoxysilane,
  • vinyltriacetoxysilane 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltris(beta-methoxyethoxy)silane and mixtures thereof.
  • the preferred silane compounds are vinyltrichlorosilane, vinyltriethoxysilane,
  • an unsaturated dicarboxylic anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, glutaconic anhydride, Nadic anhydride (Trademark for norbornene-2,3-dicarboxylic anhydride), methyl Nadic anhydride, tetrahydrophthalic anhydride, or
  • methyltetrahydrophthalic anhydride methyltetrahydrophthalic anhydride; or a mixture of two or more thereof.
  • unsaturated carboxylic acids and acid anhydrides thereof maleic acid, maleic anhydride, muconic acid, Nadic acid, methyl Nadic acid, methyl Nadic anhydride, or Nadic
  • anhydride is preferably used.
  • grafting compounds used in this invention have similar .amounts of
  • the grafting reaction must occur in the presence of a free radical generator, also called a free radical initiator.
  • a free radical generator also called a free radical initiator.
  • An organic peroxide is preferably used as the free radical initiator in the graft modification reaction as described above. More specifically, preferred examples of an organic peroxide include, but are not limited to, alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates, hydroperoxides, and other organic peroxides.
  • Examples of a ketone peroxide include methyl ethyl ketone peroxide and cyclohexanone peroxide.
  • Examples of hydroperoxide include tert-butyl hydroperoxide and cumene hydroperoxide.
  • Preferred examples of a free radical initiator are di-tert-butyl peroxide; 2,5- dimethyl-2,5-di(tert-butylperoxy)hexyne-3; 2,5- dimethyl-2,5-di(tert-butyl-peroxy)hexane, dicumyl peroxide; a,a'-bis(tert- butylperoxy)diisopropylbenzene; and mixtures thereof.
  • Higher molecular weight organic peroxide compounds are preferred because they are safer and easier to handle and store, as well as being more stable at higher temperatures.
  • the organic peroxide is present in the grafting reaction in an amount sufficient to
  • the amount is in the range of about 0.001 to about 5 parts of organic peroxide per 100 parts per polymer (phr), preferably in the range of about 0.001 to about 1 phr, and most preferably in the range of about 0.005 to about 0.4 phr. Too much organic peroxide can still initiate the grafting reaction, but polymer degradation, such as vis-breaking of the polymer, can occur. A concentration of organic peroxide which is too low does not initiate the grafting reaction.
  • the grafting reaction must occur in the polymer melt.
  • the temperature of the reaction is in the range from about the polymer melting point to about the polymer decomposition temperature.
  • the reaction temperature is in the range from about 20oC. above the polymer melting point to about the decomposition temperature of the polymer. Most preferably, the lower end of the temperature range is utilized to minimize any thermal degradation effects to the polymer.
  • the time required for the grafting reaction is a length sufficient for the grafting to occur.
  • the time is in the range of about 10 seconds to about 30 hours, preferably in the range of from about 15 seconds to about 3 hours. Most preferably, the reaction time is in the range of from about 30 seconds to about 10 minutes. Shorter times, such as less than 5 minutes, are preferred to minimize thermal degradation effects to the polymer.
  • One example of a continuous process is to add the polymer(s), stabilizer(s), grafting
  • the glass fiber reinforcement improves the properties, such as, for example, the mechanical and thermal properties, of the polymer.
  • the diameter of the glass fiber is preferably less than 20 micrometers ( ⁇ m), but may vary from about 3 to about 30 Pm. Glass fiber diameters are usually given a letter designation between A and Z. The most common diameters used in glass reinforced thermoplastics are G-filament (about 9 um) and K-filament (about 13 ⁇ m). Several forms of glass fiber products can be used for reinforcing thermoplastics. These include yarn, woven fabrics, continuous roving, chopped strand, mats, etc.
  • Continuous filament strands are generally cut into lengths of 1/8, 3/16, 1/4, 1/2, 3/4, and 1 inch or longer for compounding efficacy in various processes and products.
  • Any fiberous silicon oxide material can be used.
  • types of glass include, but are not limited to, type A glass (an alkali glass), type E glass (a boroaluminosilicate), type C glass (a calcium aluminosilicate), and type S glass (a high- strengthglass).
  • Type E glass is presently preferred due to economic reasons and commercial availability.
  • reinforcement material in thermoplastics are usually sized during either the fiber formation process or in a posttreatment, and thus are sold with sizing materials already incorporated.
  • the amount of sizing on the glass fiber product typically ranges from about 0.2 to about 1.5 weight percent based on total weight of the glass and the sizing, although loadings up to 10 percent may be added to mat products.
  • thermoplastic ethylene glycol dimethacrylate copolymer
  • the compositions are usually proprietary and many are not disclosed by the manufacturers.
  • the sizing compositions usually contain a lubricant, which provides protection for the glass fiber strand; a film-former or binder which gives the glass strand integrity and workability; and a
  • the coupling agent is usually a silane coupling agent that has a hydrolyzable moiety for bonding to the glass and a reactive organic moiety that is compatible with the polymeric material which is to be reinforced with the glass fibers.
  • the sizing compositions for use in this invention include those which have as an ingredient: (a) one or more epoxy-functional silanes as a
  • One such glass fiber reinforcement is produced by CertainTeed Corporation of Valley Forge, Pennsylvania, and marketed under the trade designation of Chopped Strand 930, K-filament glass fibers. This glass is marketed for use in polybutylene terephthalate, polycarbonate and
  • PPG Industries, Inc. of Pittsburgh, Pennsylvania, and marketed under the trade designation Type 1156 Chopped Strand, G-filament glass fibers.
  • PPG Type 1156 glass is marketed for use in thermoset resin systems such as phenolic, epoxy, DAP (diallyl phthalate), and
  • polyfunctional epoxy resins or, (c) a mixture of one or more epoxy-functional silanes and one or more polyfunctional epoxy resins is blended with the polymer prior to grafting, and/or added to the polymer melt during the grafting, and/or added during reprocessing of the grafted, glass reinforced
  • Epoxy-functional silanes and polyfunctional epoxy resins contemplated as useful in this invention are described in greater detail in the next two sections.
  • the glass fibers can be added any time during processing after the polymer has been
  • polymer stabilizer(s), grafting compound(s), free radical generator(s), commercially available glass fibers, and optionally, polyfunctional epoxy resin(s) and/or epoxy-functional silane(s) to an extruder.
  • the components can be added in any order. For example, all
  • the reactants can be added sequentially; for example, the grafting reaction occurs first within the presence of the polyfunctional epoxy resin(s) and/or epoxy-functional silane(s), and additional stabilizer(s) and then glass fibers are added downstream in the extruder after the grafting reaction has taken place. This latter example is the presently preferred process.
  • epoxysilanes contemplated as useful in making the compositions of this invention include epoxysilanes within the formula:
  • X is (a) a linear or branched alkylene, arylene or arylalkylene hydrocarbon radical having from 1 to about 15 carbon atoms, or (b) a chlorine atom;
  • R is a hydrocarbon radical having from 1 to about 8 carbon atoms
  • n is an integer of 1 to 3.
  • epoxy-functional silanes are 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyldimethylethoxysilane; [2-(3,4-epoxy-4- methylcyclohexyl)propyl]methyldiethoxysilane beta- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 2- glycidoxypropyltrimethoxysilane and mixtures of the foregoing epoxy-functional silanes.
  • the presently most preferred epoxy-functional silanes are 3- glycidoxypropyltrimethoxysilane which is commercially available from the Union Carbide Corporation under the trade designation A-187, and beta-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, which is available from the Union Carbide Corporation under the trade designation A-186.
  • a technical/modified grade of 3- glycidoxypropyltrimethoxysilane is commercially available from Union Carbide Corporation under the trade designation Ucarsil TM TC-100 organosilicon chemical.
  • epoxy resin refers to materials which contain an epoxy or oxirane group.
  • Polyfunctional epoxy resins contemplated as useful in this invention are compounds having two or more epoxy groups in the molecule.
  • the most common commercial epoxy resins are based on combining bisphenol A and excess epichlorohydrin to form liquid polymers with epoxy end-groups.
  • Liquid epoxy resins can be further reacted with bisphenol A by chain extension to form solid resins of higher molecular weight.
  • Other intermediate-molecular-weight epoxy resins can be prepared by chain extension of liquid epoxy resins and brominated bisphenol A.
  • Epoxy resins are also based on aliphatic backbone structures, such as, for example polyglycidyl ethers of 1,4-butanediol, neopentyl glycol, trimethylolpropane, or higher functionality polyols.
  • epoxy resins include the multifunctional epoxy phenol and cresol novalacs, which are based on phenol or cresol and formaldehyde and subsequent epoxidation with epichlorohydrin.
  • polyfunctional epoxy reins include, but are not limited to,
  • polyglycidol ethers of polyols such as ethylene glycol, propylene glycol, polyethylene glycol, glycerol, neopentyl glycol, trimethylol propane, and sorbitol; triglycidyl isocyanurate, N-methyl-N',N"-diglycidyl isocyanurate, and triglycidyl cyanurate.
  • the presently preferred molecular weight of these polyfunctional epoxides is about 4,000 or less, though the molecular weight could be higher.
  • the presently most preferred polyfunctional epoxy resin is a high softening point (solid)
  • One or more of the epoxy resins is present in an amount sufficient to effectuate a desired change in the properties of articles made from the glass reinforced polymers.
  • this amount is generally in the range of about 0.05 to about 5 parts by weight epoxy resin per hundred parts polymer (phr), more
  • this amount is generally in the range of about 0.15 to about 2 weight percent based on total weight of the glass and the sizing.
  • the polymethylpentene (PMP) used in the following examples was a homopolymer prepared from 4- methyl-1-pentene (4MP1) by conventional
  • the undried polymer was stabilized immediately after polymerization by mixing the polymer with about 0.1% based on total resin of a solution of a hindered phenolic prophylactic
  • Compound 1 is a silane grafted control example for comparison purposes.
  • the drum tumbled polymer mixture described above was mixed by hand with 43.24 parts glass fiber reinforcement in a plastic bag (bag mixed) to produce a mixture with 30 weight percent glass fiber reinforcement.
  • the glass reinforcement product used was a commercially
  • 457BA available product sized for compatibility with polypropylene produced by Owens-Corning Fiberglas Corporation and designated 457BA.
  • This product was also recommended by the manufacturer as appropriate for use in reinforcing stereoregular polymers of branched, higher alpha-olefins such as PMP.
  • This glass is a K-filament diameter glass fiber with a 3/16-inch fiber length.
