CN103755930A - 含有少量环丁二醇的聚酯组合物制成的膜和/或片材 - Google Patents
含有少量环丁二醇的聚酯组合物制成的膜和/或片材 Download PDFInfo
- Publication number
- CN103755930A CN103755930A CN201310616094.0A CN201310616094A CN103755930A CN 103755930 A CN103755930 A CN 103755930A CN 201310616094 A CN201310616094 A CN 201310616094A CN 103755930 A CN103755930 A CN 103755930A
- Authority
- CN
- China
- Prior art keywords
- mole
- polyester
- film
- residue
- sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
- A01G9/14—Greenhouses
- A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47F—SPECIAL FURNITURE, FITTINGS, OR ACCESSORIES FOR SHOPS, STOREHOUSES, BARS, RESTAURANTS OR THE LIKE; PAYING COUNTERS
- A47F5/00—Show stands, hangers, or shelves characterised by their constructional features
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/24—Dialysis ; Membrane extraction
- B01D61/30—Accessories; Auxiliary operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D23/00—Details of bottles or jars not otherwise provided for
- B65D23/10—Handles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D43/00—Lids or covers for rigid or semi-rigid containers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01F—ADDITIONAL WORK, SUCH AS EQUIPPING ROADS OR THE CONSTRUCTION OF PLATFORMS, HELICOPTER LANDING STAGES, SIGNS, SNOW FENCES, OR THE LIKE
- E01F8/00—Arrangements for absorbing or reflecting air-transmitted noise from road or railway traffic
- E01F8/0005—Arrangements for absorbing or reflecting air-transmitted noise from road or railway traffic used in a wall type arrangement
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D13/00—Special arrangements or devices in connection with roof coverings; Protection against birds; Roof drainage; Sky-lights
- E04D13/03—Sky-lights; Domes; Ventilating sky-lights
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/1336—Illuminating devices
- G02F1/133602—Direct backlight
- G02F1/133606—Direct backlight including a specially adapted diffusing, scattering or light controlling members
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/753—Medical equipment; Accessories therefor
- B29L2031/7542—Catheters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
-
- 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
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
-
- 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
- Y10T428/16—Two dimensionally sectional layer
- Y10T428/161—Two dimensionally sectional layer with frame, casing, or perimeter structure
-
- 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
- Y10T428/16—Two dimensionally sectional layer
- Y10T428/162—Transparent or translucent layer or section
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24058—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
- Y10T428/24074—Strand or strand-portions
- Y10T428/24091—Strand or strand-portions with additional layer[s]
- Y10T428/24099—On each side of strands or strand-portions
- Y10T428/24107—On each side of strands or strand-portions including mechanically interengaged strands, strand-portions or strand-like strips
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
-
- 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]
-
- 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]
- Y10T428/31507—Of polycarbonate
-
- 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]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
-
- 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]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Abstract
本发明涉及含有少量环丁二醇的聚酯组合物制成的膜和/或片材。其中,本发明的一个方面是一种含下述组分的聚酯:(a)二羧酸组分,其含有70-100摩尔%的对苯二甲酸残基、最多30摩尔%的芳族二羧酸残基或脂族二羧酸残基;和(b)二醇组分,其含有11-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基和75-89摩尔%的1,4-环己烷二甲醇残基,其中二羧酸组分的总摩尔%是100摩尔%,二醇组分的总摩尔%是100摩尔%。所述聚酯可以制成制品。
Description
本申请是一项发明专利申请的分案申请,其母案的申请日为2006年3月30日、申请号为200680020745.8(PCT/US2006/011968)、发明名称为“含有少量环丁二醇的聚酯组合物制成的膜和/或片材”。
技术领域
本发明总的涉及由聚酯组合物制成的膜和/或片材,该聚酯组合物由对苯二甲酸,其酯;2,2,4,4-四甲基-1,3-环丁二醇或混合物;以及1,4-环己烷二甲醇制得。用于本发明的膜和/或片材中的这些组合物具有下列性能中的两种或两种以上的独特结合,使得它们能够容易地形成膜和/或片材。这些性能包括:高冲击强度,中等到高的玻璃化转变温度(Tg),韧性,特定的比浓对数粘度,低的韧-脆转变温度,良好的色彩和清晰度,低密度,耐化学性、水解稳定性,以及长的半结晶期(半结晶期)。
背景技术
聚对苯二甲酸1,4-亚环己基二亚甲基酯(PCT)是一种仅仅基于对苯二甲酸或其酯和1,4-环己烷二甲醇的酯,它们是本领域公知的,并可从商业获得。这种聚酯能在冷却时快速地从熔体结晶,从而难以通过本领域公知的方法例如挤出、注塑等形成无定形制品。为了减慢PCT的结晶速率,可以制备含有额外二羧酸或二醇(例如间苯二甲酸或乙二醇)的共聚酯。这些被乙二醇或间苯二甲酸改性的PCT也是本领域公知的,并可从商业获得。
一种通常用于生产膜、片材和模塑制品的共聚酯是从对苯二甲酸、1,4-环己烷二甲醇和乙二醇制备的。虽然这些共聚酯可用于许多最终用途中,但是当在配料中包含足够的改性乙二醇以提供长的半结晶期时,它们显示在性能例如玻璃化转变温度和冲击强度方面的缺陷。例如,由对苯二甲酸、1,4-环己烷二甲醇和乙二醇制备并且具有足够长的半结晶期的共聚酯可以提供无定形产品,与本文公开的组合物相比,其显示出不利的较高韧脆转变温度和较低的玻璃化转变温度。
4,4’-亚异丙基二苯酚的聚碳酸酯(双酚A聚碳酸酯)已经用作本领域已知的聚酯的替代品,也是公知的工程模塑塑料。双酚A聚碳酸酯是透明的高性能塑料,其具有良好的物理性能,例如尺寸稳定性、高耐热性和良好的冲击强度。尽管双酚A聚碳酸酯具有许多良好的物理性能,但是它的较高熔体粘度导致熔体加工性差,并且聚碳酸酯的耐化学品性差。它们也难以热成型。
含有2,2,4,4-四甲基-1,3-环丁二醇的聚合物也在本领域中有描述。但是,一般而言,这些聚合物显示出高的比浓对数粘度、高熔体粘度和/或高Tg(玻璃化转变温度),使得在工业中使用的设备不足以生产或后聚合加工这些材料。
因此,本领域所需要的膜和/或片包含的聚酯应具有两种或两种以上的至少一种选自以下的性能:韧性、中等的玻璃化转变温度(Tg)、高冲击强度、低的韧-脆转变温度、耐化学性、水解稳定性、良好的色彩和清晰度、低密度,长的结晶半生期和/或热成形性,这将使得它们易于形成膜和/或片。在一些实施方案中,聚酯在熔融加工和/或加热成形前如对干燥无要求或仅有最低要求,则更容易被热成形。
发明内容
一般认为,某些含有由具有一定单体组成、比浓对数粘度和/或玻璃化转变温度的对苯二甲酸、其酯,或它们的混合物;1,4-环己烷二甲醇;以及2,2,4,4-四甲基-1,3-环丁二醇形成的组合物的膜和/或片材,在高冲击强度、水解稳定性、韧性、耐化学性、良好的色彩和清晰度、长的半结晶期、低的韧-脆转变温度、低的比重、和/或热成形性中的一项或多项性能上优于由现有技术中已知的聚酯制成的膜和/或片材,并且优于聚碳酸酯。这些膜和/或片材被认为可在标准的工业设备上加工。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)10-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-90摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度是大于0.60-1.2dL/g。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)10-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-90摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度是大于0.60-0.9dL/g。
在一方面,本发明涉及包含了至少一种聚酯的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)10-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-90摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度是0.65-1.2dL/g。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组 合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)11-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-89摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度0.80dL/g或更小。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)12-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-88摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.80dL/g或更小。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)13-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-87摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.80dL/g或更小。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-86摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.80dL/g或更小。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-86摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.75dL/g或更小。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-86摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.35-0.75dL/g。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-86摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.50-0.75dL/g。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-86摩尔%的1,4-环己烷二甲醇残基,以及
(c)来自至少一种支化剂残基中的残基;
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.5-1.2dL/g。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)17-23摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)77-83摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度是从0.60到小于0.72dL/g。
其中,聚酯的玻璃化转变温度是从95到115℃。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;
ii)75-86摩尔%的1,4-环己烷二甲醇残基,以及
iii)0.1到小于10摩尔%的乙二醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.60-0.72dL/g;以及
其中,聚酯的玻璃化转变温度是从95到115℃。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
至少一种聚酯,其包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)17-23摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;
ii)77-83摩尔%的1,4-环己烷二甲醇残基,以及
iii)0.01到小于15摩尔%的乙二醇残基;
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度是从0.35到0.75dL/g。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-86摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下, 在25℃测定的聚酯的比浓对数粘度为0.75dL/g或更小。
其中,聚酯的玻璃化转变温度是从95到115℃。
在一方面,本发明涉及包含了聚酯组合物的膜或片,该聚酯组合物包括:
(I)至少一种聚酯,其包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)10-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-90摩尔%的1,4-环己烷二甲醇残基;以及
(II)至少一种热稳定剂和/或其反应产品;
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.5-1.2dL/g。
在一方面,本发明涉及包含了聚酯组合物的膜或片,该聚酯组合物包括:
(I)至少一种聚酯,其包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-86摩尔%的1,4-环己烷二甲醇残基;以及
(II)至少一种热稳定剂和/或其反应产品;
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;并且
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.5-1.2dL/g。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)10-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-90摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.5-1.2dL/g。
其中,聚酯的玻璃化转变温度是从95到115℃。
在一方面,本发明涉及包含了含有至少一种聚酯的聚酯组合物的膜或片,该聚酯包括:
(a)二羧酸组分,包括:
i)70-100摩尔%的对苯二甲酸残基;
ii)0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii)0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b)二醇组分,包括:
i)14-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii)75-86摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;
其中,在60/40(wt/wt)的苯酚/四氯乙烷中,0.5g/100ml浓度下,在25℃测定的聚酯的比浓对数粘度为0.35-0.75dL/g。
其中,聚酯的玻璃化转变温度是从95到115℃。
在一方面,含有用于本发明中的聚酯组合物的膜和/或片材包含至少一种聚碳酸酯。
在一个方面,所述用于本发明的膜和/或片材中的聚酯组合物不含聚碳酸酯。
在一个方面,用于本发明的膜和/或片材中的聚酯含有小于15摩尔%的乙二醇残基,例如0.01摩尔%至小于15摩尔%的乙二醇残基。
在一个方面,用于本发明的膜和/或片材中的聚酯不含乙二醇残基。
在一个方面,用于本发明的膜和/或片材中的聚酯组合物含有至少一种热稳定剂和/或其反应产物。
在一个方面,用于本发明的膜和/或片材中的聚酯不含支化剂,或在聚酯的聚合之前或期间加入至少一种支化剂。
在一个方面,用于本发明的膜和/或片材中的聚酯含有至少一种支化剂,且与支化剂的添加方法或顺序无关。
在一个方面,用于本发明的膜和/或片材中的聚酯不是由1,3-丙二醇或1,4-丙二醇单独或其组合制备的。在另一个方面,1,3-丙二醇或1,4-丙二醇单独或其组合可以用于制备本发明的聚酯。
在本发明的一个方面,在本发明特定聚酯中使用的顺式-2,2,4,4-四甲基-1,3-环丁二醇的摩尔%是大于50摩尔%或大于55摩尔%的顺式-2,2,4,4-四甲基-1,3-环丁二醇,或是大于70摩尔%的顺式-2,2,4,4-四甲基-1,3-环丁二醇;其中顺式-2,2,4,4-四甲基-1,3-环丁二醇和反式-2,2,4,4-四甲基-1,3-环丁二醇的总摩尔百分比等于100摩尔%。
在本发明的一个方面,在本发明特定聚酯中使用的2,2,4,4-四甲基-1,3-环丁二醇异构体的摩尔%是30-70摩尔%的顺式-2,2,4,4-四甲基-1,3-环丁二醇和30-70摩尔%的反式-2,2,4,4-四甲基-1,3-环丁二醇,或者40-60摩尔%的顺式-2,2,4,4-四甲基-1,3-环丁二醇和40-60摩尔%的反式-2,2,4,4-四甲基-1,3-环丁二醇,其中顺式-2,2,4,4-四甲基-1,3-环丁二醇和反式-2,2,4,4-四甲基-1,3-环丁二醇的总摩尔百分比等于100摩尔%。
在一方面,使用了聚酯组合物的本发明的膜和/或片材包括但不限于挤出的和/或模塑的物品,包括但不限于挤出的膜和/或片材,压延的膜和/或片材,压缩模塑的膜和/或片材,溶液铸塑的膜和/或片材。制造膜和/或片材的方法包括但不限于挤出、压延、压缩模塑、和溶液铸塑。
在一方面,使用聚酯组合物也最大地降低了和/或消除了在进行熔融过程和/或热成形前对干燥步骤的需要。
在一方面,用于本发明的膜和/或片材中的一些聚酯可为无定 形的或半结晶的。在一方面,用于本发明的膜和/或片材中的一些聚酯具有相对较低的结晶性。用于本发明的一些聚酯因此具有相当的无定形的形态,这就意味着聚酯基本上含有无序的聚合物区域。
附图说明
图1是显示共聚单体对改性PCT共聚酯的最快半结晶期的影响的图。
图2是显示共聚单体对缺口悬臂梁式冲击强度试验(ASTM D256,1/8英寸厚,10密耳缺口)中的脆韧转变温度(Tbd)的影响的图。
图3是显示2,2,4,4-四甲基-1,3-环丁二醇的组成对共聚酯的玻璃化转变温度(Tg)的影响的图。
具体实施方式
可以参考以下对本发明具体实施方案和工作实施例的详细描述更好地理解本发明。
本文使用的术语“聚酯”包括共聚酯。根据本发明的目的,本发明的某些实施方案公开在“发明概述”中,并在以下进一步描述。本发明的其它实施方案也在下面描述。
据信具有本文所描述的组成的用于本发明的膜和/或片材中的聚酯具有以下两种或多种物理性能的独特组合:高冲击强度,中等玻璃化转变温度,耐化学品性,水解稳定性,低的韧脆转变温度,良好的颜色和透明性,低密度,长的半结晶期,以及良好的加工性,这使得它们易于成型为膜和/或片材。此外,描述于本发明的一些实施方案中的膜或片状制品无需对膜或片材进行预干燥就可加热成形。以前一直不相信,在本发明的一些实施方案中的含有这里描述的组合物的聚酯中可呈现出良好的冲击强度、耐热性、耐化学性、密度、可加工性这些性能的有利结合,和/或呈现出所描述的四种性能中的至少两种的结合。
在本文使用的术语“聚酯”包括“共聚酯”,并理解为表示通过一种或多种双官能羧酸和/或多官能羧酸与一种或多种双官能羟基化合物和/或多官能羟基化合物反应制得的合成聚合物。通常,双官能羧酸可以是二羧酸,双官能羟基化合物可以是二元醇,例如甘醇(glycol)和二醇(diol)。在本申请中使用的术语“二醇”包括但不限于二醇、 甘醇和/或多官能羟基化合物,例如支化剂。或者,双官能羧酸可以是羟基羧酸,例如对-羟基苯甲酸;双官能羟基化合物可以是带有两个羟基取代基的芳核,例如氢醌。在本文使用的术语“残基”表示任何通过与相应单体进行缩聚和/或酯化反应而被引入聚合物中的有机结构。在本文使用的术语“重复单元”表示具有经由羰基氧基键接的二羧酸残基和二醇残基的有机结构。因此,例如,二羧酸残基可以衍生自二羧酸单体或其相应的酰卤、酯、盐、酸酐或其混合物。所以,在本文使用的术语“二羧酸”表示包括二羧酸和二羧酸的任何衍生物,包括其相应的酰卤、酯、半酯、盐、半盐、酸酐、混合酸酐或其混合物,用于与二醇反应制备聚酯的过程中。此外,在本申请中使用的术语“二酸”包括但不限于多官能酸,例如支化剂。在本文使用的术语“对苯二甲酸”表示包括对苯二甲酸本身和其残基,以及对苯二甲酸的任何衍生物,包括其相应的酰卤、酯、半酯、盐、半盐、酸酐、混合酸酐或其混合物,用于与二醇反应制备聚酯的过程中。
在一个实施方案中,对苯二甲酸可以用作原料。在另一个实施方案中,对苯二甲酸二甲酯用作原料。在另一个实施方案中,对苯二甲酸和对苯二甲酸二甲酯的混合物可以用作原料和/或用作中间材料。
用于本发明的聚酯通常可以从二羧酸和二醇按照基本相等的比例反应制备,所述二羧酸和二醇作为它们的相应残基被引入聚酯聚合物中。所以,本发明的聚酯可以含有基本等摩尔比例的酸残基(100摩尔%)和二醇(和/或多官能羟基化合物)残基(100摩尔%),使得重复单元的总摩尔%等于100摩尔%。所以,在本说明书中提供的摩尔百分比可以是基于酸残基的总摩尔数、二醇残基的总摩尔数或重复单元的总摩尔数。例如,基于酸残基总量计含有30摩尔%间苯二甲酸的聚酯表示聚酯含有30摩尔%间苯二甲酸残基,基于100摩尔%的酸残基计。因此,在每100摩尔的酸残基中有30摩尔的间苯二甲酸残基。在另一个例子中,基于二醇残基总量计含有25摩尔%2,2,4,4-四甲基-1,3-环丁二醇的聚酯表示聚酯含有25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基,基于100摩尔%的二醇残基计。因此,在每100摩尔的二醇残基中有25摩尔的2,2,4,4-四甲基-1,3-环丁二醇残基。
在本发明的一个方面,用于本发明的膜和/或片材中的聚酯的Tg可以是至少一个以下范围:80-125℃;80-120℃;80-115℃;80-110 ℃;80-105℃;80-100℃;80-95℃;80-90℃;80-85℃;85-125℃;85-120℃;85-115℃;85-110℃;85-105℃;85-100℃;85-95℃;85-90℃;90-125℃;90-120℃;90-115℃;90-110℃;90-105℃;90-100℃;90-95℃;95-125℃;95-120℃;95-115℃;95-110℃;95-105℃;95至小于105℃;95-100℃;100-125℃;100-120℃;100-115℃;100-110℃;105-125℃;105-120℃;105-115℃;105-110℃;大于105至125℃;大于105至120℃;大于105至115℃;大于105至110℃;110-125℃;110-120℃;110-115℃;大于110至125℃;大于110至120℃;大于110至115℃;115-125℃;和115-120℃。
在本发明的其它方面,用于本发明的膜和/或片材中的聚酯的二醇组分包括但不限于至少一个以下范围组合:10-25摩尔%2,2,4,4-四甲基-1,3-环丁二醇和75-90摩尔%1,4-环己烷二甲醇;10-24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76-90摩尔%1,4-环己烷二甲醇;10-20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和80-90摩尔%1,4-环己烷二甲醇;10至小于20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和大于80至90摩尔%1,4-环己烷二甲醇;10-19摩尔%2,2,4,4-四甲基-1,3-环丁二醇和81-90摩尔%1,4-环己烷二甲醇;10-18摩尔%2,2,4,4-四甲基-1,3-环丁二醇和82-90摩尔%1,4-环己烷二甲醇;和10-15摩尔%2,2,4,4-四甲基-1,3-环丁二醇和85-90摩尔%1,4-环己烷二甲醇。
在本发明的其它方面,用于本发明的膜和/或片材中的聚酯的二醇组分包括但不限于至少一个以下范围组合:大于10至25摩尔%2,2,4,4-四甲基-1,3-环丁二醇和75至小于90摩尔%1,4-环己烷二甲醇;大于10至24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76至小于90摩尔%1,4-环己烷二甲醇;大于10至20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和80至小于90摩尔%1,4-环己烷二甲醇;大于10至小于20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和大于80至小于90摩尔%1,4-环己烷二甲醇;大于10至19摩尔%2,2,4,4-四甲基-1,3-环丁二醇和81至小于90摩尔%1,4-环己烷二甲醇;大于10至18摩尔%2,2,4,4-四甲基-1,3-环丁二醇和82至小于90摩尔%1,4-环己烷二甲醇;大于10至15摩尔%2,2,4,4-四甲基-1,3-环丁二醇和85至小于90摩尔%1,4-环己烷二甲醇;
在本发明的其它方面,用于本发明的膜和/或片材中的聚酯的二醇组分包括但不限于至少一个以下范围组合:11-25摩尔%2,2,4,4-四 甲基-1,3-环丁二醇和75-89摩尔%1,4-环己烷二甲醇;11-24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76-89摩尔%1,4-环己烷二甲醇;11-20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和80-89摩尔%1,4-环己烷二甲醇;11-19摩尔%2,2,4,4-四甲基-1,3-环丁二醇和81-89摩尔%1,4-环己烷二甲醇;11-18摩尔%2,2,4,4-四甲基-1,3-环丁二醇和82-89摩尔%1,4-环己烷二甲醇;11-15摩尔%2,2,4,4-四甲基-1,3-环丁二醇和85-89摩尔%1,4-环己烷二甲醇。
在本发明的其它方面,用于本发明的膜和/或片材中的聚酯的二醇组分包括但不限于至少一个以下范围组合:12-25摩尔%2,2,4,4-四甲基-1,3-环丁二醇和75-88摩尔%1,4-环己烷二甲醇;12-24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76-88摩尔%1,4-环己烷二甲醇;12-20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和80-88摩尔%1,4-环己烷二甲醇;12-19摩尔%2,2,4,4-四甲基-1,3-环丁二醇和81-88摩尔%1,4-环己烷二甲醇;12-18摩尔%2,2,4,4-四甲基-1,3-环丁二醇和82-88摩尔%1,4-环己烷二甲醇;12-18摩尔%2,2,4,4-四甲基-1,3-环丁二醇和82-88摩尔%1,4-环己烷二甲醇;12-15摩尔%2,2,4,4-四甲基-1,3-环丁二醇和85-88摩尔%1,4-环己烷二甲醇。
在本发明的其它方面,用于本发明的膜和/或片材中的聚酯的二醇组分包括但不限于至少一个以下范围组合:13-25摩尔%2,2,4,4-四甲基-1,3-环丁二醇和75-87摩尔%1,4-环己烷二甲醇;13-24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76-87摩尔%1,4-环己烷二甲醇;13-20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和80-87摩尔%1,4-环己烷二甲醇;13-19摩尔%2,2,4,4-四甲基-1,3-环丁二醇和81-87摩尔%1,4-环己烷二甲醇;和13-18摩尔%2,2,4,4-四甲基-1,3-环丁二醇和82-87摩尔%1,4-环己烷二甲醇;和13-15摩尔%2,2,4,4-四甲基-1,3-环丁二醇和85-87摩尔%1,4-环己烷二甲醇。