  • the film-former in the sizing composition for 457 BA glass fibers is a carboxylic styrene-butadiene latex and that the coupling agent is an amino-functional silane (3-aminopropyltriethoxysilane), although the exact composition of the sizing is not disclosed by -the manufacturer.
  • 457 BA glass fibers contain terephthalic acid as a
  • the amount of sizing on the product is about 0.9 weight percent of the total product weight.
  • the mixture was compounded on a Werner & Pfleiderer ZSK-30 twin screw extruder with a general purpose compounding barrel/screw
  • the screw speed was 250 rpm and the temperature profile was 260-290oC. Throughput was 20 pounds per hour.
  • the compound was stranded,
  • the glass fiber reinforcement material used was not one generally recommended for use with polyolefins but was, instead, one recommended for use with polybutylene terephthalate (a thermoplastic polyester),
  • the glass fiber reinforcement material used in this example was a commercial product from
  • CertainTeed Corporation designated Chopped Strand 930. This is a K-filament diameter glass fiber with a 1/8-inch fiber length. It is believed that the sizing composition contains both a polyfunctional epoxy resin film-former and an epoxy-functional silane. It is further believed that the
  • polyfunctional epoxy resin is a condensation product of bisphenol A and epichlorohydrin and that the epoxy-functional silane is 3-glycidoxypropyltrimethoxysilane, although the exact composition of the sizing is not disclosed by the manufacturer.
  • the amount of sizing on the product is about 0.80 weight percent based on total weight of the sized glass.
  • Example II The process described above for Example I was repeated with the exception that the glass fiber reinforcement material used was the Chopped Strand 930 glass fiber reinforcement material described above.
  • the properties of test specimens molded from the resulting compound (Compound 2) are listed in Table III.
  • glass fiber reinforcement with a sizing composition which includes both a polyfunctional epoxy resin and an epoxy-functional silane provides significantly better mechanical properties in test specimens molded from compounds of silane grafted, glass reinforced, stereoregular polymers of branched, higher alpha- olefins than glass reinforcements sized for
  • the glass fiber reinforcement product used was not one generally recommended for use with polyolefins but was,
  • Type 1156 Chopped Strand is a commercial product from PPG Industries, Inc., designated Type 1156 Chopped Strand. It is a G-filament diameter glass fiber with a 1/8-inch fiber length. Although the exact sizing composition is not disclosed by the manufacturer, it is believed that Type 1156 Chopped Strand contains both a polyfunctional epoxy resin film-former and an epoxy-functional silane. The amount of sizing on the product is about 1.15 weight percent based on total weight of the sized glass.
  • Example 3 The process described above for Example I was repeated with the exception that the glass fiber reinforcement product was Type 1156 Chopped Strand.
  • the properties of test specimens molded from the resulting compound (Compound 3) are listed in Table III.
  • glass fiber reinforcement with a sizing composition which includes both a polyfunctional epoxy resin and an epoxy-functional silane provides significantly better mechanical properties in test specimens molded from compounds of silane grafted, glass reinforced, stereoregular polymers of branched, higher alpha- olefins than glass reinforcements sized for
  • Compound 2 is due to the smaller filament diameter of the glass fiber reinforcement.
  • an epoxy-functional silane, 3-glycidoxypropyltrimethoxysilane (UcarsilTM TC-100 available from Union Carbide
  • Example II glass fiber of the type used in Example I, one sized for
  • the PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
  • test specimens molded from Compound 4 are significantly better.
  • Example II polypropylene which was used in Example I.
  • the specific epoxy compound used was a bisphenol A extended bisphenol A/epichlorohydrin condensation product available from Shell Chemical Company as EponTM 1009F.
  • EponTM 1009F The epoxide equivalent weight is approximately 2,500-4,000.
  • the procedure was that of
  • Example I with the polyfunctional epoxy resin included with the group of ingredients which were bag mixed.
  • the following ingredients were bag mixed:
  • the PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
  • test specimens molded from Compound 5 relative to the properties of those molded from Compound 1 which did not have a polyfunctional epoxy resin are significantly better.
  • Example IV both the epoxy-functional silane used in Example IV and the epoxy resin used in Example V were used in conjunction with the glass fiber reinforcement sized for compatibility with polypropylene used in Example I.
  • the procedures of Examples IV and V were repeated except that the ingredients and their relative weight levels were as follows:
  • compositions for treating glass fibers which contain (a) one or more polyfunctional epoxy resins as a film-former, (b) one or more epoxy-functional silanes as a coupling agent or, (c) a mixture of one or more polyfunctional epoxy resins and one or more epoxy-functional silanes, provide improved adhesion between the glass fiber strand and silane grafted stereoregular polymers of branched, higher alpha-olefins.
  • Compound 7 is a control example for comparison purposes.
  • the following components were dry mixed for about 60 minutes at 25oC. (room temperature) by drum tumbling.
  • This drum tumbled mixture was then mixed by hand with 43.37 parts glass fiber reinforcement in a plastic bag (bag mixed) to produce a mixture with 30 weight percent, based on weight of the polymer and
  • the glass reinforcement product used was a commercially
  • Example I available product sized for compatibility with polypropylene produced by Owens-Corning Fiberglas Corporation and designated 457 BA. This glass product was described in Example I above. The mixture was compounded, stranded, palletized and dried as described in Example I. The resulting compound was injection molded into ASTM test
  • the glass fiber reinforcement material used was not one generally recommended for use with polyolefins but is, instead, one recommended for use with polybutylene
  • the glass fiber reinforcement material used in this example was a commercial product from CertainTeed Corporation designated Chopped Strand 930. This glass fiber reinforcement material was described in Example II above.
  • Example VII The process described above for Example VII was repeated with the exception that the glass fiber reinforcement material used was the Chopped Strand 930 glass fiber reinforcement material described in Example II.
  • the properties of test specimens molded from the resulting compound (Compound 8) are listed in Table IV.
  • polyolefins such as those used in Example VII above.
  • an epoxy- functional silane, 3-glycidoxypropyltrimethoxysilane (UcarsilTM TC-100 available from Union Carbide
  • Example VII glass fiber of the type used in Example VII, one sized for compatibility with polypropylene.
  • the procedure was that of Example VII, with the epoxy-functional silane included with the group of ingredients which were bag mixed:
  • OCF 457 BA glass fiber 43.45 parts
  • the PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
  • Example VII polypropylene which was used in Example VII.
  • the specific epoxy compound used was a bisphenol A extended bisphenol A/epichlorohydrin condensation product available from Shell Chemical Company
  • EponTM 1009F EponTM 1009F.
  • the epoxide equivalent weight is approximately 2,500-4,000.
  • the procedure was that of Example VII, with the polyfunctional epoxy resin included with the group of ingredients which were bag mixed.
  • the ingredients which were bag mixed were as follows:
  • the PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
  • Example IX both the epoxy- functional silane used in Example IX and the epoxy resin used in Example X were used in conjunction with the glass fiber reinforcement sized for compatibility with polypropylene used in Example VII. Essentially, the procedures of Examples IX and X were repeated except that the ingredients were as follows:
  • the PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
  • test specimens molded from Compound 11 The increase in properties of test specimens molded from Compound 11 relative to those of Compound 7 is again apparent.
  • compositions for treating glass fibers which contain (a) one or more polyfunctional epoxy resins as a film-former, (b) one or more epoxy- functional silanes as a coupling agent or, (c) a mixture of one or more polyfunctional epoxy resins and one or more epoxy-functional silanes, provide improved adhesion between the glass fiber strand and maleic anhydride grafted stereoregular polymers of branched, higher alpha-olefins.
  • the glass fiber reinforcement material used was not one generally recommended for use with polyolefins but is, instead, one recommended for use with polybutylene
  • the glass fiber reinforcement material used in this example was a commercial product from
  • CertainTeed Corporation designated Chopped Strand 930. This glass fiber reinforcement material was described in Example II above.
  • Ciba-Geigy Corporation commercially from Ciba-Geigy Corporation as Irganox 1010), 0.50 phr muconic acid in the form of cis,cis 2,4-hexadienedioic acid (available commercially from Celgene Corporation) and 0.05 phr a,a'-bis(tert-butylperoxy)diisopropyl benzene (available from Ciba-Geigy Corporation as Irganox 1010), 0.50 phr muconic acid in the form of cis,cis 2,4-hexadienedioic acid (available commercially from Celgene Corporation) and 0.05 phr a,a'-bis(tert-butylperoxy)diisopropyl benzene (available from Ciba-Geigy Corporation as Irganox 1010), 0.50 phr muconic acid in the form of cis,cis 2,4
  • Hercules, Inc. as Vulcup R). The components were dry mixed for about 60 minutes at about 25oC. (room temperature) by drum tumbling.
  • Compound 2 was made using PMP grafted with an unsaturated hydrolyzable silane.
  • Compound 8 was made using PMP grafted with a carboxylic acid.

Abstract

Compositions of stabilized stereoregular polymers of branched higher alpha-olefins, grafting compounds, free radical generators, glass and epoxy resins and/or epoxy-functional silanes are provided as well as methods for making these compounds and articles thereof.

Description

GLASS-REINFORCED GRAFTED BRANCHED HIGHER ALPHA-OLEFINS Background of the Invention
This invention relates to glass-reinforced thermoplastics.
Polyolefins tend to have excellent physical and chemical properties. Improvement of polymer properties is a dominant factor in the development and production of olefin polymers. Several methods have been employed to improve various polymer
properties. The prior art teaches that reinforcing agents, such as glass fibers, can be incorporated into the polymer to improve the mechanical properties and/or the heat resistance of the polymer. However, merely mixing the glass fibers and the polyolefins together can result in weak bonding between the glass fibers and the polyolefin. One solution is to have a more bondable component grafted onto the polymers to facilitate reinforcement with glass fibers and other generally infusible reinforcing agents.
Polymers with relatively high melting points, such as stereoregular polymers of branched, higher alpha-olefins, have been developed. These polymers are useful in high temperature applications, such as microwave packaging. Improving the
performance and/or properties of these polymers could expand the variety of uses of these polymers.
Polymers of branched higher alpha-olefins have been modified with grafting reactions to
incorporate functional chemical moieties to improve the adhesion between the alpha-olefin matrix and the glass reinforcement as has been disclosed in U.S. Patent 4,888,394, December 19, 1989.