在本发明的其它方面,用于本发明的膜和/或片材中的聚酯的二醇组分包括但不限于至少一个以下范围组合:14-25摩尔%2,2,4,4-四甲基-1,3-环丁二醇和75-86摩尔%1,4-环己烷二甲醇;14-24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76-86摩尔%1,4-环己烷二甲醇;14-20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和80-86摩尔%1,4-环己烷二甲醇;14-19摩尔%2,2,4,4-四甲基-1,3-环丁二醇和81-86摩尔%1,4-环己烷二甲 醇;14-18摩尔%2,2,4,4-四甲基-1,3-环丁二醇和82-86摩尔%1,4-环己烷二甲醇;15-25摩尔%2,2,4,4-四甲基-1,3-环丁二醇和75-85摩尔%1,4-环己烷二甲醇;15-24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76-85摩尔%1,4-环己烷二甲醇;15-20摩尔%2,2,4,4-四甲基-1,3-环丁二醇和80-85摩尔%1,4-环己烷二甲醇;16-24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76-84摩尔%1,4-环己烷二甲醇;16-23摩尔%2,2,4,4-四甲基-1,3-环丁二醇和77-84摩尔%1,4-环己烷二甲醇;17-24摩尔%2,2,4,4-四甲基-1,3-环丁二醇和76-83摩尔%1,4-环己烷二甲醇;17-23摩尔%2,2,4,4-四甲基-1,3-环丁二醇和77-83摩尔%1,4-环己烷二甲醇;20-25摩尔%2,2,4,4-四甲基-1,3-环丁二醇和75-80摩尔%1,4-环己烷二甲醇。
除了上述二醇之外,用于本发明的膜和/或片材中的聚酯组合物的聚酯也可以由1,3-丙二醇、1,4-丁二醇或其混合物制备。认为由1,3-丙二醇、1,4-丁二醇或其混合物制备的本发明组合物可以具有至少一个本文所述的Tg范围、至少一个本文所述的比浓粘度范围和/或至少一个本文所述的二醇或二酸范围。除此之外或作为另一种选择,由1,3-丙二醇、1,4-丁二醇或其混合物制备的聚酯也可以由至少一个以下用量的1,4-环己烷二甲醇制备:0.1-80摩尔%;0.1-99摩尔%;0.1-90摩尔%;0.1-80摩尔%;0.1-70摩尔%;0.1-60摩尔%;0.1-50摩尔%;0.1-40摩尔%;0.1-35摩尔%;0.1-30摩尔%;0.1-25摩尔%;0.1-20摩尔%;0.1-15摩尔%;0.1-10摩尔%;0.1-5摩尔%;1-99摩尔%;1-90摩尔%;1-80摩尔%;1-70摩尔%;1-60摩尔%;1-50摩尔%;1-40摩尔%;1-35摩尔%;1-30摩尔%;1-25摩尔%;1-20摩尔%;1-15摩尔%;1-10摩尔%;1-5摩尔%;5-99摩尔%;5-90摩尔%;5-80摩尔%;5-70摩尔%;5-60摩尔%;5-50摩尔%;5-40摩尔%;5-35摩尔%;5-30摩尔%;5-25摩尔%;5-20摩尔%;5-15摩尔%;5-10摩尔%;10-99摩尔%;10-90摩尔%;10-80摩尔%;10-70摩尔%;10-60摩尔%;10-50摩尔%;10-40摩尔%;10-35摩尔%;10-30摩尔%;10-25摩尔%;10-20摩尔%;10-15摩尔%;20-99摩尔%;20-90摩尔%;20-80摩尔%;20-70摩尔%;20-60摩尔%;20-50摩尔%;20-40摩尔%;20-35摩尔%;20-30摩尔%;和20-25摩尔%。
对于本发明的具体实施方案,用于本发明的膜和/或片材中的聚酯的比浓对数粘度在60/40(重量/重量)的苯酚/四氯乙烷中在0.5g/100 ml的浓度下于25℃测定,可以在至少一个以下范围内:0.1-0.80dL/g;0.1-小于0.80dL/g;0.10-0.75dL/g;0.10-小于0.75dL/g;0.10-0.72dL/g;0.10-0.70dL/g;0.10至小于0.70dL/g;0.10-0.68dL/g;0.10至小于0.68dL/g;0.10-0.65dL/g;0.20-0.80dL/g;0.2至小于0.80dL/g;0.20-0.75dL/g;0.20至小于0.75dL/g;0.20-0.72dL/g;0.20-0.70dL/g;0.20至小于0.70dL/g;0.20-0.68dL/g;0.20至小于0.68dL/g;0.20-0.65dL/g;0.35-0.80dL/g;0.35-小于0.80dL/g;0.35-0.80dL/g;0.35-0.75dL/g;0.35至小于0.75dL/g;0.35-0.72dL/g;0.35-0.70dL/g;0.35至小于0.70dL/g;0.35-0.68dL/g;0.35至小于0.68dL/g;0.35-0.65dL/g;0.40-0.80dL/g;0.40至小于0.80dL/g0.40-0.75dL/g;0.40至小于0.75dL/g;0.40-0.72dL/g;0.40-0.70dL/g;0.40至小于0.70dL/g;0.40-0.68dL/g;0.40至小于0.68dL/g;0.40-0.65dL/g;0.42-0.80dL/g;0.42至小于0.80dL/g;大于0.42至0.80dL/g;大于0.42至小于0.80dL/g;大于0.42至0.75dL/g;大于0.42至小于0.75dL/g;大于0.42至0.72dL/g;大于0.42至小于0.70dL/g;大于0.42至0.68dL/g;大于0.42至小于0.68dL/g;和大于0.42至0.65dL/g。
对于本发明的具体实施方案,用于本发明的膜和/或片材中的聚酯的比浓对数粘度在60/40(重量/重量)的苯酚/四氯乙烷中在0.5g/100ml的浓度下于25℃测定,可以在至少一个以下范围内:0.45-0.80dL/g;0.45-小于0.80dL/g;0.45-0.75dL/g;0.45-小于0.75dL/g;0.45-0.72dL/g;0.45-0.70dL/g;0.45至小于0.70dL/g;0.45-0.68dL/g;0.45至小于0.68dL/g;0.45-0.65dL/g;0.50-0.80dL/g;0.50-小于0.80dL/g;0.50-0.75dL/g;0.50至小于0.75dL/g;0.50-0.72dL/g;0.50-0.70dL/g;0.50至小于0.70dL/g;0.50-0.68dL/g;0.50至小于0.68dL/g;0.50-0.65dL/g;0.55-0.80dL/g;0.55至小于0.80dL/g;0.55-0.75dL/g;0.55至小于0.75dL/g;0.55-0.72dL/g;0.55-0.70dL/g;0.55至小于0.70dL/g;0.55-0.68dL/g;0.55至小于0.68dL/g;0.55-0.65dL/g;0.58-0.80dL/g;0.58至小于0.80dL/g;0.58-0.75dL/g;0.58至小于0.75dL/g;0.58-0.72dL/g;0.58-0.70dL/g;0.58至小于0.70dL/g;0.58-0.68dL/g;0.58至小于0.68dL/g;0.58-0.65dL/g;0.60-0.80dL/g;0.60至小于0.80dL/g;0.60-0.75dL/g;0.60至小于0.75dL/g;0.60-0.72dL/g;0.60-0.70dL/g;0.60至小于0.70dL/g;0.60-0.68dL/g;0.60至小于0.68dL/g;0.60-0.65dL/g;大于0.60 至小于0.80dL/g;大于0.60至0.75dL/g;大于0.60至小于0.75dL/g;大于0.60至0.72dL/g;0.65-0.80dL/g;0.65至小于0.80dL/g;0.65-0.75dL/g;0.65至小于0.75dL/g;0.65至0.72dL/g;0.65-0.70dL/g;0.65至小于0.70dL/g;0.68-0.80dL/g;0.68-0.75dL/g;0.68至小于0.75dL/g;0.68-0.72dL/g;0.70-0.80dL/g;0.70至小于0.80dL/g;0.70-0.75dL/g;和0.70至小于0.75dL/g。
对于本发明的具体实施方案,用于本发明膜和/或片材中的聚酯的比浓对数粘度在60/40(重量/重量)的苯酚/四氯乙烷中在0.5g/100ml的浓度下于25℃测定,可以在至少一个以下范围内:0.40-1.2dL/g;0.40-1.1dL/g;0.40-1dL/g;0.40至小于1dL/g;0.40-0.98dL/g;0.40-0.95dL/g;0.40-0.90dL/g;0.40-0.85dL/g;0.45-1.2dL/g;0.45-1.1dL/g;0.45-1dL/g;0.45至小于1dL/g;0.45-0.98dL/g;0.45-0.95dL/g;0.45-0.90dL/g;0.45-0.85dL/g;0.50-1.2dL/g;0.50-1.1dL/g;0.50-1dL/g;0.50至小于1dL/g;0.50-0.98dL/g;0.50-0.95dL/g;0.50-0.90dL/g;0.50-0.85dL/g;0.55-1.2dL/g;0.55-1.1dL/g;0.55-1dL/g;0.55至小于1dL/g;0.55-0.98dL/g;0.55-0.95dL/g;0.55-0.90dL/g;0.55-0.85dL/g;0.58-1.2dL/g;0.58-1.1dL/g;0.58-1dL/g;0.58-小于1dL/g;0.58-0.98dL/g;0.58-0.95dL/g;0.58-0.90dL/g;0.58-0.85dL/g;0.60-1.2dL/g;0.60-1.1dL/g;0.60-1dL/g;0.60至小于1dL/g;0.60-0.98dL/g;0.60-0.95dL/g;0.60-0.90dL/g;0.60-0.85dL/g;0.65-1.2dL/g;0.65-1.1dL/g;0.65-1dL/g;0.65至小于1dL/g;0.65-0.98dL/g;0.65-0.95dL/g;0.65-0.90dL/g;0.65-0.85dL/g;0.68-1.2dL/g;0.68-1.1dL/g;0.68-1dL/g;0.68至小于1dL/g;0.68-0.98dL/g;0.68-0.95dL/g;0.68-0.90dL/g;0.68-0.85dL/g;0.70-1.2dL/g;0.70-1.1dL/g;0.70-1dL/g;0.70至小于1dL/g;0.70-0.98dL/g;0.70-0.95dL/g;0.70-0.90dL/g;0.70-0.85dL/g;0.75-1.2dL/g;0.75-1.1dL/g;0.75-1dL/g;0.75至小于1dL/g;0.75-0.98dL/g;0.75-0.95dL/g;0.75-0.90dL/g;0.75-0.85dL/g;大于0.76dL/g-1.2dL/g;大于0.76dL/g至1.1dL/g;大于0.76dL/g至1dL/g;大于0.76dL/g至小于1dL/g;大于0.76dL/g至0.98dL/g;大于0.76dL/g至0.95dL/g;大于0.76dL/g至0.90dL/g;大于0.80dL/g至1.2dL/g;大于0.80dL/g至1.1dL/g;大于0.80dL/g至1dL/g;大于0.80dL/g至小于1dL/g;大于0.80dL/g至1.2dL/g;大于0.80dL/g至0.98dL/g;大于0.80dL/g至0.95dL/g;大于0.80dL/g至0.90dL/g。
除特别指出外,预计用于本发明的膜和/或片材中的聚酯组合物可具有本文描述的至少一个比浓对数粘度范围,以及本文描述的组合物的至少一个单体范围。除特别指出外,预计用于本发明的膜和/或片材中的聚酯组合物可具有本文描述的至少一个Tg范围,以及本文描述的组合物的至少一个单体范围。除特别指出外,还预计用于本发明的膜和/或片材中的聚酯组合物可具有本文描述的至少一个Tg范围,本文描述的至少一个比浓对数粘度范围,以及本文描述的组合物的至少一个单体范围。
对用于本发明的膜和/或片材中的期望的聚酯而言,顺式/反式2,2,4,4-四甲基-1,3-环丁二醇的摩尔比可以从各自的纯形式或其混合物变化。在某些实施方案中,顺式和/或反式2,2,4,4-四甲基-1,3-环丁二醇的摩尔百分比是大于50摩尔%顺式和小于50摩尔%反式;或大于55摩尔%顺式和小于45摩尔%反式;或30-70摩尔%顺式和70-30%反式;或40-60摩尔%顺式和60-40摩尔%反式;或50-70摩尔%反式和50-30%顺式;或50-70摩尔%顺式和50-30%反式;或60-70摩尔%顺式和30-40摩尔%反式;或大于70摩尔%顺式和小于30摩尔%反式;其中顺式-和反式-2,2,4,4-四甲基-1,3-环丁二醇的总摩尔百分比等于100摩尔%。顺式/反式1,4-环己烷二甲醇的摩尔比可以在50/50-0/100、例如40/60-20/80的范围内变化。
在某些实施方案中,对苯二甲酸、它的酯(例如对苯二甲酸二甲酯)或对苯二甲酸和其酯的混合物占用于形成本发明的膜和/或片材中的聚酯的二羧酸组分的大部分或全部。在某些实施方案中,对苯二甲酸残基可以以至少70摩尔%、例如至少80摩尔%、至少90摩尔%、至少95摩尔%、至少99摩尔%或100摩尔%的浓度占用于形成本发明聚酯的二羧酸组分的一部分或全部。在某些实施方案中,可以使用较高量的对苯二甲酸以制备具有较高冲击强度的聚酯。为了公开的目的,术语“对苯二甲酸”和“对苯二甲酸二甲酯”在本文可以互换使用。在一个实施方案中,对苯二甲酸二甲酯是用于制备本发明聚酯的二羧酸组分的部分或全部。在所有实施方案中,可以使用70-100摩尔%或80-100摩尔%或90-100摩尔%或99-100摩尔%或100摩尔%的对苯二甲酸和/或对苯二甲酸二甲酯和/或其混合物。
除了对苯二甲酸残基之外,用于本发明的膜和/或片材中的聚 酯的二羧酸组分可以含有至多30摩尔%、至多20摩尔%、至多10摩尔%、至多5摩尔%或至多1摩尔%的改性芳族二羧酸。另一个实施方案含有0摩尔%的改性芳族二羧酸。因此,如果存在的话,认为一种或多种改性芳族二羧酸的量可以是任何上述端点值之间的范围,包括例如0.01-30摩尔%、0.01-20摩尔%、0.01-10摩尔%、0.01-5摩尔%和0.01-1摩尔%。在一个实施方案中,可以用于本发明的改性芳族二羧酸包括但不限于具有至多20个碳原子的那些,其可以是线性、对-取向或对称的。可以用于本发明的改性芳族二羧酸的例子包括但不限于间苯二甲酸、4,4’-二苯基二羧酸、1,4-、1,5-、2,6-、2,7-萘二甲酸和反-4,4’-茋二甲酸,以及它们的酯。在一个实施方案中,改性芳族二羧酸是间苯二甲酸。
用于本发明的膜和/或片材中的聚酯的羧酸组分可以进一步用至多10摩尔%、至多5摩尔%或至多1摩尔%的一种或多种含有2-16个碳原子的脂族二羧酸改性,例如丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸和十二烷二甲酸。某些实施方案也可以含有0.01摩尔%或更多、0.1摩尔%或更多、1摩尔%或更多、5摩尔%或更多或者10摩尔%或更多的一种或多种改性脂族二羧酸。另一个实施方案含有0摩尔%的改性脂族二羧酸。因此,如果存在的话,认为一种或多种改性脂族二羧酸的量可以是任何上述端点值之间的范围,包括例如0.01-10摩尔%和0.1-10摩尔%。二羧酸组分的总摩尔%是100摩尔%。
可以使用对苯二甲酸的酯和其它改性二羧酸或其相应酯和/或盐代替二羧酸。二羧酸酯的合适例子包括但不限于二甲基酯、二乙基酯、二丙基酯、二异丙基酯、二丁基酯和二苯基酯。在一个实施方案中,这些酯选自以下的至少一种:甲基酯、乙基酯、丙基酯、异丙基酯和苯基酯。
1,4-环己烷二甲醇可以是顺式、反式或其混合物,例如顺/反比例为60:40至40:60。在另一个实施方案中,反-1,4-环己烷二甲醇可以以60-80摩尔%的量存在。
在用于本发明的膜和/或片材中的聚酯组合物中,聚酯部分的二醇组分可以含有25摩尔%或更少的一种或多种与2,2,4,4-四甲基-1,3-环丁二醇或1,4-环己烷二甲醇不同的改性二醇;在一个实施方案中,用于本发明的膜和/或片材中的聚酯可以含有小于15摩尔%的一种或多种改性二醇。在另一个实施方案中,用于本发明的聚酯可以含有10摩尔% 或更少的一种或多种改性二醇。在另一个实施方案中,用于本发明的膜和/或片材中的聚酯可以含有5摩尔%或更少的一种或多种改性二醇。在另一个实施方案中,用于本发明的膜和/或片材中的聚酯可以含有3摩尔%或更少的一种或多种改性二醇。在另一个实施方案中,用于本发明的膜和/或片材中的聚酯可以含有0摩尔%的改性二醇。因此,如果存在的话,认为一种或多种改性二醇的量可以是任何上述端点值之间的范围,包括例如0.01-15摩尔%和0.1-10摩尔%。
用于形成本发明的膜和/或片材中的聚酯的改性二醇指与2,2,4,4-四甲基-1,3-环丁二醇或1,4-环己烷二甲醇不同并且含有2-16个碳原子的二醇。合适的改性二醇的例子包括但不限于乙二醇、二甘醇、1,2-丙二醇、1,3-丙二醇、新戊二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、对二甲苯二醇或它们的混合物。在一个实施方案中,改性二醇是乙二醇。在另一个实施方案中,改性二醇包括但不限于1,3-丙二醇和/或1,4-丁二醇。在另一个实施方案中,改性二醇不包括乙二醇。在另一个实施方案中,改性二醇不包括1,3-丙二醇和1,4-丁二醇。在另一个实施方案中,改性二醇不包括2,2-二甲基-1,3-丙二醇。
用于本发明的膜和/或片材中的聚酯组合物中的聚酯和/或聚碳酸酯可以含有分别基于二醇或二酸残基总摩尔百分比计的0-10摩尔%、例如0.01-5摩尔%、0.01-1摩尔%、0.05-5摩尔%、0.05-1摩尔%或0.1-0.7摩尔%或0.1-0.5摩尔%的一种或多种具有3个或更多羧基取代基、羟基取代基或其组合的支化单体的残基(在本文也称为支化剂)或其组合。在某些实施方案中,支化单体或支化剂可以在聚酯的聚合之前和/或期间和/或之后添加。用于本发明的膜和/或片材中的聚酯因此可以是线性或支化的。聚碳酸酯也可以是线性或支化的。在某些实施方案中,支化单体或支化剂可以在聚碳酸酯的聚合之前和/或期间和/或之后添加。
支化单体的例子包括但不限于多官能酸或多官能醇,例如偏苯三酸、偏苯三酸酐、苯均四酸二酐、三羟甲基丙烷、甘油、季戊四醇、柠檬酸、酒石酸、3-羟基戊二酸等。在一个实施方案中,支化单体残基可以含有0.1-0.7摩尔%的一种或多种选自至少一种以下的残基:偏苯三酸酐、苯均四酸二酐、甘油、山梨醇、1,2,6-己三醇、季戊四醇、三羟甲基乙烷和/或1,3,5-苯三酸。可以将支化单体加入聚酯反应混合物中或与 浓缩物形式的聚酯共混,例如描述在美国专利5,654,347和5,696,176中,将其中关于支化单体的公开内容引入本文供参考。
玻璃化转变温度(Tg)是使用来自Thermal Analyst Instrument的TA DSC2920以20℃/分钟的扫描速率测定的。
由于用于本发明的膜和/或片材中的一些聚酯在170℃下显示出的长的半结晶期(例如,大于5分钟),因此可生产的物品包括但不限于:注模件,注坯吹塑物,注坯拉伸吹塑物,挤出膜,挤出片,挤坯吹塑物,挤坯拉伸吹塑物,和纤维。可加热成形的片是由本发明提供的制造物品中的一个例子。用于本发明的膜和/或片材中的聚酯可以是无定形的或半结晶的。在一方面,用于本发明的膜和/或片材中的一些聚酯具有相对较低的结晶性。因此,用于本发明的膜和/或片材中的一些聚酯具有基本无定形形态,这就意味着聚酯包含基本上无序的聚合物区域。
在一个实施方案中,“无定形”聚合物的半结晶期可以在170℃大于5分钟或在170℃大于10分钟或在170℃大于50分钟或在170℃大于100分钟。在本发明的一个实施方案中,用于本发明的膜和/或片材中的聚酯的半结晶期是在170℃大于1000分钟。在另一个实施方案中,用于本发明的膜和/或片材中的聚酯的半结晶期是在170℃大于10000分钟。在本文使用的半结晶期可以使用本领域技术人员公知的方法检测。例如,聚酯的半结晶期t1/2可以通过经由激光和光探测器检测样品的透光率随着在温控加热台上的时间变化来测定。这种检测可以通过使聚合物暴露于温度Tmax、然后冷却到所需的温度来进行。然后将样品通过加热台保持在所需的温度,同时检测透射率随时间的变化。开始时,样品目测是透明的,具有高透光率,并且随着样品结晶而变浑浊。半结晶期是透光率处于初始透光率和最终透光率之间的一半时的时间。Tmax定义为熔融样品的结晶相畴所需要的温度(如果结晶相畴存在的话)。可以将样品加热到Tmax以在检测半结晶期之前调节样品。绝对Tmax对于各组合物是不同的。例如,可以将PCT加热到比290℃高的温度以熔融结晶相畴。
如实施例的表1和图1所示,2,2,4,4-四甲基-1,3-环丁二醇比其它共聚单体例如乙二醇和间苯二甲酸在增加半结晶期方面更有效,即聚合物达到其最大结晶度的一半所需的时间。通过降低PCT的结晶速率,即增加半结晶期,基于改性的PCT的无定形制品可以通过本领域公 知的方法生产,例如挤出、注塑等。如表1所示,这些材料显示比其它改性的PCT共聚酯更高的玻璃化转变温度和更低的密度。
对于一些本发明的实施方案,聚酯显示韧性和加工性组合的改进。例如,略微降低用于本发明的膜和/或片材中的聚酯的比浓对数粘度会获得加工性更好的熔体粘度,同时保持聚酯的良好物理性能例如韧性和耐热性。
提高1,4-环己烷二甲醇在基于对苯二甲酸、乙二醇和1,4-环己烷二甲醇的共聚酯中的含量可以改进韧性,这可以通过按照ASTM D256在缺口悬臂梁式冲击强度试验中检测脆韧转变温度测定。认为这种通过用1,4-环己烷二甲醇降低脆韧转变温度所实现的韧性改进是由于在共聚酯中的1,4-环己烷二甲醇的柔性和构象行为引起的。据信向PCT中引入2,2,4,4-四甲基-1,3-环丁二醇能通过降低脆韧转变温度而改进韧性,如实施例的表2和图2所示。
在一个实施方案中,在1弧度/秒下在旋转熔体流变仪中在290℃测得用于本发明的膜和/或片材中的聚酯的熔体粘度是小于30000泊。在另一个实施方案中,在1弧度/秒下在旋转熔体流变仪中在290℃测得用于本发明的膜和/或片材中的聚酯的熔体粘度是小于20000泊。
在一个实施方案中,在1弧度/秒下在旋转熔体流变仪中在290℃测得用于本发明的膜和/或片材中的聚酯的熔体粘度是小于15000泊。在一个实施方案中,在1弧度/秒下在旋转熔体流变仪中在290℃测得用于本发明的膜和/或片材中的聚酯的熔体粘度是小于10000泊。在另一个实施方案中,在1弧度/秒下在旋转熔体流变仪中在290℃测得用于本发明的膜和/或片材中的聚酯的熔体粘度是小于6000泊。在弧度/秒下的粘度与加工性相关。典型的聚合物在其加工温度下检测时在1弧度/秒下的粘度是小于10000泊。聚酯通常不在高于290℃的温度加工。聚碳酸酯通常在290℃的温度加工。在1弧度/秒的典型12熔体流速下的聚碳酸酯粘度在290℃是7000泊。
在本发明的一个实施方案中,用于本发明的膜和/或片材中的聚酯在厚度截面上显示优异的缺口悬臂梁式(Izod)冲击强度。如ASTM D256所述,缺口悬臂梁式冲击强度是常用的韧性检测方法。当通过悬臂梁式方法检测时,聚合物可以显示完全断裂破坏模式,其中试样断裂成两个独立的部件;或显示部分断裂破坏或无断裂破坏模式,其中试样 作为一个部件保留。完全断裂破坏模式与低能量破坏相关。部分断裂破坏或无断裂破坏模式与高能量破坏相关。用于检测悬臂梁式韧性的典型厚度是1/8”。在此厚度下,认为非常少的聚合物显示部分断裂破坏或无断裂破坏模式,其中聚碳酸酯是一个典型的例子。但是当试样的厚度增加到1/4”时,没有工业无定形材料会显示部分断裂破坏或无断裂破坏模式。在一个实施方案中,本发明实施例的组合物在使用1/4”厚度的试样进行悬臂梁式检测时显示出无断裂破坏模式。
用于本发明的膜和/或片材中的聚酯可以具有一个或多个以下性能。在一个实施方案中,根据ASTM D256在3.2mm(1/8英寸)厚棒中用10密耳的缺口在23℃测得用于本发明的膜和/或片材中的聚酯的缺口悬臂梁式冲击强度是至少150J/m(3ft-lb/in);在一个实施方案中,根据ASTM D256在3.2mm(1/8英寸)厚棒中用10密耳的缺口在23℃测得用于本发明的膜和/或片材中的聚酯的缺口悬臂梁式冲击强度是至少400J/m(7.5ft-lb/in);在一个实施方案中,根据ASTM D256在3.2mm(1/8英寸)厚棒中用10密耳的缺口在23℃测得用于本发明的膜和/或片材中的聚酯的缺口悬臂梁式冲击强度是至少1000J/m(18ft-lb/in)。在一个实施方案中,根据ASTM D256在6.4mm(1/4英寸)厚棒中用10密耳的缺口在23℃测得用于本发明的膜和/或片材中的聚酯的缺口悬臂梁式冲击强度是至少150J/m(3ft-lb/in);在一个实施方案中,根据ASTM D256在6.4mm(1/4英寸)厚棒中用10密耳的缺口在23℃测得用于本发明的膜和/或片材中的聚酯的缺口悬臂梁式冲击强度是至少400J/m(7.5ft-lb/in);在一个实施方案中,根据ASTM D256在6.4mm(1/4英寸)厚棒中用10密耳的缺口在23℃测得用于本发明的膜和/或片材中的聚酯的缺口悬臂梁式冲击强度是至少1000J/m(18ft-lb/in)。
在另一个实施方案中,用于本发明的膜和/或片材中的某些聚酯显示出根据ASTM D256在1/8英寸的厚棒中用10密耳的缺口在0℃测得的缺口悬臂梁式冲击强度比在-5℃测得的缺口悬臂梁式冲击强度增加至少3%或至少5%或至少10%或至少15%。另外,某些其它聚酯也可以显示出根据ASTM D256在1/8英寸的厚棒中用10密耳的缺口在0-30℃检测时保持为±5%的缺口悬臂梁式冲击强度。
在另一个实施方案中,与根据ASTM D256在1/8英寸的厚棒 中用10密耳的缺口在23℃检测的缺口悬臂梁式冲击强度相比,用于本发明的膜和/或片材中的某些聚酯显示出根据ASTM D256在1/4英寸的厚棒中用10密耳的缺口在23℃检测时损失不超过70%的缺口悬臂梁式冲击强度。
在一个实施方案中,基于根据ASTM D256在1/8英寸的厚棒中10密耳的缺口,用于本发明的膜和/或片材中的聚酯显示小于0℃的韧脆转变温度。
在一个实施方案中,使用梯度密度柱在23℃检测,用于本发明的膜和/或片材中的聚酯显示至少一个下述密度:在23℃的密度小于1.2g/ml;在23℃的密度小于1.18g/ml;在23℃的密度为0.8-1.3g/ml;在23℃的密度为0.80-1.2g/ml;在23℃的密度为0.8至小于1.2g/ml;在23℃的密度为1.0-1.3g/ml;在23℃的密度为1.0-1.2g/ml;在23℃的密度为1.0-1.1g/ml;在23℃的密度为1.13-1.3g/ml;在23℃的密度为1.13-1.2g/ml。
在一个实施方案中,用于本发明的膜和/或片材中的聚酯可以一般是目测透明的。术语“目测透明”在本文定义为当目测观察时不存在可看到的混浊、雾度和/或污浊。在另一个实施方案中,当聚酯与聚碳酸酯(包括但不限于双酚A聚碳酸酯)共混时,共混物可以是目测透明的。
在本发明的另一个实施方案中,用于本发明的膜和/或片材中的聚酯的黄变指数(ASTM D-1925)可以小于50或小于20。
在一个实施方案中,用于本发明的膜和/或片材中的聚酯和/或本发明的聚酯组合物(含或不含调色剂)可以具有色值L*、a*和b*,使用Hunter Lab Inc.Reston,Va.生产的Hunter Lab Ultrascan Spectra Colorimeter测定。颜色检测值是对聚酯的粒料或由其注塑或挤出的板材或其它制品检测的值的平均值。它们通过CIE的L*a*b*颜色体系测定(International Commission on Illumination),其中L*表示亮度坐标,a*表示红/绿坐标,b*表示黄/蓝坐标。在某些实施方案中,用于本发明的聚酯的b*值可以是-10至小于10,L*值可以是50-90。在其它实施方案中,用于本发明的聚酯的b*值可以处于以下范围之一中:-10至9;-10至8;-10至7;-10至6;-10至5;-10至4;-10至3;-10至2;-5至9;-5至8;-5至7;-5至6;-5至5;-5至4;-5至3;-5至2;0至9; 0至8;0至7;0至6;0至5;0至4;0至3;0至2;1至10;1至9;1至8;1至7;1至6;1至5;1至4;1至3;和1至2。在其它实施方案中,用于本发明的膜和/或片材中的聚酯的L*值可以处于以下范围之一中:50-60;50-70;50-80;50-90;60-70;60-80;60-90;70-80;79-90。
在一些实施方案中,使用用于本发明的膜和/或片材中的聚酯组合物能使在熔体加工和/或热成型之前的干燥步骤最小化和/或不需要干燥步骤。
在用于本发明的膜和/或片材中的聚酯组合物中的聚酯部分可以通过文献已知的方法制备,例如通过在均匀溶液中的方法,通过在熔体中的酯交换方法,和通过两相界面方法。合适的方法包括但不限于使一种或多种二羧酸与一种或多种二醇在100-315℃的温度和0.1-760mmHg的压力下反应足以形成聚酯的时间。关于生产聚酯的方法可以参见美国专利3,772,405,将关于这些方法的公开内容引入本文供参考。
在另一方面,本发明涉及一种生产用于本发明的膜和/或片材中的聚酯组合物中的聚酯的方法。该方法包括:
(I)将含有在任何用于本发明的聚酯中使用的单体的混合物在催化剂的存在下在150-240℃加热足以制备初始聚酯的时间;
(II)将来自步骤(I)的初始聚酯在240-320℃的温度加热1-4小时;和
(III)除去任何未反应的二醇。
适用于该方法的催化剂包括但不限于有机锌化合物或有机锡化合物。这种催化剂的使用是本领域公知的。用于本发明的催化剂例如包括但不限于乙酸锌、三-2-乙基己酸丁基锡、二乙酸二丁锡和/或氧化二丁锡。其它催化剂可以包括但不限于基于钛、锌、锰、锂、锗和钴的那些。催化剂的量可以是10-20000ppm或10-10000ppm,或10-5000ppm或10-1000ppm或10-500ppm,或10-300ppm或10-250ppm,基于催化剂金属和基于最终聚合物的重量计。该方法可以按照间歇或连续工艺进行。
一般,步骤(I)可以进行直到50重量%或更多的2,2,4,4-四甲基-1,3-环丁二醇已经反应。步骤(I)可以在大气压至100psig的压力下进行。在本文与本发明中所用催化剂相关使用的术语“反应产物”表 示任何与催化剂和在制备聚酯中所用单体的缩聚或酯化反应的产物,以及在催化剂和任何其它类型添加剂之间的缩聚或酯化反应的产物。
一般,步骤(II)和步骤(III)可以同时进行。这些步骤可以通过本领域公知的方法进行,例如通过将反应混合物置于0.002psig至低于大气压范围的压力下,或通过将热氮气吹过该混合物。
本发明进一步涉及一种通过上述方法生产的聚酯产品。
本发明进一步涉及一种聚合物共混物。该共混物包含:
((a)5-95重量%的至少一种上述聚酯;和
((b)5-95重量%的至少一种聚合物组分。
聚合物组分的合适例子包括但不限于聚酰胺如尼龙、与上述不同的聚酯、DuPont的聚苯乙烯;聚苯乙烯共聚物;苯乙烯/丙烯腈共聚物;丙烯腈/丁二烯/苯乙烯共聚物;聚甲基丙烯酸甲酯,丙烯酸类共聚物;聚醚酰亚胺,例如(一种来自General Electric的聚醚酰亚胺);聚苯醚,例如聚2,6-二甲基亚苯基醚或聚苯醚/聚苯乙烯共混物,例如NORYL(一种来自General Electric的聚2,6-二甲基亚苯基醚和聚苯乙烯树脂的共混物);聚苯硫醚;聚苯硫醚/砜;聚酯/碳酸酯;聚碳酸酯,例如(一种来自General Electric的聚碳酸酯);聚砜;聚砜醚;芳族二羟基化合物的聚醚酮;或任何上述聚合物的混合物。所述共混物可以通过本领域公知的常规加工技术制备,例如熔融共混或溶液共混。在一个实施方案中,在聚酯组合物中不存在聚碳酸酯。如果在用于本发明的膜和/或片材中的聚酯组合物中的共混物中使用聚碳酸酯,则该共混物可以是目测透明的。但是,用于本发明的膜和/或片材中的聚酯组合物组合物也可以排除聚碳酸酯或包含聚碳酸酯。
用于本发明的膜和/或片材中的聚碳酸酯可以根据公知的程序制备,例如通过使二羟基芳族化合物与碳酸酯前体(例如光气、卤代甲酸酯或碳酸酯)、分子量调节剂、酸受体和催化剂反应。制备聚碳酸酯的方法是本领域公知的,例如描述在美国专利4,452,933中,将其中关于聚碳酸酯制备的内容引入本文供参考。
合适的碳酸酯前体的例子包括但不限于羰基溴、羰基氯或其混合物;碳酸二苯基酯;碳酸二(卤代苯基)酯,例如碳酸二(三氯苯基)酯、碳酸二(三溴苯基)酯等;碳酸二(烷基苯基)酯,例如碳酸 二甲苯基酯;碳酸二(萘基)酯;碳酸二(氯萘基)酯,或其混合物;和二元酚的卤代甲酸酯。
合适的分子量调节剂的例子包括但不限于苯酚、环己醇、甲醇、烷基化苯酚,例如辛基酚、对叔丁基苯酚等。在一个实施方案中,分子量调节剂是苯酚或烷基化苯酚。
酸受体可以是有机酸或无机酸受体。合适的有机酸受体可以是叔胺,包括但不限于吡啶、三乙胺、二甲基苯胺、三丁胺等。无机酸受体可以是碱金属或碱土金属的氢氧化物、碳酸盐、碳酸氢盐或磷酸盐。
可以使用的催化剂包括但不限于能通常协助单体与光气的聚合反应的那些。合适的催化剂包括但不限于叔胺,例如三乙胺、三丙胺、N,N-二甲基苯胺;季铵化合物,例如四乙基溴化铵、十六烷基三乙基溴化铵、四正庚基碘化铵、四正丙基溴化铵、四甲基氯化铵、四甲基氢氧化铵、四正丁基碘化铵、苄基三甲基氯化铵;和季磷化合物,例如正丁基三苯基溴化磷和甲基三苯基溴化磷。
用于用于本发明的膜和/或片材中的聚酯组合物中的聚碳酸酯也可以是共聚酯碳酸酯,例如公开在美国专利3,169,121、3,207,814、4,194,038、4,156,069、4,430,484、4,465,820和4,981,898中的那些,将这些美国专利中关于共聚酯碳酸酯的内容引入本文供参考。
用于本发明的膜和/或片材中的共聚酯碳酸酯可以从商业获得和/或可以通过本领域公知的方法制备。例如,它们可以通常通过至少一种二羟基芳族化合物与光气和至少一种二酰氯(特别是间苯二甲酰氯、对苯二甲酰氯或这两者)的混合物反应获得。