Glass fiber reinforcement products are usually sized either during the fiber formation process or in a posttreatment. Sizing compositions for use in treating glass fibers usually contain a lubricant, which provides the protection for the glass fiber strand; a film-former or binder that gives the glass fiber strand integrity and
workability; a coupling agent that provides better adhesion between the glass fiber strand and the polymeric materials that are reinforced with the glass fiber strand; and other additives such as emulsifiers, wetting agents, nucleating agents, and the like. Various sizing compositions have been developed for glass fiber reinforcements to provide improved adhesion between various polymeric materials and the glass fiber. Sizing compositions are known for treating glass fibers for improved adhesion between the glass fiber strand and relatively low melting point polyolefins, such as polyethylene and polypropylene. The polyolefin may be modified partially or entirely with an unsaturated carboxylic acid or derivative thereof. The prior art does not teach sizing compositions for treating glass fibers for improved adhesion between glass fibers and stereoregular polymers of branched, higher alpha-olefins or stereoregular polymers of branched, higher alpha-olefins which have been modified with
unsaturated silanes, carboxylic acids, or derivatives thereof.
summary of the Invention
It is an object of this invention to provide glass-reinforced branched higher alpha-olef ins with improved adhesion between the higher alpha-olefin matrix and the glass reinforcement. It is another object of this invention to provide methods for making glass-reinforced branched higher alpha-olefins with improved adhesion between the higher alpha-olefin matrix and the glass
reinforcement.
It is an object of this invention to provide glass-reinforced thermoplastic materials from which products with improved properties can be made.
It is another object of this invention to provide methods for making glass-reinforced
thermoplastic materials from which products with improved properties can be made.
In one embodiment of this invention a composition comprises:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids;
carboxylic acid derivatives; carboxylic acid
anhydrides; carboxylic acid anhydride derivatives; and mixtures thereof;
(c) a free radical generator;
(d) glass; and
(e) at least one epoxy resin.
Another embodiment of this invention is a composition comprising:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides;
carboxylic acid anhydride derivatives; and mixtures thereof; (c) a free radical generator;
(d) glass; and
(e) at least one epoxy-functional silane. In yet another embodiment of this invention a composition comprises:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides;
carboxylic acid anhydride derivatives; and mixtures thereof;
(c) a free radical generator;
(d) glass;
(e) at least one epoxy resin; and
(f) at least one epoxy-functional silane. In accordance with this invention methods are provided for making the compositions of this invention.
Also in accordance with this invention articles made from the compositions of the invention are provided.
Detailed Description of the invention
The mechanical and thermal properties and property retention characteristics of stereoregular polymers of branched higher alpha-olefins are
improved by compounding with glass fibers. These polymers are further improved by chemical coupling of the polymer matrix to the glass reinforcing fibers. The resultant compounds have excellent electrical properties, high strength, and good thermal and chemical resistance, which are beneficial in a
variety of automotive and electrical applications. For example, products made with the glass-reinforced polymers of this invention have exhibited significantly higher heat deflection temperatures than products made with other glass-reinforced polymers.
Surprisingly excellent mechanical and thermal properties can be obtained by (a) modifying stabilized, stereoregular polymers of branched, higher alpha-olefin polymers with unsaturated silanes, carboxylic acids, and/or carboxylic acid anhydrides in the presence of a free radical
generator in the polymer melt, and then (b)
reinforcing these modified polymers with glass which has been sized with compositions which contain at least one epoxy resin or at least one epoxy-functional silane or both at least one epoxy resin and at least one epoxy-functional silane.
Polymers
Polymers considered suitable for use in this invention are olefinic polymers which have a melting point higher than about 180ºC, more
preferably, a melting point of greater than about
190*c. Polymers produced from linear monomers, such as ethylene, propylene, butene, and hexene, usually have lower melting points than polymers of branched, higher alpha-olefins. Thus, the polymers useful in this invention are homopolymers and copolymers of branched, higher alpha-olefins. The preferred alpha-olefin monomers have from about 4 to 12 carbon atoms. Exemplary monomers include, but are not limited to, 3-methyl-1-butene (3MB1), 3-methyl-1-pentene (3NP1), 4-methyl-1-pentene (4MP1), 4-methyl-1-hexene (4MH1), 3,3-dimethyl-1-butene (3,3DHB1), 4,4-dimethyl-1-hexene (4,4DHH1), 3-ethyl-1-hexene (3EH1) and other similar monomers. Most preferably, polymers of 4NP1, also called polymethylpentene (PMP), and 3MB1, also called polymethylbutene (PMB), are utilized in this invention. Table I gives the approximate melting point of each homopolymer listed above. TABLE I
Melting Points of Some of the Polymers
Useful in This Invention
Approximate Melting Polymerized Monomer Temperature, ºC.
3-methyl-1-butene 300
3-methyl-1-pentene 370
4-methyl-1-pentene 240
4-methyl-1-hexene 196
3-ethyl-1-hexene 425
3,3-dimethyl-1-butene 400
4,4-dimethyl-1-hexene 350 The term "polymer", as used in this disclosure, includes homopolymers, as well as copolymers. Copolymers comprise the product
resulting from combining a branched, higher alpha- olefin with any other olefin monomer or monomers. For example, a branched, higher alpha-olefin can be polymerized in the presence of, or in series with, one or more olefin monomers. Generally, applicable comonomers have from about 2 to about 18 carbon atoms and preferably, have from about 8 to about 16 carbon atoms. Most preferably, the commoner or comonomers are linear alpha-olefins. Longer chain linear olefins are preferred in that they are easier to copolymerize with higher, branched alpha-olefins and can impart increased clarity, stability, and impact strength to the resultant polymer. Exemplary
comonomers include, but are not limited to, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and other higher olefins. A polymer can also be obtained by physically blending homopolymers and/or copolymers.
In general, it is preferred for the polymer to comprise at least about 85 mole percent moieties derived from higher, branched alpha-olefins, and more preferably, at least about 90 mole percent moieties derived from higher, branched alpha-olefins. Most preferably, the polymer comprises at least about 95 mole percent moieties derived from higher, branched alpha-olefins, which results in a polymer of superior strength and a high melting point.
Polymer Stabilizing Package
After the polymer has been produced, it is essential, according to this invention, that the polymer be given a prophylactic charge with a
hindered phenol before additional processing of the polymer. The hindered phenol acts as an antioxidant and improves the heat, light, and/or oxidation stability of the polymer. As a result of the
prophylactic charge, the polymer product can
withstand drying and storage after the polymerization process. Any hindered phenol in an amount which improves the heat, light, and/or oxidation stability of the polymer is applicable. Exemplary hindered phenol compounds include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol; tetrakis(methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) methane; thiodiethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate); octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; and/or 2,2'-methylene bis(4-methyl-6-tert-butylphenol). Preferably the hindered phenol antioxidant used for the prophylactic charge is selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol; tetrakis(methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane;
octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; and mixtures thereof because of ease of use, availability, and economic reasons.
In addition to the essential prophylactic charge of hindered phenol, other antioxidants or stabilizers can be added to further stabilize the polymer. The type(s) of stabilizer(s) used depends on the final application or use of the polymer.
Numerous polymer additives are commercially available and are usually selected from the group consisting of additional hindered phenols, organic phosphites, hindered amine light stabilizers, thioesters, aliphatic thio compounds and mixtures thereof.
The total polymer stabilizer package that can be added prior to grafting, which comprises the essential hindered phenol antioxidant prophylactic charge, and the optional additional hindered phenol, organic phosphite, thioesters and/or hindered amine light stabilizer, is usually added to the polymer in an amount in the range of about 0.05 to about 2 parts by weight of total stabilizer(s) per 100 parts by weight of polymer (phr). Preferably, the hindered phenol prophylactic charge comprises an amount in the range of about 0.1 to about 1 phr, and most
preferably in an amount in the range of about 0.1 to about 0.8 phr. If insufficient hindered phenol is present, oxidative degradation of the polymer can occur. The presence of excess hindered phenol can interfere with the grafting process. If desired, additional stabilizers, i.e., in excess of 2 phr, can be added any time after the grafting process,
depending upon the desired polymer properties.
Other Polymer Additives
Other additives can optionally be incorporated into the polymer, before and after grafting, to achieve additionally desired beneficial polymer properties. General exemplary additives include, but are not limited to, antioxidants, antioxidant synergists, UV absorbers, nickel stabilizers, pigments, plasticizing agents, optical brighteners, antistatic agents, flame retardants, lubricating agents, metal inhibitors, and the like. Processing lubricants can also be added to enhance polymer properties. Examples of processing
lubricants include, but are not limited to, fatty acids containing from about 10 to about 20 carbon atoms and the metal salts thereof. Usually, metal stearates, such as, for example, calcium stearate and zinc stearate, and/or metal laurates are used as processing lubricants and/or acid scavengers for polyolefins. If corrosion is a potential problem, one or more corrosion inhibitors can be added.
Any additive can be combined with the polymer according to any method known in the art. Examples of incorporation methods include, but are not limited to, dry mixing in the form of a powder and wet mixing in the form of a solution or slurry. In these types of methods, the polymer can be in any form, such as, for example, fluff, powder, granulate, pellet, solution, slurry, and/or emulsion. For ease of operation, the initial prophylactic charge of hindered phenol is usually solution or slurry mixed with the polymer prior to drying and handling of the polymer. Any additional stabilizers or additives can be blended with the polymer prior to grafting, added to the polymer melt during the grafting or glass reinforcing process, and/or added during reprocessing of the grafted, glass reinforced polymer.
Grafting compounds
The stabilized, stereoregular polymers of branched, higher alpha-olefins are modified by grafting with a radically polymerizable unsaturated grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silane compounds, carboxylic acids and derivatives, carboxylic acid anhydrides and derivatives, and mixtures thereof, in the presence of a free radical generator.
The vinyl-polymerizable unsaturated, hydrolyzable silanes used in this invention contain at least one silicon-bonded hydrolyzable group, such as, for example, alkoxy, halogen, and acryloxy, and at least one silicon-bonded vinyl-polymerizable unsaturated group such as, for example, vinyl, 3- methacryloxypropyl, alkenyl, 3-acryloxypropyl, 6- acryloxyhexyl, alkylαxypropyl, ethynyl, and 2- propynyl. The silicon-bonded vinyl-polymerizable unsaturated group preferably is an ethylenically unsaturated group. Any remaining valances of silicon not satisfied by a hydrolyzable group or a vinyl- polymerizable unsaturated group are satisfied by a monovalent hydrocarbon group, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, isobutyl, isopentyl, octyl, decyl, cyclohexyl, cyclopentyl, benzyl, phenyl, phenylethyl, and
naphthyl. Suitable silanes of this type include those represented by the formula:
RaSiXbYc
wherein R is a monovalent hydrocarbon group, X is a silicon-bonded hydrolyzable group, Y is a silicon-bonded monovalent organic group containing at least one vinyl-polymerizable unsaturated bond, a is an integer of 0 to 2, preferably 0; b is an integer of 1 to 3, preferably 3; c is an integer of 1 to 3, preferably 1; and a + b + c is equal to 4.