另外,含有用于本发明的膜和/或片材中的聚酯的聚酯组合物和聚合物共混物组合物也可以含有基于聚酯组合物总重量计的0.01-25重量%或0.01-20重量%或0.01-15重量%或0.01-10重量%或0.01-5重量%的常规添加剂,例如着色剂、染料、脱模剂、阻燃剂、增塑剂、成核剂、稳定剂(包括但不限于UV稳定剂、热稳定剂和/或其反应产物)、填料和冲击改性剂。用于本发明并且本领域公知的典型可商购的冲击改性剂例如包括但不限于乙烯/丙烯三元聚合物;官能化聚烯烃,例如含有丙烯酸甲酯和/或甲基丙烯酸缩水甘油酯的那些;基于苯乙烯的嵌段共聚物冲击改性剂;和各种丙烯酸类核/壳型冲击改性剂。例如,可以通过添加到本体中、通过涂覆硬涂层或通过共挤出罩面层而将UV 添加剂引入本发明生产的制品中。这些添加剂的残基也是本发明聚酯组合物的部分。
用于本发明的膜和/或片材中的聚酯可以含有至少一种扩链剂。合适的扩链剂包括但不限于多官能(包括但不限于双官能)异氰酸酯、多官能环氧化物,包括例如环氧基化线型酚醛树脂,和苯氧基树脂。在某些实施方案中,扩链剂可以在聚合工艺结束时或在聚合工艺之后加入。如果在聚合工艺之后加入,则扩链剂可以在转化工艺例如注塑或挤出期间通过混合或通过添加来引入。扩链剂的用量可以根据所用的具体单体组成和所需的物理性能而变化,但是通常是约0.1-约10重量%,优选约0.1-约5重量%,基于聚酯的总重量计。
热稳定剂是能在聚酯生产期间和/或后聚合期间稳定聚酯的化合物,包括但不限于含磷化合物,包括但不限于磷酸、亚磷酸、膦酸、次膦酸、亚膦酸和它们的各种酯和盐。它们可以存在于用于本发明的膜和/或片材中的聚酯组合物中。这些酯可以是烷基酯、支化烷基酯、取代的烷基酯、双官能烷基酯、烷基醚、芳基酯和取代的芳基酯。在一个实施方案中,在具体含磷化合物中存在的酯基数目可以从0直至基于在所用稳定剂中存在的羟基数目计可允许的最大数目。术语“热稳定剂”表示包括其反应产物。在本文与本发明热稳定剂一起使用的术语“反应产物”表示在热稳定剂和任何在生产聚酯中所用单体之间的缩聚或酯化反应的任何产物,以及在催化剂和任何其它类型添加剂之间的缩聚或酯化反应的任何产物。
增强材料可以用于本发明的组合物中。增强材料可以包括但不限于碳单丝、硅酸盐、云母、粘土、滑石、二氧化钛、硅灰石、玻璃片、玻璃珠和纤维、聚合物纤维以及它们的混合物。在一个实施方案中,增强材料是玻璃,例如纤维状玻璃丝,玻璃和滑石的混合物,玻璃和云母的混合物,以及玻璃和聚合物纤维的混合物。
在另一种实施方式中,本发明进一步涉及包含了含有本文描述的聚酯组合物的膜和/或片材的制造物品。
用于本发明的膜和/或片材可以是对本领域技术人员而言显而易见的任意厚度。在一种实施方式中,本发明的膜的厚度不超过40密耳。在一种实施方式中,本发明的膜的厚度不超过35密耳。在一种实施方式中,本发明的膜的厚度不超过30密耳。在一种实施方式中, 本发明的膜的厚度不超过25密耳。在一种实施方式中,本发明的膜的厚度不超过20密耳。
在一种实施方式中,本发明的片的厚度不小于20密耳。在另一种实施方式中,本发明的片的厚度不小于25密耳。在另一种实施方式中,本发明的片的厚度不小于30密耳。在另一种实施方式中,本发明的片的厚度不小于35密耳。在另一种实施方式中,本发明的片的厚度不小于40密耳。
本发明进一步涉及包含本发明聚酯组合物的膜和/或片材。使聚酯形成膜和/或片材的方法为本领域熟知。本发明的膜和/或片材的例子包括但不限于:挤出的膜和/或片材,压延的膜和/或片材,压缩模塑的膜和/或片材,溶液铸塑锻膜和/或片材。制造膜和/或片材的方法包括但不限于挤出、压延、压缩模塑、和溶液铸塑。
由所述膜和/或片材生产的潜在制品的例子包括但不限于单轴拉伸的膜、双轴拉伸的膜、收缩膜(无论是否是单轴或双轴拉伸的),液晶显示膜(包括但不限于扩散片、补偿膜和保护膜)、热成型片、指示牌膜、户外标记、天窗、涂料、涂覆的制品、上漆的制品、层压材料、层压制品和/或多壁膜或片材。
指示牌膜的例子包括但不限于名片、膜转换叠层;买点显示器;在洗衣机上的平面或模内装饰板;冰箱上的平面接触面板;在烘箱上的平板;用于汽车的内装饰;汽车的仪表盘;手机盖;加热和通风控制显示器;汽车减震盘;汽车轮胎位移盘;用于汽车仪表盘的控制显示器或警示标志;家居用品上的面板、按键或显示屏;洗衣机上的面板、按键或显示屏;洗碟机上的面板、按键或显示屏;电子设备的键盘;移动电话、PDA(手提式电脑)或遥控器的键盘;电子设备的显示屏;手提式电子设备例如电话和PDA的显示器;用于汽车或标准电话的面板和外壳;电子设备上的标志;和用于手提电话的标志。
多壁膜或片材表示作为型材挤出的片材,其由彼此经由垂直条连接的多层组成。多壁膜或片材的例子包括但不限于温室和商业遮蓬。
在此本文的揭露中,术语“wt”是指“重量”。
下面的实施例进一步展示了用于膜和/或片材中的聚酯组合物以及制造聚酯组合物的方法和对其进行的评价,但这些实施例仅出于 对本发明进行解释说明的作用,而不对本发明构成任何限制。除非另外指明外,份是指重量份,温度单位是℃,或者是在室温,压力是大气压或接近大气压。
实施例
检测方法
聚酯的比浓对数粘度是在60/40(重量/重量)的苯酚/四氯乙烷中在0.5g/100ml的浓度下于25℃测定的。
除非另有说明,玻璃化转变温度(Tg)是按照ASTM D3418使用来自Thermal Analyst Instrument的TA DSC2920以20℃/分钟的扫描速率测定的。
组合物的二醇含量和顺式/反式比率是通过质子核磁共振谱(NMR)测定的。所有NMR数据记录在JEOL Eclipse Plus600MHz核磁共振光谱仪上,对于聚合物使用氯仿-三氟乙酸(70/30体积/体积),或对于低聚样品,使用60/40(wt/wt)苯酚/四氯乙烷,其中加入氘化氯仿以锁定。对于2,2,4,4-四甲基-1,3-环丁二醇共振峰的归属是通过与作为模型(model)的2,2,4,4-四甲基-1,3-环丁二醇的单-和二-苯甲酸酯比较进行的。这些模型化合物非常接近在聚合物和低聚物中的共振位置。
半结晶期t1/2是通过经由激光和光探测器检测样品的透光率随着在温控加热台上的时间变化测定的。这种检测可以通过使聚合物暴露于温度Tmax、然后冷却到所需的温度来进行。然后将样品通过加热台保持在所需的温度,同时检测透射率随时间的变化。开始时,样品目测是透明的,具有高透光率,并且随着样品结晶而变浑浊。半结晶期是透光率处于初始透光率和最终透光率之间的一半时的时间。Tmax定义为熔融样品的结晶相畴所需要的温度(如果结晶相畴存在的话)。以下实施例中的Tmax表示将样品加热以在检测半结晶期之前调节样品时的温度。Tmax取决于组成,并且对于各种聚酯通常是不同的。例如,可以将PCT加热到比290℃高的温度以熔融结晶相畴。
密度是使用梯度密度塔在23℃检测的。
本文报告的熔体粘度是使用Rheometrics Dynamic Analyzer(RDA II)检测的。熔体粘度作为剪切速率的函数在1-400弧度/秒的频率下在所报告的温度下检测。零剪切粘度(η0)是在零剪切速率下的熔 体粘度,通过根据本领域已知的模型外推数据来估计。此步骤通过Rheometrics Dynamic Analyzer(RDA II)软件自动进行。
将聚合物在80-100℃的温度下在真空烘箱中干燥24小时,并在Boy22S模塑机上注塑,得到1/8×1/2×5英寸和1/4×1/2×5英寸的挠曲棒。将这些棒切成2.5英寸的长度,并根据ASTM D256用10密耳缺口冲击掉1/2英寸的宽度。在23℃的平均悬臂梁式冲击强度是从5个样品的检测值确定的。
另外,以5℃的增量在各种温度下检测5个样品,从而测定脆韧转变温度。脆韧转变温度定义为50%的样品以ASTM D256说明的脆性方式破坏的温度。
本文报告的色值是使用Hunter Associatess Lab Inc.Reston,Va.生产的Hunter Lab Ultrascan Spectra Colorimeter测定的。色值的确定是对聚酯的粒料或由其注塑或挤出的板材或其它制品检测的值的平均值。它们通过CIE的L*a*b*颜色体系测定(International Commission on Illumination)(译出),其中L*表示亮度坐标,a*表示红/绿坐标,b*表示黄/蓝坐标。
另外,10密耳的膜使用Carver压机在240℃进行压塑。
除非另有说明,在以下实施例中使用的1,4-环己烷二甲醇的顺/反比率是约30/70,可以在35/65至25/75的范围内。除非另有说明,在以下实施例中使用的2,2,4,4-四甲基-1,3-环丁二醇的顺/反比率是约50/50。
在工作实施例和附图中使用以下缩写:
TPA | 对苯二甲酸 |
DMT | 对苯二甲酸二甲酯 |
TMCD | 2,2,4,4-四甲基-1,3-环丁二醇 |
CHDM | 1,4-环己烷二甲醇 |
IV | 比浓对数粘度 |
η0 | 零剪切粘度 |
Tg | 玻璃化转变温度 |
Tbd | 脆韧转变温度 |
Tmax | 用于检测半结晶期的调节温度 |
实施例1
本实施例说明2,2,4,4-四甲基-1,3-环丁二醇在降低PCT的结晶速率方面比乙二醇或间苯二甲酸更有效。另外,本实施例说明2,2,4,4-四甲基-1,3-环丁二醇对玻璃化转变温度和密度的益处。
如下所述制备各种共聚酯。这些共聚酯都用200ppm氧化二丁基锡作为催化剂,从而在结晶研究期间将催化剂类型和成核时的浓度的影响最小化。1,4-环己烷二甲醇的顺/反比率是31/69,而2,2,4,4-四甲基-1,3-环丁二醇的顺/反比率列在表1中。
为了本实施例的目的,样品具有足够相似的比浓对数粘度,从而有效地在结晶速率检测中不会成为变量。
熔体的半结晶期检测是在140-200℃的温度以10℃的增量检测的,列在表1中。将每个样品的最快半结晶期作为半结晶期随温度变化的最小值,通常在约170-180℃出现。将样品的最快半结晶期作为用于改性PCT的共聚单体的摩尔%的函数绘制在图1中。
数据显示2,2,4,4-四甲基-1,3-环丁二醇在降低结晶速率(即,增加半结晶期)方面比乙二醇和间苯二甲酸更有效。另外,2,2,4,4-四甲基-1,3-环丁二醇能提高Tg和降低密度。
表1
半结晶期(分钟)
1表1中聚酯的二醇组分的余量是1,4-环己烷二甲醇;表1中聚酯的二羧酸组分的余量是对苯二甲酸二甲酯;如果没有描述二羧酸,则是100摩尔%的对苯二甲酸二甲酯。
2100摩尔%的1,4-环己烷二甲醇。
3从实施例1G的研磨聚酯在240℃压制膜。所得的膜具有0.575dL/g的比浓对数粘度。
4从实施例1H的研磨聚酯在240℃压制膜。所得的膜具有0652dL/g的比浓对数粘度。
其中:A是间苯二甲酸
B是乙二醇
C是2,2,4,4-四甲基-1,3-环丁二醇(顺/反=约50/50)
D是2,2,4,4-四甲基-1,3-环丁二醇(顺/反=98/2)
E是2,2,4,4-四甲基-1,3-环丁二醇(顺/反=5/95)
如表1和图1所示,2,2,4,4-四甲基-1,3-环丁二醇在增加半结晶期(即聚合物达到其最大结晶度的一半所需的时间)方面比其它共聚单体例如乙二醇和间苯二甲酸更有效。通过降低PCT的结晶速率(增加半结晶期),本文所述的基于2,2,4,4-四甲基-1,3-环丁二醇改性PCT的无定形制品可以通过本领域公知的方法制备。如表1所示,这些材料显示出比其它改性PCT共聚酯更高的玻璃化转变温度和更低的密度。
下面描述表1中所示的聚酯的制备。
实施例1A
本实施例描述了目标组成为80摩尔%对苯二甲酸二甲酯残基、20摩尔%间苯二甲酸二甲酯残基和100摩尔%的1,4-环己烷二甲醇残基(顺/反=28/72)的共聚酯的制备。
将56.63g对苯二甲酸二甲酯、55.2g1,4-环己烷二甲醇、14.16g间苯二甲酸二甲酯和0.0419g氧化二丁锡的混合物放入配备有氮气入口、金属搅拌器和短蒸馏柱的500ml烧瓶中。将烧瓶放入已加热到210℃的Wood金属浴中。在实验过程中,搅拌速度设定为200RPM。将烧瓶内容物在210℃加热5分钟,然后在30分钟内使温度逐渐升高到290℃。反应混合物在290℃保持60分钟,然后在随后的5分钟内逐渐施加真空直到烧瓶内的压力达到100mmHg。在随后的5分钟内进一步将烧瓶内的压力降低到0.3mmHg。0.3mmHg的压力总共保持90分钟以除去过量的未反应的二醇。获得了具有高熔体粘度、目测透明且无色的聚合物,其玻璃化转变温度是87.5℃,比浓对数粘度是0.63dL/g。NMR分析表明该聚合物包含100摩尔%的1,4-环己烷二甲醇残基和20.2摩尔%间苯二甲酸二甲酯残基。
实施例1B
本实施例描述了目标组成为100摩尔%对苯二甲酸二甲酯残基、20摩尔%乙二醇残基和80摩尔%的1,4-环己烷二甲醇残基(顺/反=32/68)的共聚酯的制备。
将77.68g对苯二甲酸二甲酯、50.77g1,4-环己烷二甲醇、27.81g乙二醇和0.0433g氧化二丁锡的混合物放入配备有氮气入口、金属搅拌器和短蒸馏柱的500ml烧瓶中。将烧瓶放入已加热到200℃的Wood金属浴中。在实验过程中,搅拌速度设定为200RPM。将烧瓶内容物在200℃加热60分钟,然后在5分钟内使温度逐渐升高到210℃。反应混合物在210℃保持120分钟,然后在30分钟内加热到直至280℃。一旦达到280℃,在随后的5分钟内逐渐施加真空直到烧瓶内的压力达到100mmHg。在随后的10分钟内进一步将烧瓶内的压力降低到0.3mmHg。0.3mmHg的压力总共保持90分钟以除去过量的未反应的二醇。获得了具有高熔体粘度、目测透明且无色的聚合物,其玻璃化转变温度是87.7℃,比浓对数粘度是0.71dL/g。NMR分析表明该聚合物包含19.8 摩尔%乙二醇残基。
实施例1C
本实施例描述了目标组成为100摩尔%对苯二甲酸二甲酯残基、20摩尔%2,2,4,4-四甲基-1,3-环丁二醇残基和80摩尔%的1,4-环己烷二甲醇残基(顺/反=31/69)的共聚酯的制备。
将77.68g对苯二甲酸二甲酯、48.46g1,4-环己烷二甲醇、17.86g2,2,4,4-四甲基-1,3-环丁二醇和0.046g氧化二丁锡的混合物放入配备有氮气入口、金属搅拌器和短蒸馏柱的500ml烧瓶中。按照与实施例1A相似的方式制备聚酯。获得了具有高熔体粘度、目测透明且无色的聚合物,其玻璃化转变温度是100.5℃,比浓对数粘度是0.73dL/g。NMR分析表明该聚合物包含80.5摩尔%的1,4-环己烷二甲醇残基和19.5摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。
实施例1D
本实施例描述了目标组成为80摩尔%对苯二甲酸二甲酯残基、40摩尔%间苯二甲酸二甲酯残基和100摩尔%的1,4-环己烷二甲醇残基(顺/反=28/72)的共聚酯的制备。
将42.83g对苯二甲酸二甲酯、55.26g1,4-环己烷二甲醇、28.45g间苯二甲酸二甲酯和0.0419g氧化二丁锡的混合物放入配备有氮气入口、金属搅拌器和短蒸馏柱的500ml烧瓶中。将烧瓶放入已加热到210℃的Wood金属浴中。在实验过程中,搅拌速度设定为200RPM。将烧瓶内容物在210℃加热5分钟,然后在30分钟内使温度逐渐升高到290℃。反应混合物在290℃保持60分钟,然后在随后的5分钟内逐渐施加真空直到烧瓶内的压力达到100mmHg。在随后的5分钟内进一步将烧瓶内的压力降低到0.3mmHg。0.3mmHg的压力总共保持90分钟以除去过量的未反应的二醇。获得了具有高熔体粘度、目测透明且无色的聚合物,其玻璃化转变温度是81.2℃,比浓对数粘度是0.67dL/g。NMR分析表明该聚合物包含100摩尔%的1,4-环己烷二甲醇残基和40.2摩尔%间苯二甲酸二甲酯残基。
实施例1E
本实施例描述了目标组成为100摩尔%对苯二甲酸二甲酯残基、40摩尔%乙二醇残基和60摩尔%的1,4-环己烷二甲醇残基(顺/反=31/69)的共聚酯的制备。
将81.3g对苯二甲酸二甲酯、42.85g1,4-环己烷二甲醇、34.44g乙二醇和0.0419g氧化二丁锡的混合物放入配备有氮气入口、金属搅拌器和短蒸馏柱的500ml烧瓶中。将烧瓶放入已加热到200℃的Wood金属浴中。在实验过程中,搅拌速度设定为200RPM。将烧瓶内容物在200℃加热60分钟,然后在5分钟内使温度逐渐升高到210℃。反应混合物在210℃保持120分钟,然后在30分钟内加热到直至280℃。一旦达到280℃,在随后的5分钟内逐渐施加真空直到烧瓶内的压力达到100mmHg。在随后的10分钟内进一步将烧瓶内的压力降低到0.3mmHg。0.3mmHg的压力总共保持90分钟以除去过量的未反应的二醇。获得了具有高熔体粘度、目测透明且无色的聚合物,其玻璃化转变温度是82.1℃,比浓对数粘度是0.64dL/g。NMR分析表明该聚合物包含34.5摩尔%乙二醇残基。
实施例1F
本实施例描述了目标组成为100摩尔%对苯二甲酸二甲酯残基、40摩尔%2,2,4,4-四甲基-1,3-环丁二醇残基和60摩尔%的1,4-环己烷二甲醇残基(顺/反=31/69)的共聚酯的制备。
将77.4g对苯二甲酸二甲酯、36.9g1,4-环己烷二甲醇、32.5g2,2,4,4-四甲基-1,3-环丁二醇和0.046g氧化二丁锡的混合物放入配备有氮气入口、金属搅拌器和短蒸馏柱的500ml烧瓶中。将烧瓶放入已加热到210℃的Wood金属浴中。在实验过程中,搅拌速度设定为200RPM。将烧瓶内容物在210℃加热3分钟,然后在30分钟内使温度逐渐升高到260℃。反应混合物在260℃保持120分钟,然后在30分钟内加热到直至290℃。一旦达到290℃,在随后的5分钟内逐渐施加真空直到烧瓶内的压力达到100mmHg。在随后的5分钟内进一步将烧瓶内的压力降低到0.3mmHg。0.3mmHg的压力总共保持90分钟以除去过量的未反应的二醇。获得了具有高熔体粘度、目测透明且无色的聚合物,其玻璃化转变温度是122℃,比浓对数粘度是0.65dL/g。NMR分析表明该聚合物包含59.9摩尔%的1,4-环己烷二甲醇残基和40.1摩尔%的2,2,4,4-四甲 基-1,3-环丁二醇残基。
实施例1G
本实施例描述了目标组成为100摩尔%对苯二甲酸二甲酯残基、20摩尔%2,2,4,4-四甲基-1,3-环丁二醇残基(顺/反=98/2)和80摩尔%的1,4-环己烷二甲醇残基(顺/反=31/69)的共聚酯的制备。
将77.68g对苯二甲酸二甲酯、48.46g1,4-环己烷二甲醇、20.77g2,2,4,4-四甲基-1,3-环丁二醇和0.046g氧化二丁锡的混合物放入配备有氮气入口、金属搅拌器和短蒸馏柱的500ml烧瓶中。将烧瓶放入已加热到210℃的Wood金属浴中。在实验过程中,搅拌速度设定为200RPM。将烧瓶内容物在210℃加热3分钟,然后在30分钟内使温度逐渐升高到260℃。反应混合物在260℃保持120分钟,然后在30分钟内加热到直至290℃。一旦达到290℃,在随后的5分钟内逐渐施加真空直到烧瓶内的压力达到100mmHg,并将搅拌速度也降低到100RPM。在随后的5分钟内进一步将烧瓶内的压力降低到0.3mmHg,并将搅拌速度也降低到50RPM。0.3mmHg的压力总共保持60分钟以除去过量的未反应的二醇。获得了具有高熔体粘度、目测透明且无色的聚合物,其玻璃化转变温度是103℃,比浓对数粘度是0.65dL/g。NMR分析表明该聚合物包含85.7摩尔%的1,4-环己烷二甲醇残基和14.3摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。
实施例1H
本实施例描述了100摩尔%对苯二甲酸二甲酯残基、20摩尔%2,2,4,4-四甲基-1,3-环丁二醇残基(顺/反=5/95)和80摩尔%的1,4-环己烷二甲醇残基(顺/反=31/69)的共聚酯的制备。
将77.68g对苯二甲酸二甲酯、48.46g1,4-环己烷二甲醇、20.77g2,2,4,4-四甲基-1,3-环丁二醇和0.046g氧化二丁锡的混合物放入配备有氮气入口、金属搅拌器和短蒸馏柱的500ml烧瓶中。将烧瓶放入已加热到210℃的Wood金属浴中。在实验开始时,搅拌速度设定为200RPM。将烧瓶内容物在210℃加热3分钟,然后在30分钟内使温度逐渐升高到260℃。反应混合物在260℃保持120分钟,然后在30分钟内加热到直至290℃。一旦达到290℃,在随后的5分钟内逐渐施加真空直 到烧瓶内的压力达到100mmHg,并将搅拌速度也降低到100RPM。在随后的5分钟内进一步将烧瓶内的压力降低到0.3mmHg的设定点,并将搅拌速度也降低到50RPM。此压力总共保持60分钟以除去过量的未反应的二醇。需要注意的是真空系统未能达到上述设定点,但是产生足够的真空以获得具有高熔体粘度、目测透明且无色的聚合物,其玻璃化转变温度是99℃,比浓对数粘度是0.73dL/g。NMR分析表明该聚合物包含85摩尔%的1,4-环己烷二甲醇残基和15摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。
实施例2
本实施例说明2,2,4,4-四甲基-1,3-环丁二醇能改进PCT型共聚酯(含有对苯二甲酸和1,4-环己烷二甲醇的聚酯)的韧性。
如下所述制备基于2,2,4,4-四甲基-1,3-环丁二醇的共聚酯。对于所有样品,1,4-环己烷二甲醇的顺/反比率是约31/69。基于乙二醇和1,4-环己烷二甲醇的共聚酯是商购的聚酯。实施例2A的共聚酯(Eastar PCTG5445)从Eastman Chemical Co.获得。实施例2B的共聚酯从Eastman Chemical Co.以商品名Spectar获得。实施例2C和2D是以中试规模(各自是15-lb批次)按照实施例1A所述的工序制备的,并具有表2所示的比浓对数粘度和玻璃化转变温度。实施例2C是用300ppm的目标锡含量(氧化二丁锡)制备的。最终产物含有295ppm的锡。实施例2C的聚酯的色值是L*=77.11,a*=-1.50,b*=5.79。实施例2D是用300ppm的目标锡含量(氧化二丁锡)制备的。最终产物含有307ppm的锡。实施例2D的聚酯的色值是L*=66.72,a*=-1.22,b*=16.28。
将材料注塑成棒,随后打缺口用于悬臂梁(Izod)检测。缺口悬臂梁式冲击强度作为温度的函数获得,也列在表2中。
对于给定的样品,悬臂梁式冲击强度在短温度范围内经历主要转变。例如,基于38摩尔%乙二醇的共聚酯的悬臂梁式冲击强度在15-20℃经历这种转变。这种转变温度与破坏模式的变化有关:在较低温度下的脆性/低能量破坏和在较高温度下的韧性/高能量破坏。转变温度表示为脆韧转变温度Tbd,是衡量韧性的手段。Tbd列在表2中,并在图2中对共聚单体的摩尔%作图。
数据表明与导致PCT的Tbd提高的乙二醇相比,向PCT中 加入2,2,4,4-四甲基-1,3-环丁二醇能降低Tbd和改进韧性。
表2
缺口悬臂梁式冲击能(ft-lb/in)
1在表中的聚酯的二醇组分的余量是1,4-环己烷二甲醇。所有聚合物从100摩尔%的对苯二甲酸二甲酯制备。
NA=未获得
其中B是乙二醇
C是2,2,4,4-四甲基-1,3-环丁二醇(顺/反=50/50)
实施例3
本实施例说明2,2,4,4-四甲基-1,3-环丁二醇能改进PCT型共聚酯(含有对苯二甲酸和1,4-环己烷二甲醇的聚酯)的韧性。在本实施例中制备的聚酯含有15-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。
如下所述制备基于对苯二甲酸二甲酯、2,2,4,4-四甲基-1,3-环丁二醇和1,4-环己烷二甲醇的共聚酯,其具有下表3所示的组成和性能。在下表3中的聚酯的二醇组分的余量直至100摩尔%是1,4-环己烷二甲醇(顺/反=31/69)。
将材料注塑成3.2mm和6.4mm厚的棒,随后打缺口用于悬臂梁检测。缺口悬臂梁式冲击强度在23℃获得,列在下表3中。检测模塑棒的密度、Tg和半结晶期。在290℃检测粒料的熔体粘度。
表3
用于本发明的特定聚酯的各种性能汇总
NA=未获得
实施例3A
将21.24lb(49.71g-mol)的对苯二甲酸二甲酯、14.34lb(45.21g-mol)的1,4-环己烷二甲醇和4.58lb(14.44g-mol)的2,2,4,4-四甲基-1,3-环丁二醇一起在200ppm的催化剂三(2-乙基己酸)丁基锡的存在下反应。该反应在氮气吹扫下在18加仑的配备有冷凝柱、真空系统和HELICONE型搅拌器的不锈钢压力容器中进行。在25RPM的搅拌下,反应混合物的温度升高到250℃,压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/分钟的速率将压力降低到0psig。反应混合物的温度然后升高到270℃,压力降低到90mmHg。在270℃和90mmHg保持1小时后,搅拌器速度降低到15RPM,反应混合物的温度升高到290℃,压力降低到小于1mmHg。反应混合物在290℃和小于1mmHg压力下保持直到对搅拌器的能量拉伸不再增 加(70分钟)。然后使用氮气将压力容器的压力升高到1大气压。熔融的聚合物然后从压力容器挤出。将冷却的挤出聚合物研磨至能通过6mm筛子。聚合物的比浓对数粘度是0.736dL/g,Tg是104℃。NMR分析表明该聚合物包含85.4摩尔%的1,4-环己烷二甲醇残基和14.6摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值是:L*=78.20,a*=-1.62,b*=6.23。
实施例3B至3D
实施例3B至3D的聚酯按照与实施例3A所述相似的工序制备。这些聚酯的组成和性能列在表3中。
实施例3E
将21.24lb(49.71g-mol)的对苯二甲酸二甲酯、12.61lb(39.77g-mol)的1,4-环己烷二甲醇和6.30lb(19.88g-mol)的2,2,4,4-四甲基-1,3-环丁二醇一起在200ppm的催化剂三(2-乙基己酸)丁基锡的存在下反应。该反应在氮气吹扫下在18加仑的配备有冷凝柱、真空系统和HELICONE型搅拌器的不锈钢压力容器中进行。在25RPM的搅拌下,反应混合物的温度升高到250℃,压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/分钟的速率将压力降低到0psig。反应混合物的温度然后升高到270℃,压力降低到90mmHg。在270℃和90mmHg保持1小时后,搅拌器速度降低到15RPM,反应混合物的温度升高到290℃,压力降低到小于1mmHg。反应混合物在290℃和小于1mmHg压力下保持60分钟。然后使用氮气将压力容器的压力升高到1大气压。熔融的聚合物然后从压力容器挤出。将冷却的挤出聚合物研磨至能通过6mm筛子。聚合物的比浓对数粘度是0.715dL/g,Tg是110℃。X-射线分析显示聚酯含有223ppm的锡。NMR分析表明该聚合物包含78.6摩尔%的1,4-环己烷二甲醇残基和21.4摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值是:L*=76.45,a*=-1.65,b*=6.47。
实施例3F
实施例3F的聚酯按照与实施例3A所述相似的工序制备。 这些聚酯的组成和性能列在表3中。
实施例3H
将21.24lb(49.71g-mol)的对苯二甲酸二甲酯、12.61lb(39.77g-mol)的1,4-环己烷二甲醇和6.30lb(19.88g-mol)的2,2,4,4-四甲基-1,3-环丁二醇一起在200ppm的催化剂三(2-乙基己酸)丁基锡的存在下反应。该反应在氮气吹扫下在18加仑的配备有冷凝柱、真空系统和HELICONE型搅拌器的不锈钢压力容器中进行。在25RPM的搅拌下,反应混合物的温度升高到250℃,压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/分钟的速率将压力降低到0psig。反应混合物的温度然后升高到270℃,压力降低到90mmHg。在270℃和90mmHg保持1小时后,搅拌器速度降低到15RPM,反应混合物的温度升高到290℃,压力降低到小于1mmHg。反应混合物在290℃和小于1mmHg压力下保持12分钟。然后使用氮气将压力容器的压力升高到1大气压。熔融的聚合物然后从压力容器挤出。将冷却的挤出聚合物研磨至能通过6mm筛子。聚合物的比浓对数粘度是0.590dL/g,Tg是106℃。NMR分析表明该聚合物包含77.1摩尔%的1,4-环己烷二甲醇残基和22.9摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值是:L*=83.27,a*=-1.34,b*=5.08。
实施例3I
将21.24lb(49.71g-mol)的对苯二甲酸二甲酯、12.61lb(39.77g-mol)的1,4-环己烷二甲醇和6.30lb(19.88g-mol)的2,2,4,4-四甲基-1,3-环丁二醇一起在200ppm的催化剂三(2-乙基己酸)丁基锡的存在下反应。该反应在氮气吹扫下在18加仑的配备有冷凝柱、真空系统和HELICONE型搅拌器的不锈钢压力容器中进行。在25RPM的搅拌下,反应混合物的温度升高到250℃,压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/分钟的速率将压力降低到0psig。反应混合物的温度然后升高到270℃,压力降低到90mmHg。在270℃和90mmHg保持1小时后,搅拌器速度降低到15RPM,反应混合物的温度升高到290℃,压力降低到4mmHg。反应混合物在290℃和4mmHg压力下保持30分钟。然后使用氮气将压力容器的压力 升高到1大气压。熔融的聚合物然后从压力容器挤出。将冷却的挤出聚合物研磨至能通过6mm筛子。聚合物的比浓对数粘度是0.531dL/g,Tg是105℃。NMR分析表明该聚合物包含76.9摩尔%的1,4-环己烷二甲醇残基和23.1摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值是:L*=80.42,a*=-1.28,b*=5.13。
实施例3J
将21.24lb(49.71g-mol)的对苯二甲酸二甲酯、12.61lb(39.77g-mol)的1,4-环己烷二甲醇和6.30lb(19.88g-mol)的2,2,4,4-四甲基-1,3-环丁二醇一起在200ppm的催化剂三(2-乙基己酸)丁基锡的存在下反应。该反应在氮气吹扫下在18加仑的配备有冷凝柱、真空系统和HELICONE型搅拌器的不锈钢压力容器中进行。在25RPM的搅拌下,反应混合物的温度升高到250℃,压力升高到20psig。反应混合物在250℃和20psig压力下保持2小时。然后以3psig/分钟的速率将压力降低到0psig。反应混合物的温度然后升高到270℃,压力降低到90mmHg。在270℃和90mmHg保持1小时后,搅拌器速度降低到15RPM,反应混合物的温度升高到290℃,压力降低到4mmHg。当反应混合物达到290℃和4mmHg压力时,立即使用氮气将压力容器的压力升高到1大气压。熔融的聚合物然后从压力容器挤出。将冷却的挤出聚合物研磨至能通过6mm筛子。聚合物的比浓对数粘度是0.364dL/g,Tg是98℃。NMR分析表明该聚合物包含77.5摩尔%的1,4-环己烷二甲醇残基和22.5摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。聚合物的色值是:L*=77.20,a*=-1.47,b*=4.62。
实施例4-对比例
本实施例的对比材料的数据列在表4中。PC是来自Bayer的Makrolon2608,其标称组成是100摩尔%双酚A残基和100摩尔%的碳酸二苯酯残基。Makrolon2608的标称熔体流速是20g/10分钟,在300℃下使用1.2kg砝码测量。PET是来自Eastman Chemical Company的Eastar9921,其标称组成是100摩尔%对苯二甲酸、3.5摩尔%的环己烷二甲醇(CHDM)和96.5摩尔%的乙二醇。PETG是来自Eastman Chemical Company的Eastar6763,其标称组成是100摩尔%对苯二甲酸、31摩尔 %的环己烷二甲醇(CHDM)和69摩尔%的乙二醇。PCTG是来自Eastman Chemical Company的Eastar DN001,其标称组成是100摩尔%对苯二甲酸、62摩尔%的环己烷二甲醇(CHDM)和38摩尔%的乙二醇。PCTA是来自Eastman Chemical Company的Eastar AN001,其标称组成是65摩尔%对苯二甲酸、35摩尔%的间苯二甲酸和100摩尔%的环己烷二甲醇(CHDM)。聚砜是来自Solvay的Udel1700,其标称组成是100摩尔%的双酚A残基和100摩尔%的4,4-二氯磺酰基砜残基。Udel1700的标称熔体流速是6.5g/10分钟,在343℃下使用2.16kg砝码测量。SAN是来自Lanxess的Lustran31,其标称组成是76摩尔%的苯乙烯和24摩尔%的丙烯腈。Lustran31的标称熔体流速是7.5g/10分钟,在230℃下使用3.8kg砝码测量。与所有其它树脂相比,本发明的实施例显示改进了6.4mm厚的棒的韧性。
表4
特定商业聚合物的各种性能汇总
NA=未获得
实施例5
本实施例说明用于制备本发明聚酯的2,2,4,4-四甲基-1,3-环 丁二醇的用量对聚酯的玻璃化转变温度的影响。在本实施例中制备的聚酯含有15-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基。
实施例5A-5G
将对苯二甲酸二甲酯、1,4-环己烷二甲醇和2,2,4,4-四甲基-1,3-环丁二醇加入500ml的单颈圆底烧瓶中。对2,2,4,4-四甲基-1,3-环丁二醇原料的NMR分析显示顺/反比率是53/47。本实施例的聚酯用1.2/1的二醇/酸比率制备,其中全部过量来自2,2,4,4-四甲基-1,3-环丁二醇。加入足量的氧化二丁锡催化剂以在最终聚合物中得到300ppm的锡。烧瓶处于具有真空降低能力的0.2SCFC氮气吹扫下。将烧瓶在200℃浸入Belmont金属浴中,并在反应物熔融后于200RPM搅拌。在约2.5小时后,温度升高到210℃,并将这些条件再保持2小时。将温度升高到285℃(在约25分钟内),并在5分钟内将压力降低到0.3mmHg。随着粘度增加而降低搅拌速度,使用15RPM的最小搅拌。改变总聚合时间以达到目标比浓对数粘度。在完成聚合之后,放低Belmont金属浴,并使聚合物冷却到低于其玻璃化转变温度。在约30分钟后,将烧瓶再次浸入Belmont金属浴(在此30分钟等待期间,温度已经升高到295℃),并加热聚合物物质直到从玻璃烧瓶中取出。在中等水平下搅拌聚合物物质直到聚合物冷却。从烧瓶取出聚合物,并研磨到能通过3mm筛子。改变该工序以制备如下所述具有20摩尔%目标组成的共聚酯。
比浓对数粘度如上述“检测方法”所述检测。聚酯的组成通过在上述检测方法部分中所解释的1H NMR测定。玻璃化转变温度通过DSC使用在骤冷之后20℃/分钟的速率第二次加热来检测。
实施例5H-5Q
这些聚酯通过在分开的阶段中进行酯交换和缩聚反应来制备。酯交换实验在连续升温型(CTR)反应器中进行。CTR是3000ml的玻璃反应器,配备有单轴驱动浆式搅拌器,被电加热外套覆盖,并装配有加热的填充回流冷凝柱。向反应器中装入777g(4摩尔)的对苯二甲酸二甲酯、230g(1.6摩尔)的2,2,4,4-四甲基-1,3-环丁二醇、460.8g(3.2摩尔)的环己烷二甲醇和1.12g的三-2-乙基己酸丁基锡(使得在最终聚合物中有200ppm的锡金属)。将加热套手动调节到100%输出 功率。设定点和数据的收集是通过Camile工艺控制系统促进的。一旦反应物熔融,就开始搅拌并缓慢增加到250rpm。反应器的温度随着运行时间而逐步升高。收集的甲醇的重量通过天平记录。当甲醇的逸出停止或在260℃的预定低温时停止反应。在氮气吹扫下取出低聚物,并冷却到室温。用液氮冷冻低聚物,并破裂成足够小到称量加入500ml圆底烧瓶的小块。
在缩聚反应中,将如上制备的约150g低聚物加入500ml圆底烧瓶中。该烧瓶配备有不锈钢搅拌器和聚合物头。将玻璃器皿设定到一半摩尔数的聚合物装置上,并开始Camile顺序。一旦低聚物熔融就将搅拌器放置在圆底烧瓶中的全满位置。这些实施例的由Camile软件控制的温度/压力/搅拌速率顺序列在下表中,除非另有说明。
实施例5H和5I的Camile顺序
实施例5N至5Q的Camile顺序
实施例5K和5L的Camile顺序
实施例5J和5M的Camile顺序
所得的聚合物从烧瓶中取出,使用水力切割器切割,并研磨成6mm的筛子尺寸。每种研磨过的聚合物样品的比浓对数粘度在60/40(重量/重量)的苯酚/四氯乙烷中在0.5g/100ml的浓度下于25℃测定,催化剂水平(Sn)通过x-射线荧光谱检测,色值(L*、a*、b*)通过透射光谱检测。聚合物的组成通过1H NMR获得。使用Rheometrics Mechanical Spectrometer(RMS-800)检测样品的热稳定性和熔体粘度。
下表显示本实施例聚酯的实验数据。这些数据表明对于恒定的比浓对数粘度,提高2,2,4,4-四甲基-1,3-环丁二醇的用量能以几乎线性的方式提高玻璃化转变温度。图3也显示Tg对组成和比浓对数粘度的依赖性。
表5
玻璃化转变温度与比浓对数粘度和组成的关系
NA=未获得
实施例6-对比例
本实施例说明基于100%2,2,4,4-四甲基-1,3-环丁二醇的聚酯具有缓慢的半结晶期。
仅仅基于对苯二甲酸和2,2,4,4-四甲基-1,3-环丁二醇的聚酯按照与上述实施例1A相似的方法制备,且具有表6所示的性能。这种聚酯具有300ppm的氧化二丁锡。2,2,4,4-四甲基-1,3-环丁二醇的反/顺比率是65/35。
在320℃从研磨的聚合物压制膜。从熔体检测半结晶期是在220-250℃的温度以10℃的增量进行的,并报告在表6中。将样品的最快半结晶期作为与温度有关的半结晶期最小值。这种聚酯的最快半结晶 期是约1300分钟。将该值与具有极短半结晶期(小于1分钟)的仅仅基于对苯二甲酸和1,4-环己烷二甲醇(没有用于改性的共聚单体)的聚酯(PCT)进行比较,如图1所示。
表6
半结晶期(分钟)
其中:F是2,2,4,4-四甲基-1,3-环丁二醇(反/顺=65/35)
实施例7
使用3.5英寸单螺杆挤出机生产含有聚酯的片材,所述聚酯已经制得具有100摩尔%对苯二甲酸残基、80摩尔%1,4-环己烷二甲醇和20摩尔%2,2,4,4-四甲基-1,3-环丁二醇残基的目标组成。将片材连续地挤出,校正到177密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测比浓对数粘度和玻璃化转变温度。测得片材的比浓对数粘度是0.69dL/g。测得片材的玻璃化转变温度是106℃。然后将片材在50%相对湿度和60℃下调节两星期。随后使用Brown热成型机将片材热成型到拉伸比为2.5∶1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例G)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为106℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有至少95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
实施例8
使用3.5英寸单螺杆挤出机生产含有聚酯的片材,所述聚酯已经制得具有100摩尔%对苯二甲酸残基、80摩尔%1,4-环己烷二甲醇和20摩尔%2,2,4,4-四甲基-1,3-环丁二醇残基的目标组成。将片材连续地挤出,校正到177密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测比浓对数粘度和玻璃化转变温度。测得片材的比浓对数粘度是0.69dL/g。测得片材的玻璃化转变温度是106℃。然后将片材在100%相对湿度和25℃下调节两星期。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为60/40/40%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例G)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为106℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有至少95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
实施例9-对比例
使用3.5英寸单螺杆挤出机生产由Kelvx201组成的片材。Kelvx是一种由69.85%PCTG(来自Eastman Chemcial Co.的Eastar,具有100摩尔%对苯二甲酸残基、62摩尔%1,4-环己烷二甲醇和38摩尔%乙二醇残基)、30%PC(双酚A聚碳酸酯)和0.15%Weston619(Crompton Corporation销售的稳定剂)组成的共混物。将片材连续地挤出,校正到177密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是100℃。然后将片材在50%相对湿度和60℃下调节两星期。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例E)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为100℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有至少95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
实施例10-对比例
使用3.5英寸单螺杆挤出机生产由Kelvx201组成的片材。将片材连续地挤出,校正到177密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是100℃。然后将片材在100%相对湿度和25℃下调节两星期。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为60/40/40%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例H)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为100℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有至少95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
NA=未记录
实施例11-对比例
使用3.5英寸单螺杆挤出机生产由PCTG25976(100摩尔%对苯二甲酸残基、62摩尔%的1,4-环己烷二甲醇残基和38摩尔%的乙二醇残基)组成的片材。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是87℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.17重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例A)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为87℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有大于95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
实施例12-对比例
使用1.25英寸单螺杆挤出机生产由20重量%的Teijin L-1250聚碳酸酯(一种双酚A聚碳酸酯)、79.85重量%的PCTG25976和0.15重量%Weston619组成的可混溶性共混物。然后使用3.5英寸单螺杆挤出机生产由这种共混物组成的片材。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是94℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.25重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例(A)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为94℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有大于95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
实施例13-对比例
使用1.25英寸单螺杆挤出机生产由30重量%的Teijin L-1250聚碳酸酯、69.85重量%的PCTG 25976和0.15重量%Weston619组成的可混溶性共混物。然后使用3.5英寸单螺杆挤出机生产由这种共混物组成的片材。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是99℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.25重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5∶1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例(A)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为99℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有大于95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
NA=未获得。零值表示因为片材没有进入模具而没有形成片材(似乎是因为太冷)。
实施例14-对比例
使用1.25英寸单螺杆挤出机生产由40重量%的Teijin L-1250聚碳酸酯、59.85重量%的PCTG25976和0.15重量%Weston619组成的可混溶性共混物。然后使用3.5英寸单螺杆挤出机生产由这种共混物组成的片材。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是105℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.265重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例8A-8E)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为105℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有大于95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
实施例15-对比例
使用1.25英寸单螺杆挤出机生产由50重量%的Teijin L-1250聚碳酸酯、49.85重量%的PCTG25976和0.15重量%Weston619组成的可混溶性共混物。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是111℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.225重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5∶1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例A-D)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为111℃的热塑性片材可以在下述条件下热成型,这表现为这些片材具有大于95%的拉伸,没有起泡,且在热成型之前没有预先干燥片材。
NA=未获得。零值表示因为片材没有进入模具而没有形成片材(似乎是因为太冷)。
实施例16-对比例
使用1.25英寸单螺杆挤出机生产由60重量%的Teijin L-1250聚碳酸酯、39.85重量%的PCTG25976和0.15重量%Weston619组成的可混溶性共混物。然后使用3.5英寸单螺杆挤出机生产由这种共混物组成的片材。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是117℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.215重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例(A)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为117℃的热塑性片材可以在下述条件下不能热成型,这表现为在热成型之前没有预先干燥片材的情况下不能生产具有大于95%的拉伸且没有起泡的片材。
实施例17-对比例
使用1.25英寸单螺杆挤出机生产由65重量%的Teijin L-1250聚碳酸酯、34.85重量%的PCTG25976和0.15重量%Weston619组成的可混溶性共混物。然后使用3.5英寸单螺杆挤出机生产由这种共混物组成的片材。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是120℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.23重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5∶1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例(A)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为120℃的热塑性片材可以在下述条件下不能热成型,这表现为在热成型之前没有预先干燥片材的情况下不能生产具有大于95%的拉伸且没有起泡的片材。
实施例18-对比例
使用1.25英寸单螺杆挤出机生产由70重量%的Teijin L-1250聚碳酸酯、29.85重量%的PCTG25976和0.15重量%Weston619组成的可混溶性共混物。然后使用3.5英寸单螺杆挤出机生产由这种共混物组成的片材。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是123℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.205重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例A和(B)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为123℃的热塑性片材可以在下述条件下不能热成型,这表现为在热成型之前没有预先干燥片材的情况下不能生产具有大于95%的拉伸且没有起泡的片材。
NA=未获得。零值表示因为片材没有进入模具而没有形成片材(似乎是因为太冷)。
实施例19-对比例
使用3.5英寸单螺杆挤出机生产由Teijin L-1250聚碳酸酯组成的片材。将片材连续地挤出,校正到118密耳的厚度,然后将各种片材剪切达到尺寸要求。在一个片材上检测玻璃化转变温度,测得是149℃。然后将片材在50%相对湿度和60℃下调节四星期。测得水含量是0.16重量%。随后使用Brown热成型机将片材热成型到拉伸比为2.5:1的阴模中。热成型烘箱加热器设定为70/60/60%输出,仅仅使用顶部加热。将片材在烘箱中保持各种时间以测定片材温度对部件质量的影响,如下表所示。部件质量通过检测热成型部件的体积、计算拉伸和目测观察热成型部件来确定。拉伸通过用部件体积除以在此组实验中达到的最大部件体积(实施例(A)来计算。目测观察热成型的部件中的任何起泡,起泡程度评价为无(N)、低(L)或高(H)。下述结果证明这些玻璃化转变温度为149℃的热塑性片材可以在下述条件下不能热成型,这表现为在热成型之前没有预先干燥片材的情况下不能生产具有大于95%的拉伸且没有起泡的片材。
NA=未获得。零值表示因为片材没有进入模具而没有形成片材(似乎是因为太冷)。
从上述相关工作实施例的数据比较显然可见,与商业聚酯相比,本发明的聚酯提供了在玻璃化转变温度、密度、慢结晶速率、熔体粘度和韧性方面的显著优点。
已经参考本文公开的实施方案详细描述了本发明,但是应该理解的是可以在本发明的主旨和范围内进行变化和改进。
Claims (33)
1.包含至少一种聚酯组合物的膜或片,该聚酯组合物包含至少一种聚酯,其含有:
(a) 二羧酸组分,包括:
i) 70-100摩尔%的对苯二甲酸残基;
ii) 0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii) 0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b) 二醇组分,包括:
i) 15-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii) 75-85摩尔%的1,4-环己烷二甲醇残基,
其中,二羧酸组分的总摩尔%是100摩尔%,且
二醇组分的总摩尔%是100摩尔%,且
其中,在60/40 wt/wt的苯酚/四氯乙烷中,0.5 g/100 ml浓度下,在25℃测定的所述聚酯的比浓对数粘度为0.60-0.75 dL/g;
其中所述聚酯的Tg为85-120℃;
其中所述聚酯根据ASTM D256在1/8英寸厚棒中用10密耳的缺口在23℃测得的缺口悬臂梁式冲击强度至少为647J/m;
其中所述聚酯在290℃在旋转熔体流变仪上以1弧度/秒测得的熔体粘度小于10,000泊;并且
其中所述聚酯组合物不含聚碳酸酯。
2.权利要求1的膜或片,其中,所述聚酯的比浓对数粘度为0.60-0.72 dL/g。
3.权利要求1的膜或片,其中,所述聚酯的二醇组分包含17-23摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基,和77-83摩尔%的1,4-环己烷二甲醇残基,或包含大于20摩尔%至25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基,和75摩尔%至小于80摩尔%的1,4-环己烷二甲醇残基。
4.权利要求1的膜或片,其中,所述聚酯的二羧酸组分包含90-100摩尔%的对苯二甲酸残基。
5.权利要求1的膜或片,其中,所述聚酯包含0.1-10摩尔%的乙二醇残基。
6.权利要求1的膜或片,其中,所述2,2,4,4-四甲基-1,3-环丁二醇残基是含有70-30摩尔%的反式-2,2,4,4-四甲基-1,3-环丁二醇残基,和30-70摩尔%的顺式-2,2,4,4-四甲基-1,3-环丁二醇残基的混合物。
7.权利要求1的膜或片,其中,所述2,2,4,4-四甲基-1,3-环丁二醇残基的顺式/反式比率中的顺式部分大于50摩尔%。
8.权利要求1的膜或片,其中,所述聚酯是无定形的。
9.权利要求1的膜或片,其中,所述聚酯在170℃具有的半结晶期大于5分钟。
10.权利要求1的膜或片,其中,所述聚酯在23℃具有的密度为1.1至小于1.2g/ml。
11.权利要求1的膜或片,其中,在1/4英寸厚棒中在23℃测得的所述聚酯的缺口悬臂梁式冲击强度至少为10 英尺-磅/英寸。
12.权利要求1的膜或片,进一步包含至少一种选自以下的聚合物:聚酰胺、聚苯乙烯、苯乙烯共聚物、丙烯酸系聚合物和共聚物、聚醚酰亚胺、聚苯醚、聚苯醚/聚苯乙烯共混物、聚苯硫醚、聚苯硫醚/砜、聚(酯-碳酸酯)、聚砜、聚砜醚、或聚(醚-酮)或它们的混合物。
13.权利要求12的膜或片,其中苯乙烯共聚物为苯乙烯/丙烯腈共聚物或丙烯腈/丁二烯/苯乙烯共聚物,丙烯酸系聚合物和共聚物是聚甲基丙烯酸甲酯。
14.权利要求1的膜或片,其中,所述聚酯的玻璃化转变温度为95-115℃。
15.权利要求2的膜或片,其中,所述聚酯的玻璃化转变温度为95-115℃。
16.权利要求1的膜或片,其中,所述聚酯包含至少一种支化剂的残基,其含量基于所述酸或二醇残基的总摩尔百分数为0.01-10重量%。
17.权利要求1的膜或片,其中,所述聚酯在290℃在旋转熔体流变仪上以1弧度/秒测得的熔体粘度小于6,000泊。
18.权利要求1的膜或片,进一步包含至少一种选自以下的添加剂:着色剂、脱模剂、阻燃剂、增塑剂、成核剂、UV稳定剂、玻璃纤维、碳纤维、填料、抗冲改性剂,以及它们的混合物。
19.权利要求18的膜或片,其中所述着色剂是染料。
20.权利要求1的膜或片,其中,所述聚酯包含至少一种含锡化合物或其反应产物的催化剂的残基。
21.含有权利要求1的膜或片的生产制品。
22.权利要求21的生产制品,其中,所述聚酯根据ASTM D256在1/4英寸厚棒中用10密耳的缺口在23℃测得的缺口悬臂梁式冲击强度至少为 10 ft-lbs/in。
23.液晶显示器膜,其含有权利要求1的聚酯组合物。
24.权利要求23的液晶显示器膜,其中,液晶显示器膜是扩散片、或是补偿膜、或是保护膜。
25.权利要求1的膜或片,其含有:
(b) 二醇组分,包括:
i) 17-23摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii) 77-83摩尔%的1,4-环己烷二甲醇残基,
其中,在60/40wt/wt的苯酚/四氯乙烷中,0.5 g/100 ml浓度下,在25℃测定的所述聚酯的比浓对数粘度是0.60至小于0.72 dL/g;
其中,所述聚酯的玻璃化转变温度是95-115℃;
其中所述聚酯根据ASTM D256在1/8英寸厚棒中用10密耳的缺口在23℃测得的缺口悬臂梁式冲击强度至少为647J/m;
其中所述聚酯在290℃在旋转熔体流变仪上以1弧度/秒测得的熔体粘度小于10,000泊。
26.权利要求1的膜或片,其含有:
(b) 二醇组分,包括:
i) 15-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;
ii) 75-85摩尔%的1,4-环己烷二甲醇残基,以及
iii) 0.1摩尔%至小于10摩尔%的乙二醇残基,
其中,在60/40wt/wt的苯酚/四氯乙烷中,0.5 g/100 ml浓度下,在25℃测定的所述聚酯的比浓对数粘度为0.60-0.72 dL/g;以及
其中,聚酯的玻璃化转变温度是从95到115℃;
其中所述聚酯根据ASTM D256在1/8英寸厚棒中用10密耳的缺口在23℃测得的缺口悬臂梁式冲击强度至少为647J/m;
其中所述聚酯在290℃在旋转熔体流变仪上以1弧度/秒测得的熔体粘度小于10,000泊。
27.权利要求1的膜或片,其含有:
(b) 二醇组分,包括:
i) 17-23摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;
ii) 77-83摩尔%的1,4-环己烷二甲醇残基,以及
iii) 0.1摩尔%至小于10摩尔%的乙二醇残基;
其中,在60/40wt/wt的苯酚/四氯乙烷中,0.5 g/100 ml浓度下,在25℃测定的所述聚酯的比浓对数粘度是0.60-0.72 dL/g;
其中所述聚酯的Tg为85-120℃;
其中所述聚酯根据ASTM D256在1/8英寸厚棒中用10密耳的缺口在23℃测得的缺口悬臂梁式冲击强度至少为647J/m;
其中所述聚酯在290℃在旋转熔体流变仪上以1弧度/秒测得的熔体粘度小于10,000泊。
28.含有至少一种聚酯组合物的膜或片,该聚酯组合物包含至少一种聚酯,其含有:
(a) 二羧酸组分,包括:
i) 70-100摩尔%的对苯二甲酸残基;
ii) 0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii) 0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;
(b) 二醇组分,包括:
i) 15-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii) 75-85摩尔%的1,4-环己烷二甲醇残基;以及
(c) 来自至少一种支化剂的残基;
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;
其中,在60/40wt/wt的苯酚/四氯乙烷中,0.5 g/100 ml浓度下,在25℃测定的所述聚酯的比浓对数粘度为0.60-0.75 dL/g;
其中所述聚酯的Tg为85-120℃;
其中所述聚酯根据ASTM D256在1/8英寸厚棒中用10密耳的缺口在23℃测得的缺口悬臂梁式冲击强度至少为647J/m;
其中所述聚酯在290℃在旋转熔体流变仪上以1弧度/秒测得的熔体粘度小于10,000泊;并且
其中所述聚酯组合物不含聚碳酸酯。
29.权利要求28的含有至少一种聚酯组合物的膜或片,其中,所述聚酯包含的支化剂残基的量为基于二酸残基或二醇残基的总摩尔百分比为 0.01-10重量%。
30.权利要求28的含有至少一种聚酯组合物的膜或片,其中,所述聚酯具有的比浓对数粘度为0.6-0.72 dL/g。
31.含有至少一种聚酯组合物的膜或片,该聚酯组合物包含:
(I) 至少一种聚酯,其包括:
(a) 二羧酸组分,包括:
i) 70-100摩尔%的对苯二甲酸残基;
ii) 0-30摩尔%的具有至多20个碳原子的芳族二羧酸残基;以及
iii) 0-10摩尔%的具有至多16个碳原子的脂族二羧酸残基;以及
(b) 二醇组分,包括:
i) 15-25摩尔%的2,2,4,4-四甲基-1,3-环丁二醇残基;以及
ii) 75-85摩尔%的1,4-环己烷二甲醇残基;以及
(II) 至少一种热稳定剂或其反应产物;
其中,二羧酸组分的总摩尔%为100摩尔%,二醇组分的总摩尔%为100摩尔%;
其中,在60/40wt/wt的苯酚/四氯乙烷中,0.5 g/100 ml浓度下,在25℃测定的所述聚酯的比浓对数粘度为0.5-1.2 dL/g;
其中所述聚酯的Tg为85-120℃;
其中所述聚酯根据ASTM D256在1/8英寸厚棒中用10密耳的缺口在23℃测得的缺口悬臂梁式冲击强度至少为647J/m;
其中所述聚酯在290℃在旋转熔体流变仪上以1弧度/秒测得的熔体粘度小于10,000泊;并且
其中所述聚酯组合物不含聚碳酸酯。
32.权利要求31的含有至少一种聚酯组合物的膜或片,其中,所述聚酯具有的比浓对数粘度为0.6-0.72 dL/g。
33.权利要求31的含有至少一种聚酯组合物的膜或片,其中,所述聚酯具有的Tg为95-115℃。
Applications Claiming Priority (18)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69156705P | 2005-06-17 | 2005-06-17 | |
US60/691567 | 2005-06-17 | ||
US73138905P | 2005-10-28 | 2005-10-28 | |
US73145405P | 2005-10-28 | 2005-10-28 | |
US60/731454 | 2005-10-28 | ||
US60/731389 | 2005-10-28 | ||
US73905805P | 2005-11-22 | 2005-11-22 | |
US73886905P | 2005-11-22 | 2005-11-22 | |
US60/738869 | 2005-11-22 | ||
US60/739058 | 2005-11-22 | ||
US75069205P | 2005-12-15 | 2005-12-15 | |
US75054705P | 2005-12-15 | 2005-12-15 | |
US75068205P | 2005-12-15 | 2005-12-15 | |
US75069305P | 2005-12-15 | 2005-12-15 | |
US60/750682 | 2005-12-15 | ||
US60/750692 | 2005-12-15 | ||
US60/750693 | 2005-12-15 | ||
US60/750547 | 2005-12-15 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA2006800207458A Division CN101193946A (zh) | 2005-06-17 | 2006-03-30 | 含有少量环丁二醇的聚酯组合物制成的膜和/或片材 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103755930A true CN103755930A (zh) | 2014-04-30 |
Family
ID=36630440
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310616094.0A Pending CN103755930A (zh) | 2005-06-17 | 2006-03-30 | 含有少量环丁二醇的聚酯组合物制成的膜和/或片材 |
Country Status (18)
Country | Link |
---|---|
US (59) | US7842776B2 (zh) |
EP (49) | EP2156934B1 (zh) |
JP (38) | JP2008546603A (zh) |
KR (14) | KR20080019218A (zh) |
CN (1) | CN103755930A (zh) |
AR (1) | AR055897A1 (zh) |
AT (20) | ATE475683T1 (zh) |
AU (2) | AU2006262854A1 (zh) |
BR (3) | BRPI0613698A2 (zh) |
DE (19) | DE602006012319D1 (zh) |
ES (1) | ES2341482T3 (zh) |
HK (4) | HK1115398A1 (zh) |
IL (3) | IL188026A0 (zh) |
MX (5) | MX2007015664A (zh) |
MY (2) | MY145986A (zh) |
PL (3) | PL1907442T3 (zh) |
TW (9) | TW200700456A (zh) |
WO (39) | WO2007001529A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114206615A (zh) * | 2019-08-02 | 2022-03-18 | 伊士曼化工公司 | 多层片材 |
WO2023206073A1 (en) * | 2022-04-26 | 2023-11-02 | Eastman Chemical (China) Co., Ltd. | Flame retardant copolyester compositions |
Families Citing this family (243)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL150601A (en) * | 2001-07-19 | 2010-06-30 | Organon Nv | Process for rapid synthesis of peptides within a solution using the back of an activated carboxyl component and destruction of the residual activated carboxyl component |