Suitable vinyl-polymerizable unsaturated hydrolyzable silanes that can be used in this
invention include, but are not limited to, 3-acryloxypropyltriethoxysilane,
ethynyltriethoxysilane, 2-propynyltrichlorosilane, 3-acryloxypropyldimethylchlorosilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropylmethyldichlorosilane, 3- acryloxypropyltrichlorosilane, 3- acryloxypropyltrimethoxysilane,
allyldimethylchlorosilane, allylmethyldichlorosilane, allyltrichlorosilane, allyltriethoxysilane,
allyltrimethoxysilane, chloromethyldimethylvinylsilane, [2-(3-cyclohexenyl)ethyl]dimethylchlorosilane, 2-(3- cyclohexenyl)ethyltrimethoxysilane, 3- cyclohexenyltrichlorosilane,
diphenylvinylchlorosilane, diphenylvinylethoxysilane,
(5-hexenyl)dimethylchlorosilane, (5-hexenyl)diethylchlorosilane, 5-hexenyltrichlorosilane, 3-methacryloxpropyldimethylchlorosilane, 3-methacryloxypropyldimethylethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrichlorosilane, methyl-2-(3-cyclohexenyl)-ethyldichlorosilane, methyl-3- (trimethylsiloxy)crotonate, 7-octenyltrichlorosilane, 7-octenyltrimethoxysilane,
1-phenyl-1-trimethylsiloxyethylene,
phenylvinyldichlorosilane,
styrylethyltrimethoxysilane, 1,3-tetradecenyltrichlorosilane, 4-[2- (trichlorosilyl)ethyl]cyclohexene, 2- (trimethylsiloxy)ethylmethacrylate, 3- (trimethylsilyl)cyclopentene,
vinyldimethylchlorosilane, vinyldimethylethoxysilane, vinylethyldichlorosilane, vinylmethyldiacetoxysilane, vinylmethyldichlorosilane, vinylmethyldiethoxysilane, vinyltrimethylsilane, vinyltrichlorosilane,
vinyltriethoxysilane, vinyltrimethoxysilane,
vinyltris(beta-methoxyethoxy)silane,
vinyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltris(beta-methoxyethoxy)silane and mixtures thereof. The preferred silane compounds are vinyltrichlorosilane, vinyltriethoxysilane,
vinyltrimethoxysilane, vinyltris(beta- methoxyethoxy)silane, vinyltriacetoxysilane, 3- methacryloxypropyltrimethoxysilane, 3- methacryloxypropyltris(beta-methoxyethoxy)silane, and mixtures thereof. These compounds are preferred due to commercial availability, ease of use, as well as good polymer property improvement.
The radically polymerizable unsaturated grafting compound also can be a carboxylic acid or an anhydride thereof, with about three to about 10 carbon atoms, with preferably at least one olefinic unsaturation, and derivatives thereof. Examples of the carboxylic acid and anhydride include, but are not limited to, an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid; an
unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, muconic acid (mesaconic acid),
glutaconic acid, norbornene-2,3-dicarboxylic acid (tradename Nadic acid), methyl Nadic acid,
tetrahydrophthalic acid, or methylhexahydrophthalic acid; an unsaturated dicarboxylic anhydride such as maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, glutaconic anhydride, Nadic anhydride (Trademark for norbornene-2,3-dicarboxylic anhydride), methyl Nadic anhydride, tetrahydrophthalic anhydride, or
methyltetrahydrophthalic anhydride; or a mixture of two or more thereof. Of these unsaturated carboxylic acids and acid anhydrides thereof, maleic acid, maleic anhydride, muconic acid, Nadic acid, methyl Nadic acid, methyl Nadic anhydride, or Nadic
anhydride is preferably used.
The radically polymerizable unsaturated grafting compound is present in the reaction mixture in an amount sufficient to improve the properties of the resultant grafted polymer. Usually, the amount is in the range of about 0.1 to about 2 parts of radically polymerizable unsaturated grafting compound per 100 parts of polymer (phr), preferably in the range of about 0.2 to about 1.6 phr, and most
preferably in the range of about 0.4 to about 1.2 phr. If too much grafting compound is used, not all of the grafting compound will be grafted onto the polymer and no additional appreciable polymer
property improvement is obtained; an excess is economically undesirable. Use of too little grafting compound does not improve or enhance the polymer properties. In general, the grafting compounds used in this invention have similar .amounts of
functionality.
The grafting reaction must occur in the presence of a free radical generator, also called a free radical initiator. An organic peroxide is preferably used as the free radical initiator in the graft modification reaction as described above. More specifically, preferred examples of an organic peroxide include, but are not limited to, alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates, hydroperoxides, and other organic peroxides. Examples of an alkyl peroxide include diisopropyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3; a,a'-bis(tert-butylperoxy)diisopropyl benzene; and 2,5-dimethyl-2,5-di(tertbutylperoxy)hexane. An example of an aryl peroxide is dicumyl peroxide. An example of an acyl peroxide is dilauroyl peroxide. An example of an aroyl peroxide is dibenzoyl peroxide. Examples of a ketone peroxide include methyl ethyl ketone peroxide and cyclohexanone peroxide. Examples of hydroperoxide include tert-butyl hydroperoxide and cumene hydroperoxide. Preferred examples of a free radical initiator are di-tert-butyl peroxide; 2,5- dimethyl-2,5-di(tert-butylperoxy)hexyne-3; 2,5- dimethyl-2,5-di(tert-butyl-peroxy)hexane, dicumyl peroxide; a,a'-bis(tert- butylperoxy)diisopropylbenzene; and mixtures thereof. Higher molecular weight organic peroxide compounds are preferred because they are safer and easier to handle and store, as well as being more stable at higher temperatures.
The organic peroxide is present in the grafting reaction in an amount sufficient to
effectuate a grafting reaction. Usually, the amount is in the range of about 0.001 to about 5 parts of organic peroxide per 100 parts per polymer (phr), preferably in the range of about 0.001 to about 1 phr, and most preferably in the range of about 0.005 to about 0.4 phr. Too much organic peroxide can still initiate the grafting reaction, but polymer degradation, such as vis-breaking of the polymer, can occur. A concentration of organic peroxide which is too low does not initiate the grafting reaction.
The grafting reaction must occur in the polymer melt. Thus, the temperature of the reaction is in the range from about the polymer melting point to about the polymer decomposition temperature.
Preferably, the reaction temperature is in the range from about 20ºC. above the polymer melting point to about the decomposition temperature of the polymer. Most preferably, the lower end of the temperature range is utilized to minimize any thermal degradation effects to the polymer.
The time required for the grafting reaction is a length sufficient for the grafting to occur.
Usually, the time is in the range of about 10 seconds to about 30 hours, preferably in the range of from about 15 seconds to about 3 hours. Most preferably, the reaction time is in the range of from about 30 seconds to about 10 minutes. Shorter times, such as less than 5 minutes, are preferred to minimize thermal degradation effects to the polymer.
The grafting reaction can be carried out by either batch or continuous processes, provided that all components are well dispersed and well blended. A continuous process is preferred for ease of
operation. One example of a continuous process is to add the polymer(s), stabilizer(s), grafting
compound(s), and free radical generator(s) to an extruder. The order of addition of the components is not critical. For example, all components can be dry mixed and then extruded. If preferred, the reactants can be added sequentially wherein, for example, the grafting reaction occurs first, and additional stabilizer(s) is added downstream from the extruder. Reinforcement Materials
The glass fiber reinforcement improves the properties, such as, for example, the mechanical and thermal properties, of the polymer. Glass
reinforcements having a variety of compositions, filament diameters and forms are useful in this invention.
The diameter of the glass fiber is preferably less than 20 micrometers (μm), but may vary from about 3 to about 30 Pm. Glass fiber diameters are usually given a letter designation between A and Z. The most common diameters used in glass reinforced thermoplastics are G-filament (about 9 um) and K-filament (about 13 μm). Several forms of glass fiber products can be used for reinforcing thermoplastics. These include yarn, woven fabrics, continuous roving, chopped strand, mats, etc.
Continuous filament strands are generally cut into lengths of 1/8, 3/16, 1/4, 1/2, 3/4, and 1 inch or longer for compounding efficacy in various processes and products. Any fiberous silicon oxide material can be used. Examples of types of glass include, but are not limited to, type A glass (an alkali glass), type E glass (a boroaluminosilicate), type C glass (a calcium aluminosilicate), and type S glass (a high- strengthglass). Type E glass is presently preferred due to economic reasons and commercial availability.
Commercial glasses sold for use as
reinforcement material in thermoplastics are usually sized during either the fiber formation process or in a posttreatment, and thus are sold with sizing materials already incorporated.
The amount of sizing on the glass fiber product typically ranges from about 0.2 to about 1.5 weight percent based on total weight of the glass and the sizing, although loadings up to 10 percent may be added to mat products.
Depending upon what thermoplastic is to be used, the intended applications, and variations in glass processed by different manufacturers even for the same intended end uses, there are differences in the sizing compositions. The compositions are usually proprietary and many are not disclosed by the manufacturers.
The sizing compositions usually contain a lubricant, which provides protection for the glass fiber strand; a film-former or binder which gives the glass strand integrity and workability; and a
coupling agent which provides better adhesion between the glass fiber strand and the polymeric materials that are being reinforced with the glass fiber strand. The lubricant, film-former, and coupling agent can be a single compound or a mixture of two or more compounds. Additional agents which may be used in sizing compositions include emulsifiers, wetting agents, nucleating agents, and the like.
The film-former is usually water soluble or water emulsifiable during processing and must be non- sensitive to water after curing. Examples of film- formers include, but are not limited to, polyesters, epoxy resins, polyurethanes, polyacrylates, polyvinyl acetates, polyvinyl alcohols, styrene-butadiene latexes, starches, and the like.
The coupling agent is usually a silane coupling agent that has a hydrolyzable moiety for bonding to the glass and a reactive organic moiety that is compatible with the polymeric material which is to be reinforced with the glass fibers.
The sizing compositions for use in this invention include those which have as an ingredient: (a) one or more epoxy-functional silanes as a
coupling agent or, (b) one or more polyfunctional epoxy resins as a film-former or, (c) a mixture of one or more epoxy-functional silanes and one or more polyfunctional epoxy resins. One such glass fiber reinforcement is produced by CertainTeed Corporation of Valley Forge, Pennsylvania, and marketed under the trade designation of Chopped Strand 930, K-filament glass fibers. This glass is marketed for use in polybutylene terephthalate, polycarbonate and
styrenic resin systems. Another glass fiber
reinforcement which is suitable for use in this invention is that manufactured by PPG Industries, Inc., of Pittsburgh, Pennsylvania, and marketed under the trade designation Type 1156 Chopped Strand, G-filament glass fibers. PPG Type 1156 glass is marketed for use in thermoset resin systems such as phenolic, epoxy, DAP (diallyl phthalate), and
thermoset polyesters. Alternatively, commercially sized glass without one or more of these ingredients can be used for this invention if (a) one or more epoxy-functional silanes or, (b) one or more
polyfunctional epoxy resins or, (c) a mixture of one or more epoxy-functional silanes and one or more polyfunctional epoxy resins is blended with the polymer prior to grafting, and/or added to the polymer melt during the grafting, and/or added during reprocessing of the grafted, glass reinforced
polymer.