US7842776B2 (en) | 2005-06-17 | 2010-11-30 | Eastman Chemical Company | Appliance parts comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
WO2007053549A1 (en) * | 2005-10-28 | 2007-05-10 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US20130072628A1 (en) * | 2005-06-17 | 2013-03-21 | Eastman Chemical Company | Coating compositions containing cyclobutanediol |
US7704605B2 (en) * | 2006-03-28 | 2010-04-27 | Eastman Chemical Company | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
ATE411360T1 (de) * | 2005-06-17 | 2008-10-15 | Eastman Chem Co | Verfahren zur herstellung von ein cyclobutandiol umfassenden polyester enthaltenden transparenten formkörpern |
US8586701B2 (en) | 2005-10-28 | 2013-11-19 | Eastman Chemical Company | Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
ATE505500T1 (de) * | 2005-10-28 | 2011-04-15 | Eastman Chem Co | Polyesterzusammensetzungen mit cyclobutandiol mit hoher glasübergangstemperatur und daraus hergestellte artikel |
US9598533B2 (en) | 2005-11-22 | 2017-03-21 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US9169388B2 (en) | 2006-03-28 | 2015-10-27 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof |
JP4923671B2 (ja) * | 2006-03-29 | 2012-04-25 | ソニー株式会社 | 液晶表示装置 |
US8083094B2 (en) | 2006-08-10 | 2011-12-27 | Capitol Vial Inc. | Container and cap assembly |
US20110089187A1 (en) * | 2006-08-10 | 2011-04-21 | Capitol Vial Inc. | Shatterproof Container And Cap Assembly |
US20080053752A1 (en) * | 2006-09-06 | 2008-03-06 | Peter Miller | System and method for securing a window in a panel |
US8287991B2 (en) * | 2006-10-04 | 2012-10-16 | Eastman Chemical Company | Using branched polymers to control the dimensional stability of articles in the lamination process |
US20080085390A1 (en) | 2006-10-04 | 2008-04-10 | Ryan Thomas Neill | Encapsulation of electrically energized articles |
US8080191B2 (en) * | 2006-10-20 | 2011-12-20 | Pepsico, Inc. | Extrudable polyethylene terephthalate blend |
WO2008088336A1 (en) * | 2007-01-18 | 2008-07-24 | Sabic Innovative Plastics Ip B.V. | COATED ARTICLES OF MANUFACTURE MADE OF HIGH Tg POLYMER BLENDS |
CN101711374B (zh) * | 2007-03-08 | 2011-11-02 | 澳加光学有限公司 | 乙二醇改性聚酯眼镜和眼镜镜架 |
JP5346443B2 (ja) | 2007-04-16 | 2013-11-20 | ローム株式会社 | 半導体発光素子およびその製造方法 |
KR101549455B1 (ko) * | 2007-04-20 | 2015-09-03 | 티+잉크, 인코포레이티드 | 인몰드된 정전용량 방식 스위치 |
US8198979B2 (en) * | 2007-04-20 | 2012-06-12 | Ink-Logix, Llc | In-molded resistive and shielding elements |
EP2789639B1 (en) * | 2007-05-10 | 2017-01-25 | Eastman Chemical Company | Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutane diol and 1,4-cyclohexanedimethanol |
US7748137B2 (en) * | 2007-07-15 | 2010-07-06 | Yin Wang | Wood-drying solar greenhouse |
US20090023885A1 (en) * | 2007-07-16 | 2009-01-22 | Texas State University - San Marcos | Treatment method for imparting high impact resistance in certain cbdo copolymers |
US7772362B2 (en) * | 2007-07-16 | 2010-08-10 | Texas State University | Treatment method for imparting self-healing and shape memory properties to certain CBDO copolymers |
CN101434744B (zh) * | 2007-11-14 | 2013-12-18 | 财团法人工业技术研究院 | 混掺物及封装材料 |
US8501287B2 (en) * | 2007-11-21 | 2013-08-06 | Eastman Chemical Company | Plastic baby bottles, other blow molded articles, and processes for their manufacture |
CN101868340B (zh) * | 2007-11-21 | 2016-04-20 | 伊士曼化工公司 | 塑料乳瓶、其它吹塑物品及其制备方法 |
GB0800459D0 (en) * | 2008-01-11 | 2008-02-20 | Innovata Biomed Ltd | Improvements in or relating to inhalers |
DE102008011721B4 (de) * | 2008-02-28 | 2011-06-09 | Mapa Gmbh | Beruhigungssauger mit an einem Mundschild fixiertem Lutschteil |
EP2268737B1 (en) | 2008-04-18 | 2019-01-16 | PepsiCo, Inc. | Polyester compositions and method for preparing articles by extrusion blow molding |
US7901780B2 (en) * | 2008-06-25 | 2011-03-08 | Solutia Inc. | Polymer interlayers comprising blends of plasticized poly(vinyl butyral) and poly(cyclohexanedimethylene terephthalate-co-ethylene terephthalate) copolyester |
US8198371B2 (en) * | 2008-06-27 | 2012-06-12 | Eastman Chemical Company | Blends of polyesters and ABS copolymers |
US7960007B2 (en) * | 2008-07-11 | 2011-06-14 | Teknor Apex Company | Retortable liners and containers |
US20100143546A1 (en) * | 2008-12-09 | 2010-06-10 | The Coca-Cola Company | Container and composition for enhanced gas barrier properties |
US8110265B2 (en) | 2008-12-09 | 2012-02-07 | The Coca-Cola Company | Pet container and compositions having enhanced mechanical properties and gas barrier properties |
US8895654B2 (en) * | 2008-12-18 | 2014-11-25 | Eastman Chemical Company | Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid |
US20100168328A1 (en) * | 2008-12-30 | 2010-07-01 | Ganesh Kannan | Process for the manufacture of polycyclohexane dimethylene terephthalate copolymers from polyethylene terephthalate, and compositions and articles thereof |
US9161888B2 (en) | 2009-01-13 | 2015-10-20 | Michelle Lamar | Pacifier apparatus |
US9029461B2 (en) | 2009-02-06 | 2015-05-12 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
US9029460B2 (en) | 2009-02-06 | 2015-05-12 | Stacey James Marsh | Coating compositions containing acrylic and aliphatic polyester blends |
US8324316B2 (en) * | 2009-02-06 | 2012-12-04 | Eastman Chemical Company | Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom |
US20100210775A1 (en) | 2009-02-13 | 2010-08-19 | Eastman Chemical Company | Reinforced polyester compositions having improved toughness |
US9062197B2 (en) * | 2009-03-27 | 2015-06-23 | Eastman Chemical Company | Polyester blends |
EP2414426B1 (en) * | 2009-04-01 | 2014-12-10 | Eastman Chemical Company | Improved process for the production of polyesters |
US9008321B2 (en) | 2009-06-08 | 2015-04-14 | Nokia Corporation | Audio processing |
JP5586177B2 (ja) * | 2009-06-23 | 2014-09-10 | 三菱樹脂株式会社 | 積層シート、及び積層シートを被覆した金属板 |
ES2355220B2 (es) * | 2009-08-17 | 2011-09-19 | Sp Kloner Ecotec, S.L. | Perfiles estructurales para la fabricacion de utensilios domesticos y proceso para obtener esos perfiles. |
KR20110028696A (ko) * | 2009-09-14 | 2011-03-22 | 에스케이케미칼주식회사 | 아이소소바이드와 1,4-사이클로헥산디메탄올이 공중합된 폴리에스테르 수지 및 그 제조방법 |
US8586652B2 (en) * | 2009-10-09 | 2013-11-19 | Eastman Chemical Company | Polyester compositions for molding clear parts |
US20110091705A1 (en) * | 2009-10-19 | 2011-04-21 | Eastman Chemical Company | Radio-frequency sealable polymer and articles thereof |
US20110104342A1 (en) * | 2009-11-03 | 2011-05-05 | Kevin David Glaser | Chlorine-Free Packaging Sheet with Tear-Resistance Properties |
US8574694B2 (en) | 2009-11-03 | 2013-11-05 | Curwood, Inc. | Packaging sheet with improved cutting properties |
JP4888853B2 (ja) | 2009-11-12 | 2012-02-29 | 学校法人慶應義塾 | 液晶表示装置の視認性改善方法、及びそれを用いた液晶表示装置 |
EP2521526B1 (en) * | 2009-11-20 | 2019-07-03 | DENTSPLY SIRONA Inc. | Dental materials using 2,2,4,4-tetramethyl-1,3-cyclobutanediol |
FR2957152B1 (fr) | 2010-03-04 | 2012-08-03 | Christian Dalloz Sunoptics | Nouveau materiau composite a usage optique ainsi que son procede d'obtention |
MY153955A (en) * | 2010-03-16 | 2015-04-20 | Sumitomo Bakelite Co | Resin composition sheet,and method for molding thereof |
JP5653061B2 (ja) * | 2010-04-09 | 2015-01-14 | 株式会社ジェイエスピー | 建築又は土木用熱可塑性樹脂押出発泡断熱板 |
BR112012026240B1 (pt) | 2010-04-16 | 2021-08-03 | Swimc Llc | Artigo, método, e, composição de revestimento |
US8283800B2 (en) | 2010-05-27 | 2012-10-09 | Ford Global Technologies, Llc | Vehicle control system with proximity switch and method thereof |
US8707739B2 (en) | 2012-06-11 | 2014-04-29 | Johns Manville | Apparatus, systems and methods for conditioning molten glass |
US8707740B2 (en) | 2011-10-07 | 2014-04-29 | Johns Manville | Submerged combustion glass manufacturing systems and methods |
US10322960B2 (en) | 2010-06-17 | 2019-06-18 | Johns Manville | Controlling foam in apparatus downstream of a melter by adjustment of alkali oxide content in the melter |
US9032760B2 (en) | 2012-07-03 | 2015-05-19 | Johns Manville | Process of using a submerged combustion melter to produce hollow glass fiber or solid glass fiber having entrained bubbles, and burners and systems to make such fibers |
US8991215B2 (en) | 2010-06-17 | 2015-03-31 | Johns Manville | Methods and systems for controlling bubble size and bubble decay rate in foamed glass produced by a submerged combustion melter |
US9021838B2 (en) | 2010-06-17 | 2015-05-05 | Johns Manville | Systems and methods for glass manufacturing |
US9776903B2 (en) | 2010-06-17 | 2017-10-03 | Johns Manville | Apparatus, systems and methods for processing molten glass |
US8769992B2 (en) | 2010-06-17 | 2014-07-08 | Johns Manville | Panel-cooled submerged combustion melter geometry and methods of making molten glass |
US8973405B2 (en) | 2010-06-17 | 2015-03-10 | Johns Manville | Apparatus, systems and methods for reducing foaming downstream of a submerged combustion melter producing molten glass |
US8875544B2 (en) | 2011-10-07 | 2014-11-04 | Johns Manville | Burner apparatus, submerged combustion melters including the burner, and methods of use |
US8973400B2 (en) | 2010-06-17 | 2015-03-10 | Johns Manville | Methods of using a submerged combustion melter to produce glass products |
US9096452B2 (en) | 2010-06-17 | 2015-08-04 | Johns Manville | Methods and systems for destabilizing foam in equipment downstream of a submerged combustion melter |
US8650914B2 (en) | 2010-09-23 | 2014-02-18 | Johns Manville | Methods and apparatus for recycling glass products using submerged combustion |
US8997525B2 (en) | 2010-06-17 | 2015-04-07 | Johns Manville | Systems and methods for making foamed glass using submerged combustion |
JP4962661B2 (ja) | 2010-06-22 | 2012-06-27 | 東洋紡績株式会社 | 液晶表示装置、偏光板および偏光子保護フィルム |
US8686072B2 (en) | 2010-06-29 | 2014-04-01 | Sabic Innovative Plastics Ip B.V. | Flame resistant polyester compositions, method of manufacture, and articles therof |
US8604105B2 (en) | 2010-09-03 | 2013-12-10 | Eastman Chemical Company | Flame retardant copolyester compositions |
CA2818247C (en) * | 2010-12-06 | 2014-10-28 | Colgate-Palmolive Company | Laminate tube having enhanced resiliency by a block copolymer |
US20120184668A1 (en) | 2011-01-17 | 2012-07-19 | Eastman Chemical Company | Clear Ternary Blends of Polycarbonate with an Aliphatic Polyester and an Aromatic-Aliphatic Polyester |
DE102011009820A1 (de) * | 2011-01-31 | 2011-10-13 | Mitsubishi Polyester Film Gmbh | Schwarze oder graue biaxial gestreckte Polyesterfolie mit hohem Cyclohexandimethanolanteil und einem primären und sekundären Dicarbonsäureanteil sowie ein Verfahren zu ihrer Herstellung und ihre Verwendung |
EP4219634A1 (en) | 2011-02-07 | 2023-08-02 | Swimc Llc | Coating compositions for containers and other articles and methods of coating |
CN103370372B (zh) | 2011-02-18 | 2016-06-15 | 绿安全股份有限公司 | 在自然环境条件下和比其严酷的自然环境条件下或者与其同样或在其以上的严酷的使用条件下稳定,耐化学性和耐久性优异的透明树脂组合物及使用其的制品 |
US9421308B2 (en) | 2011-02-22 | 2016-08-23 | Polyone Corporation | Polyester compounds suitable for hydroclaving |
US9090769B2 (en) | 2011-04-05 | 2015-07-28 | Ticona Llc | Molded articles having a swirl-like or marble-like appearance and compositions for producing same |
US20120305575A1 (en) * | 2011-06-01 | 2012-12-06 | Eastman Chemical Company | High strength bottle |
US8928336B2 (en) | 2011-06-09 | 2015-01-06 | Ford Global Technologies, Llc | Proximity switch having sensitivity control and method therefor |
US8975903B2 (en) | 2011-06-09 | 2015-03-10 | Ford Global Technologies, Llc | Proximity switch having learned sensitivity and method therefor |
JP2013001089A (ja) * | 2011-06-21 | 2013-01-07 | Nippon Kararingu Kk | カード用シート |
WO2012176533A1 (ja) * | 2011-06-21 | 2012-12-27 | 日本カラリング株式会社 | カード用シート |
JP2013001090A (ja) * | 2011-06-21 | 2013-01-07 | Nippon Kararingu Kk | カード用シート |
US9150006B2 (en) | 2011-06-23 | 2015-10-06 | Eastman Chemical Company | Lamination process optimization utilizing neopentyl glycol-modified polyesters |
EP2546282A1 (de) * | 2011-07-14 | 2013-01-16 | Basf Se | Thermoplastische Formmasse |
US10004286B2 (en) | 2011-08-08 | 2018-06-26 | Ford Global Technologies, Llc | Glove having conductive ink and method of interacting with proximity sensor |
WO2013034950A1 (en) * | 2011-09-08 | 2013-03-14 | Société Anonyme Des Eaux Minerales D'evian | Method for producing a bio-pet polymer |
EP2753468B1 (en) * | 2011-09-09 | 2017-03-08 | LG Innotek Co., Ltd. | A method of fabricating thick film of large area substrate and thick film, backlight unit and liquid crystal display using the same |
US9143126B2 (en) | 2011-09-22 | 2015-09-22 | Ford Global Technologies, Llc | Proximity switch having lockout control for controlling movable panel |
EP2578412B1 (en) * | 2011-10-07 | 2014-06-25 | 3M Innovative Properties Company | Printable film |
US10800877B2 (en) * | 2011-10-14 | 2020-10-13 | Eastman Chemical Company | Polyester compositions containing furandicarboxylic acid or an ester thereof, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol |
JP5892518B2 (ja) * | 2011-10-28 | 2016-03-23 | 株式会社ニッシン | 歯科用成形体 |
JP5806326B2 (ja) | 2011-11-01 | 2015-11-10 | ミドリ安全株式会社 | 樹脂組成物及び成形体 |
US8994228B2 (en) | 2011-11-03 | 2015-03-31 | Ford Global Technologies, Llc | Proximity switch having wrong touch feedback |
US10112556B2 (en) | 2011-11-03 | 2018-10-30 | Ford Global Technologies, Llc | Proximity switch having wrong touch adaptive learning and method |
US8878438B2 (en) | 2011-11-04 | 2014-11-04 | Ford Global Technologies, Llc | Lamp and proximity switch assembly and method |
JP5899235B2 (ja) * | 2011-11-04 | 2016-04-06 | 旭化成メディカル株式会社 | 血液処理用分離膜、及びその膜を組み込んだ血液処理器 |
EP2782990B1 (en) * | 2011-11-21 | 2020-10-07 | Innovation Hammer LLC | Method for growing plants using silicate microbeads and photosafening by utilization of exogenous glycopyranosides |
CN102676591A (zh) * | 2012-01-12 | 2012-09-19 | 河南科技大学 | 一种制备含3-羟基戊二酸单元聚酯的方法 |
US8669314B2 (en) | 2012-02-03 | 2014-03-11 | Sabic Innovative Plastics Ip B.V. | Hydrolytic stability in polycarbonate compositions |
US20130217830A1 (en) * | 2012-02-16 | 2013-08-22 | Eastman Chemical Company | Clear Semi-Crystalline Articles with Improved Heat Resistance |
KR101417250B1 (ko) | 2012-02-20 | 2014-07-08 | (주)엘지하우시스 | 고내열성 다층 광학필름 및 그의 제조방법 |
EP2820113B1 (en) | 2012-02-28 | 2017-07-12 | SABIC Global Technologies B.V. | Processes and compositions for cleaning mixing devices to improve polycarbonate production |
US9219472B2 (en) | 2012-04-11 | 2015-12-22 | Ford Global Technologies, Llc | Proximity switch assembly and activation method using rate monitoring |