Epoxy-functional silanes and polyfunctional epoxy resins contemplated as useful in this invention are described in greater detail in the next two sections.
The glass fiber reinforcement should be present in the range of about 10 to about 200 parts by weight glass fiber per hundred parts by weight of polymer (phr). Preferably, the glass fibers are present in the range of about 10 to about 120 phr, and most preferably in the range of about 10 to about 80 phr. Expressed in other terms, the glass fibers should be present in about 10 to about 67 weight percent, based on the weight of the total product. Preferably, the glass fibers are present in the range of about 10 to about 55 weight percent, and more preferably in the range of about 10 to about 45 weight percent. Using too small an amount of glass fiber does not improve the polymer properties.
Having too much glass fiber results in not enough polymer to coat the glass fibers; i.e., the fibers are not "wetted out."
The glass fibers can be added any time during processing after the polymer has been
initially stabilized with the hindered phenol
prophylactic charge. Batch or continuous processes can be used, as long as all components are well dispersed and well blended. A continuous process is presently preferred for ease of operation. One example of a continuous process is to add the
polymer, stabilizer(s), grafting compound(s), free radical generator(s), commercially available glass fibers, and optionally, polyfunctional epoxy resin(s) and/or epoxy-functional silane(s) to an extruder. As with the grafting reaction process, the components can be added in any order. For example, all
components can be dry mixed and then extruded. If preferred, the reactants can be added sequentially; for example, the grafting reaction occurs first within the presence of the polyfunctional epoxy resin(s) and/or epoxy-functional silane(s), and additional stabilizer(s) and then glass fibers are added downstream in the extruder after the grafting reaction has taken place. This latter example is the presently preferred process.
Epoxv-functional Silanes
The epoxysilanes contemplated as useful in making the compositions of this invention include epoxysilanes within the formula:
wherei
Figure imgf000021_0001
n
Figure imgf000021_0002
or O
X is (a) a linear or branched alkylene, arylene or arylalkylene hydrocarbon radical having from 1 to about 15 carbon atoms, or (b) a chlorine atom;
R is a hydrocarbon radical having from 1 to about 8 carbon atoms;
m is an integer of at least 1; and n is an integer of 1 to 3.
The two different R groups will not necessarily be the same. Presently preferred are epoxysilanes within the formula above wherein n is equal to 3.
Examples of particularly suitable epoxy-functional silanes are 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropyldimethylethoxysilane; [2-(3,4-epoxy-4- methylcyclohexyl)propyl]methyldiethoxysilane beta- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 2- glycidoxypropyltrimethoxysilane and mixtures of the foregoing epoxy-functional silanes. The presently most preferred epoxy-functional silanes are 3- glycidoxypropyltrimethoxysilane which is commercially available from the Union Carbide Corporation under the trade designation A-187, and beta-(3,4- epoxycyclohexyl)ethyltrimethoxysilane, which is available from the Union Carbide Corporation under the trade designation A-186.
A technical/modified grade of 3- glycidoxypropyltrimethoxysilane is commercially available from Union Carbide Corporation under the trade designation Ucarsil™ TC-100 organosilicon chemical.
One or more of the epoxy-functional silanes is present in an amount sufficient to effectuate a desired change in the properties of articles made from the glass reinforced polymer. When the epoxy- functional silanes are added to the polymer, this amount is generally in the range of about 0.05 to about 5 parts by weight epoxy-functional silane per hundred parts polymer (phr), more preferably, in an amount in the range of about 0.2 to about 1.6 phr and, most preferably, in an amount of about 0.4 to about 1.2 phr. When the epoxy-functional silanes are components of the sizing on the glass, this amount is generally in the range of about 0.05 to about 0.5 weight percent based on total weight of the glass and sizing on the glass.
Epoxy Pegins
The term epoxy resin refers to materials which contain an epoxy or oxirane group.
Polyfunctional epoxy resins contemplated as useful in this invention are compounds having two or more epoxy groups in the molecule. The most common commercial epoxy resins are based on combining bisphenol A and excess epichlorohydrin to form liquid polymers with epoxy end-groups. Liquid epoxy resins can be further reacted with bisphenol A by chain extension to form solid resins of higher molecular weight. Other intermediate-molecular-weight epoxy resins can be prepared by chain extension of liquid epoxy resins and brominated bisphenol A. Epoxy resins are also based on aliphatic backbone structures, such as, for example polyglycidyl ethers of 1,4-butanediol, neopentyl glycol, trimethylolpropane, or higher functionality polyols. Other prominant types of epoxy resins include the multifunctional epoxy phenol and cresol novalacs, which are based on phenol or cresol and formaldehyde and subsequent epoxidation with epichlorohydrin. Examples of polyfunctional epoxy reins include, but are not limited to,
bisphenol A epoxy compounds, bisphenol F epoxy compounds, aliphatic ether epoxy compounds, novalac epoxides, isocyanurate epoxides, and mixtures
thereof. Specific examples of these include
condensates between bisphenol A and epichlorohydrin; polyglycidol ethers of polyols such as ethylene glycol, propylene glycol, polyethylene glycol, glycerol, neopentyl glycol, trimethylol propane, and sorbitol; triglycidyl isocyanurate, N-methyl-N',N"-diglycidyl isocyanurate, and triglycidyl cyanurate. The presently preferred molecular weight of these polyfunctional epoxides is about 4,000 or less, though the molecular weight could be higher.
The presently most preferred polyfunctional epoxy resin is a high softening point (solid)
condensation product of bisphenol A and
epichlorohydrin.
One or more of the epoxy resins is present in an amount sufficient to effectuate a desired change in the properties of articles made from the glass reinforced polymers. When the epoxy resin is added to the polymer, this amount is generally in the range of about 0.05 to about 5 parts by weight epoxy resin per hundred parts polymer (phr), more
preferably, in an amount in the range of about 0.1 to about 5 phr and, most preferably, in an amount of about 0.1 to about 2.5 phr. When the epoxy resin is a component of the sizing on the glass, this amount is generally in the range of about 0.15 to about 2 weight percent based on total weight of the glass and the sizing.
Examples
The polymethylpentene (PMP) used in the following examples was a homopolymer prepared from 4- methyl-1-pentene (4MP1) by conventional
polymerization processes, such as, for example, according to the processes disclosed in U.S. Patent 4,342,854, which is hereby incorporated herein by reference.
The undried polymer was stabilized immediately after polymerization by mixing the polymer with about 0.1% based on total resin of a solution of a hindered phenolic prophylactic
stabilizer, octadecyl (3,5-di-tert-tert-butyl-4-hydroxyphenyl)propionate. See U.S. Patent 4,888,394, which is hereby incorporated herein by reference.
These combined solutions were then dried to remove the liquids and produce a treated, stabilized
polymer. The polymer had a nominal melt index of about 26 grams/10 minutes. The melt index was
measured according to ASTM Method D1238 using a 5 kilogram weight at 260ºC.
In each of the following Examples I through
VI, 100 parts of treated, stabilized polymer were mixed with 0.04 phr zinc stearate, 0.25 phr tetrakis(methylene 3-(3,5-di-tert-butyl-4- hydroxyphenyl)proprionate)methane (available
commercially from Ciba-Geigy Corporation as Irganox 1010), 0.50 phr3-methacryloxypropyltrimethoxysilane (available from Union Carbide Corporation as A-174 organofunctional silane), and 0.10 phr
2,5-dimethyl-2,5-(di-tert-butylperoxy)hexane
(available from Catalyst Resources, Inc., as Aztec 2,5-Di). The components were dry mixed for about 60 minutes at about 25ºC. (room temperature) by drum tumbling.
In each of the following Examples VII through XI, the same procedure for preparing, stabilizing and grafting the polymer was used, with the exception that 0.80 phr of maleic anhydride was used in place of the 3-methacryloxypropyltrimethoxysilane.
In the following example XII, a similar procedure for preparing, stabilizing and grafting the polymer was used, with the exception that 0.50 phr of muconic acid was used in place of the 3- methacryloxypropyltrimethoxysilane.
Example I
Compound 1 is a silane grafted control example for comparison purposes. The drum tumbled polymer mixture described above was mixed by hand with 43.24 parts glass fiber reinforcement in a plastic bag (bag mixed) to produce a mixture with 30 weight percent glass fiber reinforcement. The glass reinforcement product used was a commercially
available product sized for compatibility with polypropylene produced by Owens-Corning Fiberglas Corporation and designated 457BA. This product was also recommended by the manufacturer as appropriate for use in reinforcing stereoregular polymers of branched, higher alpha-olefins such as PMP. This glass is a K-filament diameter glass fiber with a 3/16-inch fiber length. It is believed that the film-former in the sizing composition for 457 BA glass fibers is a carboxylic styrene-butadiene latex and that the coupling agent is an amino-functional silane (3-aminopropyltriethoxysilane), although the exact composition of the sizing is not disclosed by -the manufacturer. It is also believed that 457 BA glass fibers contain terephthalic acid as a
nucleating agent. The amount of sizing on the product is about 0.9 weight percent of the total product weight. The mixture was compounded on a Werner & Pfleiderer ZSK-30 twin screw extruder with a general purpose compounding barrel/screw
configuration. The screw speed was 250 rpm and the temperature profile was 260-290ºC. Throughput was 20 pounds per hour. The compound was stranded,
pelletized and dried overnight at 110ºC. The
resulting compound was injection molded into ASTM test specimens using a Model EC88 Engel injection molding machine with a 55-ton clamp force. The mold temperature was set at 93ºC. and the barrel
temperature at 270 to 280ºC., ascending from the beginning to the end of the barrel. Cycle time was approximately 30 seconds. Measured properties of test specimens molded from the resin of Compound 1 are listed in Table III. The following test
procedures were utilized to test all of the Compounds given in these examples.
TABLE II
Test Procedures Used
Analysis ASTM Method No.