US9531379B2 (en) | 2012-04-11 | 2016-12-27 | Ford Global Technologies, Llc | Proximity switch assembly having groove between adjacent proximity sensors |
US8933708B2 (en) | 2012-04-11 | 2015-01-13 | Ford Global Technologies, Llc | Proximity switch assembly and activation method with exploration mode |
US9944237B2 (en) | 2012-04-11 | 2018-04-17 | Ford Global Technologies, Llc | Proximity switch assembly with signal drift rejection and method |
US9660644B2 (en) | 2012-04-11 | 2017-05-23 | Ford Global Technologies, Llc | Proximity switch assembly and activation method |
US9197206B2 (en) | 2012-04-11 | 2015-11-24 | Ford Global Technologies, Llc | Proximity switch having differential contact surface |
US9065447B2 (en) | 2012-04-11 | 2015-06-23 | Ford Global Technologies, Llc | Proximity switch assembly and method having adaptive time delay |
US9559688B2 (en) | 2012-04-11 | 2017-01-31 | Ford Global Technologies, Llc | Proximity switch assembly having pliable surface and depression |
US9831870B2 (en) | 2012-04-11 | 2017-11-28 | Ford Global Technologies, Llc | Proximity switch assembly and method of tuning same |
US9520875B2 (en) | 2012-04-11 | 2016-12-13 | Ford Global Technologies, Llc | Pliable proximity switch assembly and activation method |
US9287864B2 (en) | 2012-04-11 | 2016-03-15 | Ford Global Technologies, Llc | Proximity switch assembly and calibration method therefor |
US9184745B2 (en) | 2012-04-11 | 2015-11-10 | Ford Global Technologies, Llc | Proximity switch assembly and method of sensing user input based on signal rate of change |
US9568527B2 (en) | 2012-04-11 | 2017-02-14 | Ford Global Technologies, Llc | Proximity switch assembly and activation method having virtual button mode |
US9533905B2 (en) | 2012-10-03 | 2017-01-03 | Johns Manville | Submerged combustion melters having an extended treatment zone and methods of producing molten glass |
US9136840B2 (en) | 2012-05-17 | 2015-09-15 | Ford Global Technologies, Llc | Proximity switch assembly having dynamic tuned threshold |
US9080763B2 (en) | 2012-05-17 | 2015-07-14 | GE Lighting Solutions, LLC | Edge lit luminaires for windows |
US8981602B2 (en) | 2012-05-29 | 2015-03-17 | Ford Global Technologies, Llc | Proximity switch assembly having non-switch contact and method |
US9337832B2 (en) | 2012-06-06 | 2016-05-10 | Ford Global Technologies, Llc | Proximity switch and method of adjusting sensitivity therefor |
US9641172B2 (en) | 2012-06-27 | 2017-05-02 | Ford Global Technologies, Llc | Proximity switch assembly having varying size electrode fingers |
US9273206B2 (en) | 2012-07-09 | 2016-03-01 | Eastman Chemical Company | Ternary blends of terephthalate or isophthalate polyesters containing EG, CHDM and TMCD |
EP3483227B1 (en) | 2012-08-09 | 2020-12-16 | Swimc, LLC | Compositions for containers and other articles and methods of using same |
US9475328B2 (en) | 2012-08-09 | 2016-10-25 | Valspar Sourcing, Inc. | Developer for thermally responsive record materials |
KR102093405B1 (ko) | 2012-08-09 | 2020-03-25 | 에스더블유아이엠씨 엘엘씨 | 용기 코팅 시스템 |
WO2014025410A1 (en) | 2012-08-09 | 2014-02-13 | Valspar Sourcing, Inc. | Stabilizer and coating compositions thereof |
EP2882792A4 (en) | 2012-08-09 | 2016-04-13 | Valspar Sourcing Inc | POLYCARBONATE |
EP2882401A4 (en) | 2012-08-09 | 2016-03-30 | Valspar Sourcing Inc | DENTAL MATERIALS AND MANUFACTURING METHOD |
US9102597B2 (en) | 2012-09-05 | 2015-08-11 | Sabic Global Technologies B.V. | Indane bisphenols, polymers derived therefrom, and methods of use thereof |
US8922340B2 (en) | 2012-09-11 | 2014-12-30 | Ford Global Technologies, Llc | Proximity switch based door latch release |
US9788765B2 (en) | 2012-09-28 | 2017-10-17 | Dexcom, Inc. | Zwitterion surface modifications for continuous sensors |
EP2903941A4 (en) | 2012-10-03 | 2016-06-08 | Johns Manville | METHOD AND SYSTEMS FOR DESTABILIZING FOAM IN A DEVICE HAVING BEEN SWITCHED DOWN UNDERWATER COMBUSTION FURNACE |
US20150247037A1 (en) * | 2012-10-15 | 2015-09-03 | Asahi Kasei Chemicals Corporation | Thermoplastic resin composition and molded article thereof |
US8623483B1 (en) | 2012-10-23 | 2014-01-07 | Eastman Chemical Company | Copolyesters containing neopentyl glycol and 2,2,4,4-tetraalkyl 1,3-cyclobutanediol |
US9127122B2 (en) | 2012-10-23 | 2015-09-08 | Eastman Chemical Company | Copolyesters containing neopentyl glycol and 2,2,4,4-tetraalkyl 1,3-cyclobutanediol |
US8796575B2 (en) | 2012-10-31 | 2014-08-05 | Ford Global Technologies, Llc | Proximity switch assembly having ground layer |
US9227865B2 (en) | 2012-11-29 | 2016-01-05 | Johns Manville | Methods and systems for making well-fined glass using submerged combustion |
US9296894B2 (en) | 2013-03-13 | 2016-03-29 | Sabic Global Technologies B.V. | Reinforced polyestercarbonate, polycarbonate-polydiorganosiloxane, poly(butylene-terephthalate) blend, and article comprising same |
US9311204B2 (en) | 2013-03-13 | 2016-04-12 | Ford Global Technologies, Llc | Proximity interface development system having replicator and method |
WO2014189504A1 (en) | 2013-05-22 | 2014-11-27 | Johns Manville | Submerged combustion burners |
WO2014189501A1 (en) | 2013-05-22 | 2014-11-27 | Johns Manville | Submerged combustion burners, melters, and methods of use |
US10138151B2 (en) | 2013-05-22 | 2018-11-27 | Johns Manville | Submerged combustion burners and melters, and methods of use |
EP2999923B1 (en) | 2013-05-22 | 2018-08-15 | Johns Manville | Submerged combustion melter with improved burner and corresponding method |
US9777922B2 (en) | 2013-05-22 | 2017-10-03 | Johns Mansville | Submerged combustion burners and melters, and methods of use |
EP3003997B1 (en) | 2013-05-30 | 2021-04-28 | Johns Manville | Submerged combustion burners with mixing improving means for glass melters, and use |
PL3003996T3 (pl) | 2013-05-30 | 2020-12-28 | Johns Manville | Układy do topienia szkła ze spalaniem zanurzeniowym i sposoby ich zastosowania |
WO2014196378A1 (ja) | 2013-06-03 | 2014-12-11 | 東洋紡株式会社 | ポリエステル樹脂、及びそれを使用した表面実装型led反射板用ポリエステル樹脂組成物 |
US20140370218A1 (en) | 2013-06-14 | 2014-12-18 | Eastman Chemical Company | Foamed articles with deep undercuts |
WO2015009300A1 (en) | 2013-07-18 | 2015-01-22 | Johns Manville | Fluid cooled combustion burner and method of making said burner |
US10259922B2 (en) | 2013-11-06 | 2019-04-16 | The Board Of Trustees Of The Leland Stanford Junior University | Methods for modifying a hydrophobic polymer surface and devices thereof |
JP5630795B1 (ja) | 2014-03-24 | 2014-11-26 | 有限会社金栄堂 | 着色レンズの設計方法 |
CN110790914A (zh) | 2014-04-14 | 2020-02-14 | 宣伟投资管理有限公司 | 制备用于容器和其它制品的组合物的方法以及使用所述组合物的方法 |
CN104017365B (zh) * | 2014-05-19 | 2016-05-11 | 安徽省康利亚实业有限公司 | 一种轨道车辆用高强度电缆料及其制备方法 |
US9238609B2 (en) | 2014-05-23 | 2016-01-19 | Sabic Global Technologies B.V. | Dicarboxylic acid monomers and methods of making and using the same |
JP2015028177A (ja) * | 2014-09-22 | 2015-02-12 | イーストマン ケミカル カンパニー | ポリエステルを製造するための改善された方法 |
US10038443B2 (en) | 2014-10-20 | 2018-07-31 | Ford Global Technologies, Llc | Directional proximity switch assembly |
US9650539B2 (en) | 2014-10-27 | 2017-05-16 | Eastman Chemical Company | Thermosetting compositions based on unsaturated polyesters and phenolic resins |
US9487619B2 (en) | 2014-10-27 | 2016-11-08 | Eastman Chemical Company | Carboxyl functional curable polyesters containing tetra-alkyl cyclobutanediol |
US9598602B2 (en) | 2014-11-13 | 2017-03-21 | Eastman Chemical Company | Thermosetting compositions based on phenolic resins and curable poleyester resins made with diketene or beta-ketoacetate containing compounds |
US11229095B2 (en) | 2014-12-17 | 2022-01-18 | Campbell Soup Company | Electromagnetic wave food processing system and methods |
CN107278213B (zh) | 2015-02-27 | 2020-10-23 | 沙特基础工业全球技术有限公司 | 通过卤素置换制备低色聚醚酰亚胺的方法及低色聚醚酰亚胺 |
EP3262101A1 (en) | 2015-02-27 | 2018-01-03 | SABIC Global Technologies B.V. | Polyetherimide with improved color, and methods of manufacture thereof |
US9654103B2 (en) | 2015-03-18 | 2017-05-16 | Ford Global Technologies, Llc | Proximity switch assembly having haptic feedback and method |
MX2017013229A (es) * | 2015-04-13 | 2018-02-23 | Coca Cola Co | Botella de polimero rellenable y metodo para resistencia mejorada al agrietamiento por estrés cáustico.. |
CN107548352A (zh) | 2015-04-28 | 2018-01-05 | 沙特基础工业全球技术有限公司 | 多层材料和由其制造的制品以及制造方法 |
US20160340471A1 (en) * | 2015-05-19 | 2016-11-24 | Eastman Chemical Company | Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol |
US9548733B2 (en) | 2015-05-20 | 2017-01-17 | Ford Global Technologies, Llc | Proximity sensor assembly having interleaved electrode configuration |
WO2016196268A1 (en) | 2015-05-29 | 2016-12-08 | Sabic Global Technologies B.V. | Polyetherimide of improved color and process of preparing |
JP6487287B2 (ja) * | 2015-07-16 | 2019-03-20 | リケンテクノス株式会社 | 金属板被覆用化粧シート |
JP6656253B2 (ja) * | 2015-08-05 | 2020-03-04 | リケンテクノス株式会社 | 制電性樹脂組成物 |
US9751792B2 (en) | 2015-08-12 | 2017-09-05 | Johns Manville | Post-manufacturing processes for submerged combustion burner |
US10670261B2 (en) | 2015-08-27 | 2020-06-02 | Johns Manville | Burner panels, submerged combustion melters, and methods |
US10041666B2 (en) | 2015-08-27 | 2018-08-07 | Johns Manville | Burner panels including dry-tip burners, submerged combustion melters, and methods |
US9815726B2 (en) | 2015-09-03 | 2017-11-14 | Johns Manville | Apparatus, systems, and methods for pre-heating feedstock to a melter using melter exhaust |
US9982884B2 (en) | 2015-09-15 | 2018-05-29 | Johns Manville | Methods of melting feedstock using a submerged combustion melter |
US10837705B2 (en) | 2015-09-16 | 2020-11-17 | Johns Manville | Change-out system for submerged combustion melting burner |
US10081563B2 (en) | 2015-09-23 | 2018-09-25 | Johns Manville | Systems and methods for mechanically binding loose scrap |
US20170088665A1 (en) | 2015-09-25 | 2017-03-30 | Eastman Chemical Company | POLYMERS CONTAINING CYCLOBUTANEDIOL AND 2,2 BIS(HYDROXYMETHYL) AlKYLCARBOXYLIC ACID |
US10144666B2 (en) | 2015-10-20 | 2018-12-04 | Johns Manville | Processing organics and inorganics in a submerged combustion melter |
TWI614275B (zh) | 2015-11-03 | 2018-02-11 | Valspar Sourcing Inc | 用於製備聚合物的液體環氧樹脂組合物 |
US10767041B2 (en) | 2015-11-24 | 2020-09-08 | Eastman Chemical Company | Polymer compositions and substrates for high temperature transparent conductive film applications |
EP3387038A1 (en) | 2015-12-11 | 2018-10-17 | Societe Anonyme des Eaux Minerales d'Evian Et en Abrege "S.A.E.M.E" | Pet polymer with an anti-crystallization comonomer that can be bio-sourced |
US10767005B2 (en) | 2015-12-22 | 2020-09-08 | Exxonmobil Chemical Patents Inc. | Bibenzoate copolyesters and methods to produce them |
CN108368223A (zh) * | 2015-12-22 | 2018-08-03 | 埃克森美孚化学专利公司 | 对苯二甲酸酯-共聚-联苯甲酸酯聚酯 |
KR102593983B1 (ko) * | 2015-12-28 | 2023-10-24 | 니폰 제온 가부시키가이샤 | 광학 적층체 및 그 제조 방법, 편광판 및 표시 장치 |
US20170188905A1 (en) * | 2015-12-30 | 2017-07-06 | Dexcom, Inc. | Biointerface layer for analyte sensors |
US9988553B2 (en) | 2016-02-22 | 2018-06-05 | Eastman Chemical Company | Thermosetting coating compositions |
US10011737B2 (en) | 2016-03-23 | 2018-07-03 | Eastman Chemical Company | Curable polyester polyols and their use in thermosetting soft feel coating formulations |
JP6256721B2 (ja) * | 2016-03-28 | 2018-01-10 | 東洋紡株式会社 | 偏光子保護フィルム、偏光板、それを用いた液晶表示装置 |
US10287402B2 (en) | 2016-04-29 | 2019-05-14 | Exxonmobil Chemical Patents Inc. | Polycarbonate-polyolefin block copolymers and methods of making them |
US10246362B2 (en) | 2016-06-22 | 2019-04-02 | Johns Manville | Effective discharge of exhaust from submerged combustion melters and methods |
CN106188553A (zh) * | 2016-08-11 | 2016-12-07 | 苏州柯创电子材料有限公司 | 共聚酯电子绝缘垫块及其制造方法 |
EP3496944A4 (en) * | 2016-08-15 | 2020-07-01 | Klöckner Pentaplast of America, Inc. | HOT FILL LAMINATE |
US10337732B2 (en) | 2016-08-25 | 2019-07-02 | Johns Manville | Consumable tip burners, submerged combustion melters including same, and methods |
US10301208B2 (en) | 2016-08-25 | 2019-05-28 | Johns Manville | Continuous flow submerged combustion melter cooling wall panels, submerged combustion melters, and methods of using same |
US10282682B2 (en) | 2016-08-29 | 2019-05-07 | Axon Enterprise, Inc. | Systems and methods for assignment of equipment to an officer |
US10196294B2 (en) | 2016-09-07 | 2019-02-05 | Johns Manville | Submerged combustion melters, wall structures or panels of same, and methods of using same |
US10233105B2 (en) | 2016-10-14 | 2019-03-19 | Johns Manville | Submerged combustion melters and methods of feeding particulate material into such melters |
US10633315B2 (en) | 2016-10-19 | 2020-04-28 | Eastman Chemical Company | Synthesis of bicyclo[2.2.2]octanes |
US11427688B2 (en) * | 2017-04-17 | 2022-08-30 | Eastman Chemical Company | Copolyesters plasticized with polymeric plasticizer |
KR102435819B1 (ko) | 2017-04-28 | 2022-08-24 | (주)스마트큐브랩스 | 스마트 매직 큐브 및 그의 동작방법 |
US11512198B2 (en) * | 2017-06-21 | 2022-11-29 | Eastman Chemical Company | Polyvinyl chloride and copolyester compositions and articles made using these compositions |
US10384854B2 (en) | 2017-06-28 | 2019-08-20 | Bemis Company, Inc. | Packaging sheet for elevated-temperature use |
WO2019046061A1 (en) | 2017-08-30 | 2019-03-07 | Eastman Chemical Company | COPOLYESTER RESIN COMPOSITION HAVING IMPROVED FLUIDITY PROPERTIES |
US11518726B2 (en) | 2017-10-11 | 2022-12-06 | Eastman Chemical Company | Synthesis of bicyclo[2.2.2]octane derivatives |
CN111630122B (zh) | 2018-01-23 | 2023-07-28 | 伊士曼化工公司 | 新型聚酯酰胺、其制备方法以及聚酯酰胺组合物 |
JP2019167460A (ja) * | 2018-03-23 | 2019-10-03 | プランティック・テクノロジーズ・リミテッド | 樹脂組成物 |
WO2019217675A1 (en) * | 2018-05-11 | 2019-11-14 | Sabic Global Technologies B.V. | Noise reducing filled polyester |
DE102018112817A1 (de) | 2018-05-29 | 2019-12-05 | Klöckner Pentaplast Gmbh | Transparente Polymerfolie mit Verfärbungskompensation |
CN108995252B (zh) * | 2018-06-27 | 2020-12-01 | 成都飞机工业(集团)有限责任公司 | 一种复合材料零部件结构胶接的校验方法 |
EP3822319A4 (en) * | 2018-07-11 | 2022-04-13 | Mitsubishi Engineering-Plastics Corporation | THERMOPLASTIC RESIN COMPOSITION AND MOLDED ARTICLE MANUFACTURING METHOD |
JP7017131B2 (ja) * | 2018-08-20 | 2022-02-08 | 三菱エンジニアリングプラスチックス株式会社 | ハードコート層付成形品及びその製造方法 |
MX2021005845A (es) * | 2018-11-19 | 2021-07-15 | Arkema France | Compuestos acrilicos con propiedades superficiales mejoradas. |
CN109801731B (zh) * | 2018-12-03 | 2020-11-17 | 中国辐射防护研究院 | 一种模拟放射性核素湿沉积的装置 |
US10836899B2 (en) | 2018-12-13 | 2020-11-17 | Eastman Chemical Company | Polyesters with specified crystallization half-times |
JP2022527471A (ja) * | 2019-03-29 | 2022-06-02 | ディディピー スペシャルティ エレクトロニック マテリアルズ ユーエス,エルエルシー | 非晶性ポリエステル組成物及び作製方法 |