Tensile Strength at Break (psi) D638, at 5 mm/min
Elongation at Break (%) D638, at 5 mm/min
Flexural Strength (psi) D790, 2 inch span,
1 mm/min
Flexural Modulus (ksi) D790, 2 inch span,
1 mm/min
Izod Impact Strength, Notched
and Unnotched (ft-lb/in) D256
Heat Deflection Temperature (ºC.) D648, at 264 psi load
Example II
In this inventive example, the glass fiber reinforcement material used was not one generally recommended for use with polyolefins but was, instead, one recommended for use with polybutylene terephthalate (a thermoplastic polyester),
polycarbonate and styrenic resin systems.
The glass fiber reinforcement material used in this example was a commercial product from
CertainTeed Corporation designated Chopped Strand 930. This is a K-filament diameter glass fiber with a 1/8-inch fiber length. It is believed that the sizing composition contains both a polyfunctional epoxy resin film-former and an epoxy-functional silane. It is further believed that the
polyfunctional epoxy resin is a condensation product of bisphenol A and epichlorohydrin and that the epoxy-functional silane is 3-glycidoxypropyltrimethoxysilane, although the exact composition of the sizing is not disclosed by the manufacturer. The amount of sizing on the product is about 0.80 weight percent based on total weight of the sized glass.
The process described above for Example I was repeated with the exception that the glass fiber reinforcement material used was the Chopped Strand 930 glass fiber reinforcement material described above. The properties of test specimens molded from the resulting compound (Compound 2) are listed in Table III.
It is clear from the data that glass fiber reinforcement with a sizing composition which includes both a polyfunctional epoxy resin and an epoxy-functional silane provides significantly better mechanical properties in test specimens molded from compounds of silane grafted, glass reinforced, stereoregular polymers of branched, higher alpha- olefins than glass reinforcements sized for
compatibility with polyolefins such as those
described in Example I above.
Example III
In this inventive example, the glass fiber reinforcement product used was not one generally recommended for use with polyolefins but was,
instead, one recommended for use in phenolic, epoxy, DAP (diallyl phenalate), and thermoset polyester resin systems. The specific product is a commercial product from PPG Industries, Inc., designated Type 1156 Chopped Strand. It is a G-filament diameter glass fiber with a 1/8-inch fiber length. Although the exact sizing composition is not disclosed by the manufacturer, it is believed that Type 1156 Chopped Strand contains both a polyfunctional epoxy resin film-former and an epoxy-functional silane. The amount of sizing on the product is about 1.15 weight percent based on total weight of the sized glass.
The process described above for Example I was repeated with the exception that the glass fiber reinforcement product was Type 1156 Chopped Strand. The properties of test specimens molded from the resulting compound (Compound 3) are listed in Table III.
It is again clear from the data that glass fiber reinforcement with a sizing composition which includes both a polyfunctional epoxy resin and an epoxy-functional silane provides significantly better mechanical properties in test specimens molded from compounds of silane grafted, glass reinforced, stereoregular polymers of branched, higher alpha- olefins than glass reinforcements sized for
compatibility with polyolefins such as those
described in Example I above. The additional
improvement in properties of test specimens molded from Compound 3 compared to those molded from
Compound 2 is due to the smaller filament diameter of the glass fiber reinforcement.
Example IV
In this inventive example, an epoxy-functional silane, 3-glycidoxypropyltrimethoxysilane (Ucarsil™ TC-100 available from Union Carbide
Corporation) was used in conjunction with glass fiber of the type used in Example I, one sized for
compatibility with polypropylene. The procedure was that of Example I, with the epoxy-functional silane included with the group of ingredients which were bag mixed.
PMP, vinyl-polymerizable silane and additives 100.89 parts epoxy-functional silane 0.50 parts
OCF 457 BA glass fiber 43.45 parts
The PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
Properties of the resulting compound (Compound 4) are listed in Table III.
The mechanical properties of test specimens molded from Compound 4 relative to the properties of those molded from Compound 1 which did not have an epoxy-functional silane are significantly better.
Example V
In this inventive example, a polyfunctional epoxy resin typical of "epoxy film formers" used in some glass fiber reinforcement sizing compositions was used in conjunction with the glass fiber
reinforcement sized for compatibility with
polypropylene which was used in Example I. The specific epoxy compound used was a bisphenol A extended bisphenol A/epichlorohydrin condensation product available from Shell Chemical Company as Epon™ 1009F. The epoxide equivalent weight is approximately 2,500-4,000. The procedure was that of
Example I, with the polyfunctional epoxy resin included with the group of ingredients which were bag mixed. The following ingredients were bag mixed:
PMP, vinyl-polymerizable silane and additives 100.89 parts epoxy-resin (Epon™ 1009) 1.00 parts
OCF 457 BA glass fiber 43.67 parts
The PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
Properties of test specimens molded from the
resulting compound (Compound 5) are given in Table III.
The mechanical properties of test specimens molded from Compound 5 relative to the properties of those molded from Compound 1 which did not have a polyfunctional epoxy resin are significantly better.
Example VI
In this inventive example both the epoxy-functional silane used in Example IV and the epoxy resin used in Example V were used in conjunction with the glass fiber reinforcement sized for compatibility with polypropylene used in Example I. Essentially, the procedures of Examples IV and V were repeated except that the ingredients and their relative weight levels were as follows:
PMP, vinyl-polymerizable silane and additives 100.89 parts epoxy-functional silane 0.50 parts epoxy resin 1.00 parts 0CF 457 BA glass fiber 43.88 parts
The PMP with additives was a drum tumbled mixture as described in the introduction to these examples. The properties of the resulting compound (Compound 6) are listed in Table III.
The increase in properties of Compound 6 relative to those of Compound 1 is again apparent.
This example, as well as the inventive Examples II, ill, IV and V described above, indicates that sizing compositions for treating glass fibers which contain (a) one or more polyfunctional epoxy resins as a film-former, (b) one or more epoxy-functional silanes as a coupling agent or, (c) a mixture of one or more polyfunctional epoxy resins and one or more epoxy-functional silanes, provide improved adhesion between the glass fiber strand and silane grafted stereoregular polymers of branched, higher alpha-olefins.
This example, as well as the proceding examples described above, also indicates that as an alternative commercially sized glass fiber products without one or more of these ingredients can be used to provide improved adhesion between the glass fiber strand and silane grafted stereoregular polymers of branched higher alpha-olefins if (a) one or more polyfunctional epoxy resins or, (b) one or more epoxy-functional silanes or, (c) a mixture of one or more polyfunctional epoxy resins and one or more epoxy-functional silanes is blended with the PMP and additives for silane grafting described in this invention. TABLE III
Properties of Glass Reinforoed Silane Grafted Branched Higher Alpha-Olef in Polymers
with Epoxy-Functional Silaneg and/or Epoxy Resins
Compound 1 Compound Compound Compound Compound Compound
Properties (Control) 2 3 4 5 6
Tensile Strength, 8,900 11,200 11,700 10,100 9,800 10,300 psi
Flexural Strength, 12,700 15,400 16,100 13,700 13,400 13,700 psi
Flexural Modulus, 765 855 812 788 780 780 ksi
Elongation, % 3.5 4.7 5.0 3.8 3.9 3.9
Notched Izod I mpact
Strength, ft-lb/in 1.1 1.4 1.2 1.2 1.1 1.1
Unnotched Izod Impact
Strength, ft-lb/in 3.5 6.5 5.9 4.2 4.4 4.5
Heat Distortion
Tamperature at
264 psi, ºC. 187 188 196 183 185 186
Example VII
Compound 7 is a control example for comparison purposes. The following components were dry mixed for about 60 minutes at 25ºC. (room temperature) by drum tumbling.
PMP homopolymer 100 parts
zinc stearate 0.04 parts
Irganox 1010 0.25 parts maleic anhydride 0.80 parts Aztec 2,5-Di 0.10 parts
This drum tumbled mixture was then mixed by hand with 43.37 parts glass fiber reinforcement in a plastic bag (bag mixed) to produce a mixture with 30 weight percent, based on weight of the polymer and
additives, of glass fiber reinforcement. The glass reinforcement product used was a commercially
available product sized for compatibility with polypropylene produced by Owens-Corning Fiberglas Corporation and designated 457 BA. This glass product was described in Example I above. The mixture was compounded, stranded, palletized and dried as described in Example I. The resulting compound was injection molded into ASTM test
specimens and tested as described in Example I.
Measured properties of test specimens molded from the resin of Compound 7 are listed in Table IV. The test procedures shown in Table II above were utilized to test all of the Compounds given in these examples.
Example VIII
In this inventive example, the glass fiber reinforcement material used was not one generally recommended for use with polyolefins but is, instead, one recommended for use with polybutylene
terephthalate (a thermoplastic polyester),
polycarbonate and styrenic resin systems.
The glass fiber reinforcement material used in this example was a commercial product from CertainTeed Corporation designated Chopped Strand 930. This glass fiber reinforcement material was described in Example II above.
The process described above for Example VII was repeated with the exception that the glass fiber reinforcement material used was the Chopped Strand 930 glass fiber reinforcement material described in Example II. The properties of test specimens molded from the resulting compound (Compound 8) are listed in Table IV.
It is clear from the data that glass fiber reinforcement with a sizing composition which
includes both a polyfunctional epoxy resin and an epoxy-functional silane provides significantly better mechanical properties in test specimens molded from compounds of maleic anhydride grafted, glass
reinforced, stereoregular polymers of branched, higher alpha-olefins than does use of glass
reinforcements sized for compatibility with
polyolefins such as those used in Example VII above.
Example IX
In this inventive example, an epoxy- functional silane, 3-glycidoxypropyltrimethoxysilane (Ucarsil™ TC-100 available from Union Carbide
Corporation) was used in conjunction with glass fiber of the type used in Example VII, one sized for compatibility with polypropylene. The procedure was that of Example VII, with the epoxy-functional silane included with the group of ingredients which were bag mixed:
PMP, carboxylic anhydride and
additives 101.19 parts epoxy-functional silane 0.50 parts
OCF 457 BA glass fiber 43.45 parts The PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
Properties of the resulting compound (Compound 9) are listed in Table IV. The increase in mechanical properties of test specimens molded from Compound 9 relative to the properties in compounds of maleic anhydride grafted, glass reinforced, stereoregular polymers of branched, higher alpha-olefins such as that of Compound 7 which did not have an epoxy-functional silane is readily apparent.
Example X
In this inventive example, a polyfunctional epoxy resin typical of "epoxy film formers" used in some glass fiber reinforcement sizing compositions was used in conjunction with the glass fiber
reinforcement sized for compatibility with
polypropylene which was used in Example VII. The specific epoxy compound used was a bisphenol A extended bisphenol A/epichlorohydrin condensation product available from Shell Chemical Company
as Epon™ 1009F. The epoxide equivalent weight is approximately 2,500-4,000. The procedure was that of Example VII, with the polyfunctional epoxy resin included with the group of ingredients which were bag mixed. The ingredients which were bag mixed were as follows:
PMP, carboxylic anhydride and
additives 101.19 parts epoxy resin 1.00 parts
OCF 457 BA glass fiber 43.67 parts
The PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
Properties of test specimens molded from the resulting compound (Compound 10) are given in
Table IV.
The increase in mechanical properties of test specimens molded from Compound 10 relative to the properties of test specimens molded from Compound
7 which did not have a polyfunctional epoxy resin is readily apparent. Example XI
In this inventive example both the epoxy- functional silane used in Example IX and the epoxy resin used in Example X were used in conjunction with the glass fiber reinforcement sized for compatibility with polypropylene used in Example VII. Essentially, the procedures of Examples IX and X were repeated except that the ingredients were as follows:
PMP, carboxylic anhydride and
additives 101.19 parts epoxy-functional silane 0.50 parts epoxy resin 1.00 parts
OCF 457 BA glass fiber 43.88 parts
The PMP with additives was a drum tumbled mixture as described in the introduction to these examples.
The properties of test specimens molded from the resulting compound (Compound 11) are listed in Table IV.
The increase in properties of test specimens molded from Compound 11 relative to those of Compound 7 is again apparent.
This example, as well as the inventive Examples VIII, IX and X described above, indicates that sizing compositions for treating glass fibers which contain (a) one or more polyfunctional epoxy resins as a film-former, (b) one or more epoxy- functional silanes as a coupling agent or, (c) a mixture of one or more polyfunctional epoxy resins and one or more epoxy-functional silanes, provide improved adhesion between the glass fiber strand and maleic anhydride grafted stereoregular polymers of branched, higher alpha-olefins.
This example, as well as the preceding examples described above, also indicates that as an alternative commercially sized glass fiber products without one or more of these ingredients can be used to provide improved adhesion between the glass fiber strand and maleic anhydride grafted stereoregular polymers of branched higher alpha-olefins if (a) one or more polyfunctional epoxy resins or, (b) one or more epoxy-functional silanes or, (c) a mixture of one or more polyfunctional epoxy resins and one or more epoxy-functional silanes is blended with the PMP and additives for maleic anhydride grafting described in this invention.
TABLE IV
Properties of Glass Reinforced Carboxylic Anhydride Grafted Baranched Higher
Alpha-Qlefin Polymers with Epoxy-Functional Silanes and/or Epoxy Resin
Compound 7 Compound Compound Compound Compound
Properties (Control) 8 9 10 11
Tensile Strength, 7,800 11,300 10,700 9,800 10,500 psi
Flexural Strength, 10,700 16,300 15,700 14,100 15,300 psi
Flexural Modulus, 741 779 784 746 792 ksi
Elongation, % 2.7 5.0 4.8 4.2 4.3
Notched Izod Impact
Strength, ft-lb/in 0.8 1.9 1.6 1.2 1.5
Unnotched Izod Impact
Strength, ft-lb/in 3.2 10.3 9.5 6.0 7.2
Heat Distortion
Temperature at
264 psi, ºC. 162 195 194 189 189
Example XII
In this inventive example, the glass fiber reinforcement material used was not one generally recommended for use with polyolefins but is, instead, one recommended for use with polybutylene
terephthalate (a thermoplastic polyester),
polycarbonate and styrenic resin systems.
The glass fiber reinforcement material used in this example was a commercial product from
CertainTeed Corporation designated Chopped Strand 930. This glass fiber reinforcement material was described in Example II above.
The process similar to that described above for Example VII was repeated with the exceptions that: (a) the glass fiber reinforcement material used was the Chopped Strand 930 glass fiber
reinforcement material described in Example II; and (b) the PMP was modified with muconic acid instead of 3-methacryloxypropyltrimethoxysilane. The PMP, after being stabilized with a hindered phenol as described in the introduction to these examples, was mixed with 0.04 phr zinc stearate, 0.10 phr tetrakis(methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)proprionate)methane (available
commercially from Ciba-Geigy Corporation as Irganox 1010), 0.50 phr muconic acid in the form of cis,cis 2,4-hexadienedioic acid (available commercially from Celgene Corporation) and 0.05 phr a,a'-bis(tert-butylperoxy)diisopropyl benzene (available from
Hercules, Inc., as Vulcup R). The components were dry mixed for about 60 minutes at about 25ºC. (room temperature) by drum tumbling.
The drum tumbled polymer mixture described above was grafted using the processing conditions as described in Example I and subsequently mixed with
43.24 parts glass fiber reinforcement in the extruder to produce a mixture with 30 weight percent glass fiber reinforcement.
Articles made from the compound produced in this Example XII (Compound 12) were tested using the same test methods as were used in all the foregoing examples. The resulting properties shown in the following Table V indicated that articles made from PMP which had been grafted with muconic acid and reinforced with glass having sizing containing materials with epoxy functionality also demonstrated improved properties when compared with articles made from PMP which had been grafted with unsaturated hydrolyzable silane or carboxylic anhydride and reinforced with the same glass reinforcement.
TABLE V
Properties of Glass Reinforced Muconic Acid Grafted Branched Higher Alpha-Olefin Polymers with EPOXV - Functional Salines and/or EPOXV Resins
Compound Properties Compound 2a Compound 8a 12
Tensile Strength,
psi 11 ,200 11,300 10,700
Elongation, % 4.7 5.0 5.1
Notched Izod
Impact Strength,
ft-lb/in 1.4 1.9 1.2
Unnotched Izod
Impact Strength,
ft-lb/in 6.5 10.3 6.1
Heat Distortion
Temperature
at 264º psi, ºC. 188 195 199 aRuns 2 and 8 are repeated here for purposes of easier comparison. Compound 2 was made using PMP grafted with an unsaturated hydrolyzable silane. Compound 8 was made using PMP grafted with a carboxylic acid.
While the polymers and methods of this invention have been described in detail for the purpose of illustration, the inventive polymers and methods are not to be construed as limited thereby. This patent is intended to cover all changes and modifications within the spirit and scope thereof.

Claims

C L A I M S
1. A composition comprising:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides;
carboxylic acid anhydride derivatives; and mixtures thereof;
(c) a free radical generator;
(d) glass; and
(e) at least one epoxy resin.
2. A composition as recited in claim 1, wherein said epoxy resin is selected from the group of bisphenol A epoxy compounds, bisphenol F epoxy compounds, aliphatic ether epoxy compounds, novalac epoxides, isocyanurate epoxides and mixtures thereof.
3. A composition as recited in claim 2, wherein said epoxy resin is a condensation product of bisphenol A and epichlorohydrin.
4. A composition as recited in claim 1, wherein said stereoregular polymer of branched, higher alpha-olefins is selected from the group of 3-methyl-1-butene; 3-methyl-1-pentene; 4-methyl-1-pentene; 4-methyl-1-hexene; 3,3-dimethyl-1-butene; 4,4-dimethyl-1-hexene; 3-ethyl-1-hexene and mixtures thereof.
5. A composition as recited in claim 4, wherein said stereoregular polymer of branched, higher alpha-olefins is 4-methyl-1-pentene.
6. A composition as recited in claim 4, wherein said stereoregular polymer of branched, higher alpha-olefins is 3-methyl-1-butene.
7. A composition as recited in claim 1,
wherein said grafting compound is at least one vinyl- polymerizable, unsaturated, hydrolyzable silane selected from those within the formula:
RaSiXbYc
wherein R is a monovalent hydrocarbon group, X is a silicon-bonded hydrolyzable group, Y is a silicon- bonded monovalent organic group containing at least one vinyl-polymerizable unsaturated bond, a is an integer of 0 to 2, preferably 0; b is an integer of 1 to 3, preferably 3; c is an integer of 1 to 3, preferably 1; and a + b + c is equal to 4; and
wherein said free radical generator is an organic peroxide selected from the group of alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates and hydroperoxides.
8. A composition as recited in claim 1, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 4-methyl-1-pentene;
wherein said grafting compound is a vinyl-polymerizable, unsaturated, hydrolyzable silane selected from the group of 3-methacrylpropyltrimethoxysilane;
vinyltrichlorosilane; vinyltriethoxysilane;
vinyltrimethoxysilane; vinyltris(beta-methoxyethoxy)silane; vinyltriacetoxysilane; 3-methacryloxypropyltris(beta-methoxyethoxy)silane; and mixtures thereof;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3; a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy resin is a condensation product of bisphenol A and epichlorohydrin.
9. A composition as recited in claim 1, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 3-methyl-1- butene;
wherein said grafting compound is a vinyl- polymerizable, unsaturated, hydrolyzable silane selected from the group of 3- methacrylpropyltrimethoxysilane;
vinyltrichlorosilane; vinyltriethoxysilane;
vinyltrimethoxysilane; vinyltris(beta- methoxyethoxy)silane; vinyltriacetoxysilane; 3- methacryloxypropyltris(beta-methoxyethoxy)silane; and mixtures thereof;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert- butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert- butylperoxy)hexyne-3;
a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy resin is a condensation product of bisphenol A and epichlorohydrin.
10. A composition as recited in claim 1, wherein said grafting compound is selected from the group of carboxylic acids, carboxylic acid
anhydrides, carboxylic acid derivatives, carboxylic acid anhydride derivatives; and mixtures thereof; and wherein said free radical generator is selected from the group of alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates and hydroperoxides.
11. A composition as recited in claim 10, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 4-methyl-1-pentene;
wherein said grafting compound is muconic acid;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3; a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy resin is a condensation product of bisphenol A and epichlorohydrin.
12. A composition as recited in claim 10, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 4-methyl-1-pentene;
wherein said grafting compound is a
carboxylic acid anhydride;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexyne-3; a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy resin is a condensation product of bisphenol A and epichlorohydrin.
13. A composition as recited in claim 10, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 3-methyl-1-butene;
wherein said grafting compound is a carboxylic acid anhydride;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3; a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy resin is a condensation product of bisphenol A and epichlorohydrin.
14. A composition as recited in claim 1, wherein said grafting compound is present in an amount ranging from 0.1 parts by weight to about 2 parts by weight grafting compound per 100 parts by weight polymer;
wherein said free radical generator is present in an amount in the range of about 0.001 to about 5 parts by weight of free radical generator per 100 parts by weight polymer;
wherein said glass is present in an amount in the range of about 10 to about 200 parts by weight per 100 parts by weight polymer;
wherein said epoxy resin is present in said polymer in a range from about 0.05 to about 5 parts by weight of epoxy resin per 100 parts by weight polymer.