CN109988408B (zh) * | 2019-04-18 | 2022-02-08 | 重庆市智翔铺道技术工程有限公司 | 多元聚合物合金钢桥面铺装材料及其制备方法 |
CN109971176B (zh) * | 2019-04-18 | 2021-12-17 | 重庆市智翔铺道技术工程有限公司 | 基于聚芳硫醚、聚碳酸酯的钢桥面铺装材料及其制备方法 |
US11946000B2 (en) | 2019-05-24 | 2024-04-02 | Eastman Chemical Company | Blend small amounts of pyoil into a liquid stream processed into a gas cracker |
US11365357B2 (en) | 2019-05-24 | 2022-06-21 | Eastman Chemical Company | Cracking C8+ fraction of pyoil |
US20220325036A1 (en) | 2019-07-29 | 2022-10-13 | Eastman Chemical Company | Process for the preparation of polyesters with recycled monomers from pyrolysis and methanolysis |
CN114206979B (zh) * | 2019-07-31 | 2023-10-24 | 伊士曼(中国)投资管理有限公司 | 具有改进的硬涂层的聚酯制品 |
KR102103927B1 (ko) * | 2019-09-27 | 2020-04-24 | 코오롱플라스틱 주식회사 | 고강성 고내열 열가소성 복합소재 조성물 및 이로부터 제조된 성형품 |
US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
US11319262B2 (en) | 2019-10-31 | 2022-05-03 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
WO2022067113A1 (en) * | 2020-09-24 | 2022-03-31 | Prosomnus Sleep Technologies Inc. | Polymeric mandibular advancement devices and methods for making and using them |
EP4236745A1 (en) * | 2020-10-27 | 2023-09-06 | Eastman Chemical Company | Coating composition containing tmcd polyester and a modifying polyester |
WO2022099164A1 (en) | 2020-11-09 | 2022-05-12 | Eastman Chemical Company | Washing machine door assembly |
JP2023551656A (ja) | 2020-11-18 | 2023-12-12 | クロックナー、ペンタプラスト、オブ、アメリカ、インコーポレイテッド | 熱成形包装およびその形成方法 |
US20220305713A1 (en) * | 2021-03-24 | 2022-09-29 | Celanese International Corporation | Thermoformed Articles Made From Bio-Based Polymers and Compositions Therefore |
US11631814B2 (en) | 2021-07-15 | 2023-04-18 | Wisconsin Alumni Research Foundation | Two-dimensional carbon nanotube liquid crystal films for wafer-scale electronics |
CN117813337A (zh) | 2021-08-03 | 2024-04-02 | 伊士曼化工公司 | 阻燃共聚酯组合物 |
US11787759B2 (en) | 2021-08-12 | 2023-10-17 | Saudi Arabian Oil Company | Dimethyl ether production via dry reforming and dimethyl ether synthesis in a vessel |
WO2023244956A1 (en) | 2022-06-13 | 2023-12-21 | Eastman Chemical Company | Copolyester compositions having low coefficient of friction |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3313777A (en) * | 1959-12-18 | 1967-04-11 | Eastman Kodak Co | Linear polyesters and polyester-amides from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols |
US5962625A (en) * | 1998-06-24 | 1999-10-05 | Eastman Chemical Company | High clarity polyester containing sub-visual antimony phosphate derivatives particles |
US6043322A (en) * | 1996-12-28 | 2000-03-28 | Eastman Chemical Company | Clear polycarbonate and polyester blends |
CN1293696A (zh) * | 1998-03-17 | 2001-05-02 | 伊斯曼化学公司 | 用于压延的聚酯树脂组合物 |
CN1501954A (zh) * | 2001-04-11 | 2004-06-02 | �Ϻ���ͨ��ѧ | 由增塑聚酯制备的薄膜 |
Family Cites Families (460)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US873016A (en) | 1907-12-10 | James Burnham | Pneumatic and solid tire for vehicle-wheels. | |
US360547A (en) * | 1887-04-05 | Shelving | ||
US589404A (en) | 1897-09-07 | bettini | ||
US300906A (en) * | 1884-06-24 | William d | ||
US516994A (en) * | 1894-03-20 | Game apparatus | ||
US644833A (en) * | 1898-11-18 | 1900-03-06 | Sims Hydraulic Engine Company | Impact water-motor. |
US696854A (en) * | 1900-06-06 | 1902-04-01 | Wesley R Cain | Lamplighter and match-extinguisher. |
US729775A (en) * | 1902-06-03 | 1903-06-02 | Arthur E Krause | Method of removing oil or oily matter from water. |
US858012A (en) * | 1906-10-17 | 1907-06-25 | C J De Boor | Smoke-consuming furnace. |
US1187437A (en) * | 1914-08-27 | 1916-06-13 | david r Lucas | Ladder-bracket. |
NL16356C (zh) | 1924-07-22 | |||
GB478303A (en) | 1936-07-13 | 1938-01-13 | Henry Dreyfus | Improvements in the manufacture of ketene, acetic anhydride or a homologue thereof |
GB478326A (en) * | 1936-07-17 | 1938-01-17 | Henry Dreyfus | Improvements in the manufacture of ketene, acetic anhydride or a homologue thereof |
US2278537A (en) | 1937-10-19 | 1942-04-07 | Celanese Corp | Manufacture of aliphatic compounds |
US2720507A (en) | 1952-10-03 | 1955-10-11 | Eastman Kodak Co | Organo-metallic tin catalysts for preparation of polyesters |
NL104015C (zh) | 1953-10-16 | |||
US2806064A (en) | 1954-02-23 | 1957-09-10 | Celanese Corp | Production of anhydrous ketenes |
DE1007996B (de) | 1955-03-26 | 1957-05-09 | Bayer Ag | Verfahren zur Herstellung thermoplastischer Kunststoffe |
US3153008A (en) | 1955-07-05 | 1964-10-13 | Gen Electric | Aromatic carbonate resins and preparation thereof |
BE592181A (zh) | 1955-12-22 | |||
US2991273A (en) | 1956-07-07 | 1961-07-04 | Bayer Ag | Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates |
US3148172A (en) | 1956-07-19 | 1964-09-08 | Gen Electric | Polycarbonates of dihydroxyaryl ethers |
US2999846A (en) | 1956-11-30 | 1961-09-12 | Schnell Hermann | High molecular weight thermoplastic aromatic sulfoxy polycarbonates |
IT595468A (zh) | 1957-08-22 | |||
US2936324A (en) * | 1958-04-14 | 1960-05-10 | Eastman Kodak Co | Preparation of 2, 2, 4, 4-tetraalkylcyclobutane-1, 3-diols |
US2999835A (en) | 1959-01-02 | 1961-09-12 | Gen Electric | Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same |
US3030335A (en) * | 1959-01-02 | 1962-04-17 | Gen Electric | Aromatic polycarbonate reaction products |
FR1291273A (fr) | 1959-01-21 | 1962-04-20 | Eastman Kodak Co | Nouveau procédé pour la préparation d'un superpolyester linéaire et produit obtenu |
GB993121A (en) | 1959-01-21 | 1965-05-26 | Eastman Kodak Co | Linear superpolyester production |
US3075952A (en) * | 1959-01-21 | 1963-01-29 | Eastman Kodak Co | Solid phase process for linear superpolyesters |
US3075852A (en) * | 1959-08-12 | 1963-01-29 | Matthew J Bonora | Fingerprinting |
US3201474A (en) | 1959-09-24 | 1965-08-17 | Eastman Kodak Co | Process of manufacturing dialkyl ketenes |
FR83790E (fr) | 1959-12-18 | 1964-10-09 | Kodak Pathe | Nouveaux polymères dérivés des 2, 2, 4, 4-tétraalcoyl-1, 3-cyclobutanediols et leurs applications industrielles |
FR1278284A (fr) | 1959-12-18 | 1961-12-08 | Kodak Pathe | Nouveaux polymères dérivés des 2, 2, 4, 4-tétraalcoyl-1, 3-cyclobutanediols et leurs applications industrielles |
US3000906A (en) | 1960-02-05 | 1961-09-19 | Eastman Kodak Co | Purification of pivalolactone |
US3062852A (en) | 1960-03-30 | 1962-11-06 | Eastman Kodak Co | Esters of 2, 2, 4, 4-tetraalkylcyclobutane-1, 3-diols |
BE615850Q (fr) | 1960-12-16 | 1962-07-16 | Eastman Kodak Co | Nouveaux polymères dérivés des 2,2,4,4-tétraalcoyl-1,3-cyclobutanediols et leurs applications industrielles |
US3227764A (en) | 1960-12-30 | 1966-01-04 | Eastman Kodak Co | Separation of cis and trans isomers of tetraalkyl - 1,3 - cyclobutanediols and novel compound obtained thereby |
US3207814A (en) | 1961-01-03 | 1965-09-21 | Gen Electric | Carbonate-polyester copolymer resinous compositions |
US3091600A (en) | 1961-01-05 | 1963-05-28 | Eastman Kodak Co | Linear aromatic acid copolyesters modified with dimer glycols having 36 carbons |
US3236899A (en) * | 1961-02-23 | 1966-02-22 | Eastman Kodak Co | Treatment of 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols |
GB1002372A (en) | 1961-04-25 | 1965-08-25 | Chisso Corp | Process for continuously hydrogenating higher aldehydes in liquid phase |
US3360547A (en) | 1961-05-01 | 1967-12-26 | Eastman Kodak Co | Polyesters of tetraalkylcyclobutanediol |
US3259469A (en) * | 1961-07-26 | 1966-07-05 | Eastman Kodak Co | Apparatus for manufacturing ketenes |
US3218372A (en) | 1961-08-18 | 1965-11-16 | Kunoshima Kagaku Kogyo Kabushi | Molding material and molded articles |
US3287390A (en) | 1961-08-21 | 1966-11-22 | Mcneilab Inc | 2, 2, 4, 4-tetramethylcyclobutyl compounds |
US3317466A (en) | 1961-09-14 | 1967-05-02 | Eastman Kodak Co | Three-dimensional polycyclic bisphenol polycarbonates and polyesters |
US3254047A (en) * | 1961-09-14 | 1966-05-31 | Eastman Kodak Co | Additives for increasing modulus of elasticity of polycarbonate films |
US3190928A (en) | 1961-09-27 | 1965-06-22 | Eastman Kodak Co | Preparation of tetraalkylcyclo-butanediols |
US3236999A (en) * | 1962-10-01 | 1966-02-22 | North American Aviation Inc | Computer having floating point division |
US3249652A (en) * | 1962-10-24 | 1966-05-03 | Du Pont | Segmented copolyester of 2, 2, 4, 4-tetramethyl-1, 3-cyclobutylene terephthalate andethylene terephthalate |
DE1520178A1 (de) | 1963-02-09 | 1969-12-04 | Kalle Ag | Verfahren zur Herstellung von Polyaethylenterephthalat |
US3312741A (en) * | 1963-04-29 | 1967-04-04 | Eastman Kodak Co | 2, 2-dialkyl-3-alkoxy cyclobutanone derivatives |
US3317465A (en) * | 1963-06-26 | 1967-05-02 | Robertson Co H H | Combination catalyst-inhibitor for betahydroxy carboxylic esters |
US3288854A (en) | 1963-07-05 | 1966-11-29 | Eastman Kodak Co | Addition of dialkylketenes to alkoxyacetylenes |
US3329722A (en) * | 1964-01-10 | 1967-07-04 | Englehard Ind Inc | Production of 3-hydroxy-2, 2, 4, 4-tetraalkyl-cyclobutanones |
DE1443821A1 (de) | 1964-05-04 | 1968-11-14 | Eastman Kodak Co | Verfahren und Vorrichtung zur Herstellung von Ketenen |
GB1090241A (en) | 1964-05-13 | 1967-11-08 | Kodak Ltd | Polyester insulating layers |
FR1434658A (fr) | 1964-05-13 | 1966-04-08 | Eastman Kodak Co | Conducteurs électriques à nouvelle couche isolante |
FR1456345A (fr) | 1964-12-07 | 1966-10-21 | Eastman Kodak Co | Nouveau procédé de préparation de polyesters et nouveaux produits obtenus |
US3544514A (en) * | 1965-01-15 | 1970-12-01 | Bayer Ag | Process for the production of thermoplastic polycarbonates |
US3366689A (en) | 1965-03-31 | 1968-01-30 | Daikin Ind Ltd | Process for manufacturing ketenes |
FR1432471A (fr) | 1965-05-12 | 1966-03-18 | Eastman Kodak Co | Procédé de préparation de diols cycliques par hydrogénation catalytique des cétones correspondantes |
US3484339A (en) | 1966-05-02 | 1969-12-16 | Eastman Kodak Co | Blends of polyesters containing free carboxyl groups and laminate thereof |
JPS541040B1 (zh) | 1967-02-17 | 1979-01-19 | ||
US3541059A (en) | 1967-04-19 | 1970-11-17 | Calgon C0Rp | Novel reaction products of glycidyl esters and alkali metal sulfite or bisulfite,and polymers thereof |
US3502620A (en) | 1967-05-11 | 1970-03-24 | Eastman Kodak Co | Branched polyesters containing terminal carboxyl groups |
US3456177A (en) * | 1967-05-29 | 1969-07-15 | Web Press Eng Inc | Operational amplifier and regenerative motor control incorporating an operational amplifier |
US3504002A (en) * | 1967-08-29 | 1970-03-31 | Du Pont | Selected 6-difluoromethylene steroids of the pregnane series |
US3546008A (en) | 1968-01-03 | 1970-12-08 | Eastman Kodak Co | Sizing compositions and fibrous articles sized therewith |
US3546177A (en) | 1968-03-07 | 1970-12-08 | Eastman Kodak Co | Polyesters containing sterically hindered trialkyl phosphates |
GB1251834A (zh) * | 1968-04-02 | 1971-11-03 | ||
GB1278284A (en) | 1969-08-16 | 1972-06-21 | Norman Wood | Improvements in or relating to the manufacture of resonators of stringed musical instruments |
US3629202A (en) | 1969-09-12 | 1971-12-21 | Eastman Kodak Co | Treating polyesters with organic acids for improved stability |
UST875010I4 (en) * | 1969-11-20 | 1970-06-09 | Defensive publication | |
UST873016I4 (en) | 1969-11-28 | 1970-04-28 | Defensive publication | |
US3734874A (en) | 1970-02-27 | 1973-05-22 | Eastman Kodak Co | Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt |
JPS4920078B1 (zh) | 1970-09-26 | 1974-05-22 | ||
BE774720A (fr) | 1970-11-02 | 1972-02-14 | Fiber Industries Inc | Polyesters thermo-stabilises et leur procede de fabrication |
BE794938A (fr) | 1972-02-02 | 1973-08-02 | Eastman Kodak Co | Nouveau procede de preparation de copolyesters et applications |
US3915913A (en) | 1972-08-15 | 1975-10-28 | Eastman Kodak Co | Hot melt polymer blends |
US3799953A (en) | 1972-09-01 | 1974-03-26 | Bayer Ag | 1,4-bis(4,'4''-dihydroxy-triphenylmethyl)benzene |
US3845884A (en) | 1973-06-05 | 1974-11-05 | Hall & Myers | Bottle with an inverted portion support and sealing ring |
US3907754A (en) | 1974-06-19 | 1975-09-23 | Eastman Kodak Co | Process and catalyst-inhibitor system for preparing synthetic linear polyester |
DE2431072C3 (de) | 1974-06-28 | 1980-04-30 | Bayer Ag, 5090 Leverkusen | Thermoplastische Copolyester und Verfahren zu ihrer Herstellung |
US4056504A (en) | 1974-08-16 | 1977-11-01 | Bayer Aktiengesellschaft | Polycarbonate molding compositions |
US3962189A (en) | 1974-11-01 | 1976-06-08 | Eastman Kodak Company | Process and catalyst-inhibitor systems for preparing synthetic linear polyesters |
US4185009A (en) | 1975-01-03 | 1980-01-22 | Bayer Aktiengesellschaft | Branched, high-molecular weight thermoplastic polycarbonates |
US4136089A (en) | 1975-02-22 | 1979-01-23 | Bayer Aktiengesellschaft | Molded articles of crystalline poly (ethylene/alkylene) terephthalates which crystallize rapidly |
US4001184A (en) | 1975-03-31 | 1977-01-04 | General Electric Company | Process for preparing a branched polycarbonate |
US4010145A (en) * | 1975-05-12 | 1977-03-01 | Eastman Kodak Company | Process and catalyst inhibitor systems for preparing synthetic linear polyesters |
US4046933A (en) | 1975-09-16 | 1977-09-06 | Ppg Industries, Inc. | Laminated window structure and its method of fabrication |
JPS5285255A (en) * | 1976-01-09 | 1977-07-15 | Toray Industries | Method of producing hollow formed article of thermoplastic polyester resin |
US4156069A (en) * | 1976-04-02 | 1979-05-22 | Allied Chemical Corporation | Bisphenol-A/terephthalate/carbonate melt processable copolymers |
US4084889A (en) | 1976-07-28 | 1978-04-18 | Vischer Optics, Inc. | Eyeglass frame |
US4188314A (en) | 1976-12-14 | 1980-02-12 | General Electric Company | Shaped article obtained from a carbonate-polyester composition |
US4391954A (en) | 1976-12-14 | 1983-07-05 | General Electric Company | Thermoplastic molding composition |
US4125572A (en) | 1976-12-14 | 1978-11-14 | General Electric Company | Thermoplastic molding composition |
US4123436A (en) | 1976-12-16 | 1978-10-31 | General Electric Company | Polycarbonate composition plasticized with esters |
IT1076001B (it) * | 1977-01-04 | 1985-04-22 | Also Lab Di Dr P Sorbini & C S | Composizione per il trattamento del cuoio capelluto e contro la caduta dei capelli |
DE2715932A1 (de) | 1977-04-09 | 1978-10-19 | Bayer Ag | Schnellkristallisierende poly(aethylen/alkylen)-terephthalate |
US4111846A (en) | 1977-05-06 | 1978-09-05 | W. R. Grace & Co. | Hydrosol and catalyst preparation |
US4160383A (en) * | 1977-12-27 | 1979-07-10 | Will Ross Inc. | Unitary sample-vent-valve assembly |