15. A composition as recited in claim 1, wherein said grafting compound is present in an amount ranging from 0.1 parts by weight to about 2 parts by weight grafting compound per 100 parts by weight polymer;
wherein said free radical generator is present in an amount in the range of about 0.001 to about 5 parts by weight of free radical generator per 100 parts by weight polymer;
wherein said glass is present in an amount in the range of about 10 to about 200 parts by weight per 100 parts by weight polymer;
wherein said epoxy resin is present in sizing on said glass in said polymer in a range from about 0.15 to about 2 weight percent based on total weight of said sizing and said glass.
16. A composition comprising:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides;
carboxylic acid anhydride derivatives; and mixtures -thereof;
(c) a free radical generator;
(d) glass; and
(e) at least one epoxy-functional silane.
17. A composition as recited in claim 16, wherein said epoxy-functional silane is one within the formula:
Figure imgf000047_0001
wherein Z is
Figure imgf000047_0002
or O
X is (a) a linear or branched alkylene, arylene or arylalkylene hydrocarbon radical having from 1 to about 15 carbon atoms, or (b) a chlorine atom;
R is a hydrocarbon radical having from 1 to about 8 carbon atoms;
m is an integer of at least 1; and n is an integer of 1 to 3.
18. A composition as recited in claim 16, wherein said epoxy-functional silane is one selected from the group of 3-glycidoxypropyltrimethoxysilane, beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, [2-(3,4-epoxy-4-methylcyclohexyl)propyl]methyldiethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2-glycidoxypropyltrimethoxysilane, and mixtures
thereof.
19. A composition as recited in claim 18, wherein said epoxy-functional silane is 3- glycidoxypropyltrimethoxysilane.
20. A composition as recited in claim 18, wherein said epoxy-functional silane is beta-(3,4- epoxycyclohexyl)ethyltrimethoxysilane.
21. A composition as recited in claim 16, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of a monomer selected from the group of 4-methyl-1-pentene, 3- methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1- hexene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene and mixtures thereof.
22. A composition as recited in claim 21, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 4-methyl-1- pentene.
23. A composition as recited in claim 21, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 3-methyl-1- butene.
24. A composition as recited in claim 16, wherein said grafting compound is a vinyl-polymerizable, unsaturated, hydrolyzable silane selected from the group of 3-methacrylpropyltrimethoxysilane;
vinyltrichlorosilane; vinyltriethoxysilane;
vinyltrimethoxysilane;
vinyltris(beta-methoxyethoxy)silane;
vinyltriacetoxysilane; 3-methacryloxypropyltris(beta-methoxyethoxy)silane; and mixtures thereof; and
wherein said free radical generator is selected from the group of alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates and hydroperoxides.
25. A composition as recited in claim 16, wherein said grafting compound is 3-methacrylpropyltrimethoxysilane.
26. A composition as recited in claim 16, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 4-methyl-1-pentene;
wherein said grafting compound is a vinyl-polymerizable, unsaturated, hydrolyzable silane selected from the group of 3- methacrylpropyltrimethoxysilane;
vinyltrichlorosilane; vinyltriethoxysilane;
vinyltrimethoxysilane; vinyltrie(beta- methoxyethoxy)silane; vinyltriacetoxysilane; 3-methacryloxypropyltris(beta-methoxyethoxy)silane; and mixtures thereof;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3; a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy-functional silane is 3-glycidoxypropyltrimethoxysilane.
27. A composition as recited in claim 16, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 3-methyl-1-butene;
wherein said grafting compound is a vinyl-polymerizable, unsaturated, hydrolyzable silane selected from the group of 3-methacrylpropyltrimethoxysilane;
vinyltrichlorosilane; vinyltriethoxysilane;
vinyltrimethoxysilane; vinyltris(beta-methoxyethoxy)silane; vinyltriacetoxysilane; 3-methacryloxypropyltris(beta-methoxyethoxy)silane; and mixtures thereof; wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert- butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert- butylperoxy)hexyne-3; a,a'-bis(tert- butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy-functional silane is 3- glycidoxypropyltrimethoxysilane.
28. A composition as recited in claim 16, wherein said grafting compound is selected from the group of carboxylic acids, carboxylic anhydrides, carboxylic acid derivatives and carboxylic acid anhydride derivatives; and mixtures thereof; and
wherein said free radical generator is selected from the group of alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates and hydroperoxides.
29. A composition as recited in claim 16, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 4-methyl-1-pentene;
wherein said grafting compound is muconic acid;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3; a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy-functional silane is 3-glycidoxypropyltrimethoxysilane.
30. A composition as recited in claim 16, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 4-methyl-1- pentene;
wherein said grafting compound is a
carboxylic anhydride;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3; a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy-functional silane is 3-glycidoxypropyltrimethoxysilane.
31. A composition as recited in claim 16, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of 3-methyl-1-butene;
wherein said grafting compound is a carboxylic anhydride;
wherein said free radical generator is selected from the group of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; dicumyl peroxide; di-tert-butyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3; a,a'-bis(tert-butylperoxy)diisopropylbenzene; and mixtures thereof; and
wherein said epoxy-functional silane is 3-glycidoxypropyltrimethoxysilane.
32. A composition as recited in claim 16, wherein said grafting compound is present in an amount ranging from 0.1 parts by weight to about 2 parts by weight grafting compound per 100 parts by weight polymer;
wherein said free radical generator is present in an amount in the range of about 0.001 to about 5 parts by weight of free radical generator per 100 parts by weight polymer;
wherein said glass is present in an amount in the range of about 10 to about 200 parts by weight per 100 parts by weight polymer;
wherein said epoxy-functional silane is present in said polymer in a range from about 0.05 to about 5 parts per 100 parts polymer.
33. A composition as recited in claim 16, wherein said grafting compound is present in an amount ranging from 0.1 parts by weight to about 2 parts by weight grafting compound per 100 parts by weight polymer;
wherein said free radical generator is present in an amount in the range of about 0.001 to about 5 parts by weight of free radical generator per
100 parts by weight polymer;
wherein said glass is present in an amount in the range of about 10 to about 200 parts by weight per 100 parts by weight polymer;
wherein said epoxy-functional silane is present in sizing on said glass in a range from about 0.05 to about 0.5 weight percent based on total weight of said sizing and said glass.
34. A composition comprising:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides;
carboxylic acid anhydride derivatives; and mixtures thereof;
(c) a free radical generator;
(d) glass;
(e) at least one epoxy resin; and (f) at least one epoxy-functional silane.
35. A composition as recited in claim 34, wherein said epoxy resin is selected from the group of bisphenol A epoxy compounds, bisphenol F epoxy compounds, aliphatic ether epoxy compounds, novalac epoxides, isocyanurate epoxides and mixtures thereof; and
wherein said epoxy-functional silane is one within the formula:
wherein
Figure imgf000053_0001
Z is
Figure imgf000053_0002
or O
X is (a) a linear or branched alkylene, arylene or arylalkylene hydrocarbon radical having from 1 to about 15 carbon atoms, or (b) a chlorine atom;
R is a hydrocarbon radical having from 1 to about 8 carbon atoms;
m is an integer of at least 1; and n is an integer of 1 to 3.
36. A composition as recited in claim 34, wherein said grafting compound is a vinyl- polymerizable, unsaturated, hydrolyzable silane selected from the group of 3-methacrylpropyltrimethoxysilane;
vinyltrichlorosilane; vinyltriethoxysilane;
vinyltrimethoxysilane; vinyltris(beta-methoxyethoxy)silane; 5-vinyltriacetoxysilane; 3-methacryloxypropyltris(beta-methoxyethoxy)silane; and mixtures thereof; and
wherein said free radical generator is selected from the group of alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates and hydroperoxides.
37. A composition as recited in claim 34, wherein said grafting compound is selected from the group consisting of carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides; carboxylic acid anhydride derivatives; and mixtures thereof.
38. A composition as recited in claim 34, wherein said stereoregular polymer of branched, higher alpha-olefins is a polymer of a monomer selected from the group of 4-methyl-1-pentene, 3- methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1- hexene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene and mixtures thereof.
39. A composition as recited in claim 34, wherein said grafting compound is present in an amount ranging from about 0.1 parts by weight to about 2 parts by weight grafting compound per 100 parts by weight polymer;
wherein said free radical generator is present in an amount in the range of about 0.001 to about 5 parts by weight of free radical generator per 100 parts by weight polymer;
wherein said glass is present in an amount in the range of about 10 to about 200 parts by weight per 100 parts by weight polymer;
wherein said epoxy resin is present in said polymer in a range from about 0.05 to about 5 parts per 100 parts polymer;
wherein said epoxy-functional silane is present in said polymer in a range from about 0.05 to about 5 parts per 100 parts polymer.
40. A composition as recited in claim 34, wherein said grafting compound is present in an amount ranging from about 0.1 parts by weight to about 2 parts by weight grafting compound per 100 parts by weight polymer;
wherein said free radical generator is present in an amount in the range of about 0.001 to about 5 parts by weight of free radical generator per 100 parts by weight polymer; wherein said glass is present in an amount in the range of about 10 to about 200 parts by weight per 100 parts by weight polymer;
wherein said epoxy resin is present in sizing on said glass in a range from about 0.15 to about 2 weight percent based on total weight of said sizing and said glass;
wherein said epoxy-functional silane is present in sizing on said glass in a range from about 0.05 to about 0.5 weight percent based on total weight of said sizing and said glass.
41. A process for making a reinforced
thermoplastic material comprising combining:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides;
carboxylic acid anhydride derivatives; and mixtures thereof;
(c) a free radical generator;
(d) glass; and
(e) at least one epoxy resin.
42. A process for making a reinforced
thermoplastic material comprising combining:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides;
carboxylic acid anhydride derivatives; and mixtures thereof;
(c) a free radical generator; (d) glass ; and
(e) at least one epoxy-functional silane.
43. A process for making a reinforced
thermoplastic material comprising combining:
(a) a stereoregular polymer of branched, higher alpha-olefins which has been stabilized with at least one hindered phenol;
(b) a grafting compound selected from the group consisting of vinyl-polymerizable, unsaturated, hydrolyzable silanes; carboxylic acids; carboxylic acid derivatives; carboxylic acid anhydrides;
carboxylic acid anhydride derivatives; and mixtures thereof;
(c) a free radical generator;
(d) glass;
(e) at least one epoxy resin; and
(f) at least one epoxy-functional silane.
44. An article of manufacture produced from the composition of claim 1.
45. An article of manufacture produced from the composition of claim 16.
46. An article of manufacture produced from the composition of claim 34.
PCT/US1992/002210 1991-03-22 1992-03-19 Glass-reinforced grafted branched higher alpha-olefins WO1992016582A1 (en)

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