DE2811982A1 (de) | 1978-03-18 | 1979-09-27 | Huels Chemische Werke Ag | Verfahren zur herstellung von hochmolekularem poly(ethylenterephthalat) |
DE2842004A1 (de) * | 1978-09-27 | 1980-04-10 | Bayer Ag | Verfahren zur herstellung von modifizierten polycarbonat-formmassen |
US4194038A (en) | 1979-01-25 | 1980-03-18 | Allied Chemical Corporation | Poly(ester-carbonates) from dicarboxylic acid chlorides |
US4233196A (en) | 1979-04-30 | 1980-11-11 | Eastman Kodak Company | Polyester and polyesteramide compositions |
DE2921868A1 (de) | 1979-05-30 | 1980-12-04 | Karl Obser | Sportkabine |
US4238593B1 (en) | 1979-06-12 | 1994-03-22 | Goodyear Tire & Rubber | Method for production of a high molecular weight polyester prepared from a prepolymer polyester having an optional carboxyl content |
US4263364A (en) | 1979-12-14 | 1981-04-21 | Eastman Kodak Company | Stampable reinforced thermoplastic polyester sheets |
JPS5688440A (en) | 1979-12-21 | 1981-07-17 | Daicel Chem Ind Ltd | Noval cellulose acetate resin composition |
US4264751A (en) | 1980-03-12 | 1981-04-28 | The Goodyear Tire & Rubber Company | Copolyester resin having minimal carboxyl terminated ends and method for producing the same |
EP0039838B2 (en) | 1980-04-30 | 1989-11-02 | Dainippon Ink And Chemicals, Inc. | Greenhouse |
EP0078609B1 (en) | 1980-04-30 | 1987-05-06 | Imperial Chemical Industries Plc | 3-hydroxybutyric acid polymers |
US4430484A (en) * | 1981-01-14 | 1984-02-07 | General Electric Company | Polyester-carbonate resin blends |
JPS5883344A (ja) * | 1981-11-13 | 1983-05-19 | Ricoh Co Ltd | 光学的情報記録媒体 |
US4356299A (en) | 1982-02-04 | 1982-10-26 | Rohm And Haas Company | Catalyst system for a polyethylene terephthalate polycondensation |
US4384106A (en) | 1982-03-09 | 1983-05-17 | Owens-Illinois, Inc. | Copolyesters |
US4379802A (en) | 1982-04-21 | 1983-04-12 | Eastman Kodak Company | Stampable reinforced thermoplastic polyester sheet with improved surface finish |
US4424140A (en) | 1982-06-03 | 1984-01-03 | Union Carbide Corporation | Stabilization of polycondensation catalysts |
US4431793A (en) | 1982-06-09 | 1984-02-14 | General Electric Company | Aromatic polycarbonate end capped with branched chain alkyl acyl halide or acid |
US4786692A (en) | 1982-12-20 | 1988-11-22 | General Electric Company | High strength, reduced heat distortion temperature thermoplastic composition |
US4469861A (en) | 1982-12-27 | 1984-09-04 | General Electric Company | Polycarbonate composition from branched chain dihydric phenol |
US4465820A (en) | 1983-06-03 | 1984-08-14 | General Electric Company | Copolyestercarbonates |
US4426512A (en) * | 1983-06-09 | 1984-01-17 | Eastman Kodak Company | Polyester containers having improved gas barrier properties |
US4452933A (en) * | 1983-06-09 | 1984-06-05 | General Electric Company | Stabilized polyester-polycarbonate blends and stabilization process therefor |
US4578437A (en) | 1983-08-01 | 1986-03-25 | Eastman Kodak Company | Copolyester/polyester blends having reduced carbon dioxide permeability |
US4480086A (en) | 1983-09-09 | 1984-10-30 | Eastman Kodak Company | Radiation-resistant copolyesters |
US4525504A (en) * | 1983-10-24 | 1985-06-25 | Eastman Kodak Company | Stabilized polyester compositions suitable for outdoor applications |
US4642959A (en) | 1983-11-29 | 1987-02-17 | Swiech Jr Tom E | Vending machine panels |
US4939186A (en) | 1984-02-10 | 1990-07-03 | General Electric Company | Enhancing color stability to sterilizing radiation of polymer compositions |
US4587437A (en) * | 1984-03-19 | 1986-05-06 | Rockwell International Corporation | Coupling/decoupling capacitor multiplier |
US4578295A (en) * | 1984-07-16 | 1986-03-25 | Owens-Illinois, Inc. | High barrier polymer blend and articles prepared therefrom |
JPS6199954A (ja) * | 1984-10-18 | 1986-05-19 | Toray Ind Inc | 光学記録体 |
JPS61213147A (ja) * | 1985-03-18 | 1986-09-22 | 鐘淵化学工業株式会社 | 芳香族ポリエステル系積層体及び液晶表示部品 |
US5239020A (en) | 1985-08-21 | 1993-08-24 | Eastman Kodak Company | Polyester/polycarbonate blends |
AU603076B2 (en) | 1985-12-09 | 1990-11-08 | W.R. Grace & Co.-Conn. | Polymeric products and their manufacture |
AU8276287A (en) | 1986-12-11 | 1988-06-30 | Raymond L. Larson | Container and liquid dispenser |
EP0273144A3 (en) | 1986-12-15 | 1990-03-21 | General Electric Company | Cross-linked branched polycarbonate composition |
JPH0741907B2 (ja) | 1986-12-27 | 1995-05-10 | 三菱瓦斯化学株式会社 | 多層容器 |
GB8705712D0 (en) | 1987-03-11 | 1987-04-15 | Du Pont Canada | Lid for food trays |
US4733880A (en) * | 1987-03-17 | 1988-03-29 | Wilhelm Iii Donald | Ridable arm exercise bicycle |
SE8702840D0 (sv) | 1987-07-10 | 1987-07-10 | Plm Ab | Barrierforsterkning |
US4749773A (en) | 1987-07-27 | 1988-06-07 | Eastman Kodak Company | Condensation polymers containing methine ultraviolet radiation-absorbing residues and shaped articles produced therefrom |
US5326821A (en) | 1987-10-28 | 1994-07-05 | Unitika Ltd. | Resin composition for powder coatings |
US4982342A (en) * | 1987-11-05 | 1991-01-01 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Image processor system having multifunction look-up table units |
JP2608429B2 (ja) | 1987-11-09 | 1997-05-07 | 東レ・ダウコーニング・シリコーン株式会社 | パターン形成用材料およびパターン形成方法 |
US4882412A (en) | 1987-11-30 | 1989-11-21 | Eastman Kodak Company | Polyester polymer containing the residue of the UV absorbing benzopyran compound and shaped articles produced therefrom |
US4892922A (en) | 1987-11-30 | 1990-01-09 | Eastman Kodak Company | Polyester polymer containing the residue of a benzopyran colorant compound and shaped articles produced therefrom |
US4846359A (en) | 1987-12-18 | 1989-07-11 | The Procter & Gamble Company | Multi-layered plastic bottle having integrally formed handle and method of making |
US4981898A (en) * | 1987-12-31 | 1991-01-01 | General Electric Company | Polycarbonate-polyester blends |
JP2873823B2 (ja) * | 1988-02-15 | 1999-03-24 | 大日本印刷株式会社 | 包装袋 |
US4826903A (en) * | 1988-02-22 | 1989-05-02 | Eastman Kodak Company | Condensation polymer containing the residue of an acyloxystyrl compound and shaped articles produced therefrom |
US4892923A (en) * | 1988-02-22 | 1990-01-09 | Eastman Kodak Company | Polyester compositions containing the residue of a naphthopyran compound and shaped articles produced therefrom |
GB2216919B (en) | 1988-04-08 | 1991-11-13 | Stc Plc | Kiosk housing for telephone equipment |
GB8817061D0 (en) * | 1988-07-18 | 1988-08-24 | Protein Tech Int | Functional protein product from vegetable protein materials |
US4976057A (en) | 1988-07-21 | 1990-12-11 | Bianchi Dennis R | Simulated neon sign |
JPH0779833B2 (ja) * | 1988-08-10 | 1995-08-30 | 川澄化学工業株式会社 | 耐γ線照射性体液処理装置 |
NO170326C (no) | 1988-08-12 | 1992-10-07 | Bayer Ag | Dihydroksydifenylcykloalkaner |
US4845188A (en) | 1988-08-19 | 1989-07-04 | Eastman Kodak Company | Condensation polymers containing methine ultraviolet radiation-absorbing residues and shaped articles produced therefrom |
CA2004300C (en) | 1988-12-01 | 1999-05-11 | Motoshige Hayashi | Process for producing polyester resin foam and polyester resin foam sheet |
US4946932A (en) | 1988-12-05 | 1990-08-07 | Eastman Kodak Company | Water-dispersible polyester blends |
DE3926719A1 (de) | 1988-12-23 | 1990-07-05 | Bayer Ag | Polycarbonate aus alkylcyclohexylidenbisphenolen |
US4937134A (en) | 1989-04-17 | 1990-06-26 | The Dow Chemical Company | Elastomeric optical interference films |
US5326584A (en) | 1989-04-24 | 1994-07-05 | Drexel University | Biocompatible, surface modified materials and method of making the same |
JPH02305816A (ja) * | 1989-05-18 | 1990-12-19 | Kuraray Co Ltd | 酸素透過性成形体 |
US5191038A (en) | 1989-06-01 | 1993-03-02 | General Electric Company | Preparation of branched polycarbonate composition from cyclic aromatic polycarbonate oligomer, polyhydric phenol and polycarbonate |
US5017679A (en) | 1989-08-30 | 1991-05-21 | Eastman Kodak Company | Polyesters terminated with carboxycyclohexanecarboxylate groups |
JPH03207743A (ja) | 1990-01-09 | 1991-09-11 | Mitsubishi Rayon Co Ltd | 光の透過性及び拡散性に優れたメタクリル樹脂成形体 |
US6288161B1 (en) | 1990-01-31 | 2001-09-11 | Pechiney Emballage Flexible Europe | Barrier compositions and articles made therefrom |
CA2035149A1 (en) | 1990-02-06 | 1991-08-07 | Charles E. Lundy | Blends of polycarbonates and aliphatic polyesters |
IE65907B1 (en) * | 1990-02-26 | 1995-11-29 | Lonza Ag | New 3-hydroxy-2-cyclobuten-1-one salts their preparation and use |
US5224958A (en) | 1990-05-04 | 1993-07-06 | The Research Foundation Of State University Of New York | Silicone elastomer line prosthetic devices and methods of manufacture |
US5017680A (en) * | 1990-07-03 | 1991-05-21 | Eastman Kodak Company | Process and catalyst-inhibitor systems for preparing poly(ethylene terephthalate) |
US5486562A (en) | 1990-07-12 | 1996-01-23 | General Electric Company | Modifications of poly(alkylene cyclohexanedicarboxylate) blends |
AU649710B2 (en) | 1990-09-11 | 1994-06-02 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition and film therefrom |
US5219510A (en) * | 1990-09-26 | 1993-06-15 | Eastman Kodak Company | Method of manufacture of cellulose ester film |
US5104450A (en) | 1990-09-26 | 1992-04-14 | Eastman Kodak Company | Formulations of cellulose esters with arylene-bis(diaryl phosphate)s |
DE4036359A1 (de) | 1990-11-15 | 1992-05-21 | Hoechst Ag | Verfahren zur verminderung der verfaerbung einer kunststoff-formmasse bei der verarbeitungstemperatur |
ATE199383T1 (de) | 1990-11-30 | 2001-03-15 | Eastman Chem Co | Aliphatisch-aromatische copolyester |
US6495656B1 (en) | 1990-11-30 | 2002-12-17 | Eastman Chemical Company | Copolyesters and fibrous materials formed therefrom |
US5292783A (en) | 1990-11-30 | 1994-03-08 | Eastman Kodak Company | Aliphatic-aromatic copolyesters and cellulose ester/polymer blends |
US5118760A (en) | 1990-12-26 | 1992-06-02 | Eastman Kodak Company | Impact resistant polymer blends |
US5142088A (en) | 1991-01-28 | 1992-08-25 | General Electric Company | Preparation of branched polycarbonates and chloroformates, and intermediates therefor |
US5434227A (en) | 1991-05-08 | 1995-07-18 | Daicel Chemical Industries, Ltd. | Process for producing polycarbonate |
JP2613502B2 (ja) | 1991-05-31 | 1997-05-28 | 東洋紡績株式会社 | 制振材料用粘弾性樹脂組成物 |
US5310787A (en) * | 1991-06-04 | 1994-05-10 | Du Pont-Mitsui Polychemicals Co., Ltd. | Polyester packaging material |
WO1992022837A1 (en) | 1991-06-17 | 1992-12-23 | Seiko Epson Corporation | Phase difference elemental film, phase difference plate and liquid crystal display using same |
US5254610A (en) * | 1991-08-02 | 1993-10-19 | Eastman Kodak Company | Polyester/polycarbonate blends containing phosphites |
US5169994A (en) | 1991-08-20 | 1992-12-08 | Eastman Kodak Company | Process for the manufacture of 2,2,4,4-tetramethycyclobutanediol |
US5256761A (en) | 1991-09-23 | 1993-10-26 | Eastman Kodak Company | Polyester coatings containing covalently-bound mesogenic monomers |
DE69216343T2 (de) | 1991-10-04 | 1997-07-31 | Oki Electric Ind Co Ltd | Thermoreversibles Aufzeichnungsmaterial und thermoreversibles Aufzeichnungsverfahren, das dieses Material verwendet |
US5217128A (en) | 1991-10-28 | 1993-06-08 | Johnson Enterprises, Inc. | Thermoplastic bottle with reinforcing ribs |
FR2682956B1 (fr) | 1991-10-29 | 1994-01-07 | Rhone Poulenc Chimie | Procede de preparation de polyesters hydrosolubles et/ou hydrodispersables et utilisation de ces polyesters pour l'encollage de fils textiles. |
JP2797804B2 (ja) | 1992-01-09 | 1998-09-17 | 日本電気株式会社 | バックライト及び液晶表示装置 |
US5207967A (en) | 1992-03-02 | 1993-05-04 | Eastman Kodak Company | Multicomponent polyester/polycarbonate blends with improved impact strength and processability |
US5422189A (en) | 1992-10-01 | 1995-06-06 | Minnesota Mining And Manufacturing Company | Flexible optically uniform sign face substrate |
BE1006297A3 (nl) | 1992-10-26 | 1994-07-12 | Axxis Nv | Kunststofplaat, een werkwijze voor de vervaardiging daarvan en vormdelen die de plaat bevatten. |
US5288764A (en) | 1993-01-29 | 1994-02-22 | Amoco Corporation | Increased throughput in foaming and other melt fabrication of polyester |
US5494992A (en) | 1993-01-29 | 1996-02-27 | Daicel Chemical Industries, Ltd. | (Co)polycarbonate and process for producing the same |
US5258556A (en) | 1993-02-01 | 1993-11-02 | Eastman Kodak Company | Process for the manufacture of 2,2,4,4-tetramethylcyclobutanediol |
US5372879A (en) | 1993-02-22 | 1994-12-13 | Teijin Limited | Biaxially oriented polyester film |
CN1099044A (zh) | 1993-04-16 | 1995-02-22 | 大世吕化学工业株式会社 | (共)聚碳酸酯的制备方法 |
US5463011A (en) * | 1993-06-28 | 1995-10-31 | Zeneca Limited | Acid derivatives |
US5382292A (en) * | 1993-07-28 | 1995-01-17 | Eastman Kodak Company | Edge guide lubricating fluid delivery apparatus |
JP3380556B2 (ja) | 1993-08-12 | 2003-02-24 | イーストマン ケミカル カンパニー | 被覆に使用する水分散性アクリル変性ポリエステル樹脂及びその製造方法 |
US5372864A (en) | 1993-09-03 | 1994-12-13 | Eastman Chemical Company | Toners for polyesters |
US5474735A (en) | 1993-09-24 | 1995-12-12 | Continental Pet Technologies, Inc. | Pulse blow method for forming container with enhanced thermal stability |
IL110514A0 (en) | 1993-10-04 | 1994-10-21 | Eastman Chem Co | Concentrates for improving polyester compositions and a method for preparing such compositions |
US5354791A (en) | 1993-10-19 | 1994-10-11 | General Electric Company | Epoxy-functional polyester, polycarbonate with metal phosphate |
WO1995018191A1 (en) | 1993-12-29 | 1995-07-06 | Eastman Chemical Company | Water-dispersible adhesive composition and process |
US5543488A (en) | 1994-07-29 | 1996-08-06 | Eastman Chemical Company | Water-dispersible adhesive composition and process |
US5413870A (en) | 1994-01-03 | 1995-05-09 | Flood; Christopher J. | Decorative bathroom panel including embedded fabric |
US5378796A (en) | 1994-02-09 | 1995-01-03 | Eastman Chemical Company | Process for preparing copolyesters |
US5475144A (en) | 1994-06-08 | 1995-12-12 | The University Of Delaware | Catalyst and process for synthesis of ketenes from carboxylic acids |
DE4425143A1 (de) * | 1994-07-15 | 1996-01-18 | Basf Ag | Substituierte Pyrimidinverbindungen und deren Verwendung |
AT401611B (de) | 1994-08-19 | 1996-10-25 | Bumba Walter Ing | Dekubitusbett |
DE69529032T2 (de) | 1994-08-25 | 2003-05-08 | Nippon Kokan Kk | Copolyesterharz, Polymermischung und Verpackungsmaterial daraus |
US5442036A (en) | 1994-09-06 | 1995-08-15 | Eastman Chemical Company | Branched copolyesters especially suitable for extrusion blow molding |
US6162890A (en) | 1994-10-24 | 2000-12-19 | Eastman Chemical Company | Water-dispersible block copolyesters useful as low-odor adhesive raw materials |
DE69532875T2 (de) | 1994-10-24 | 2004-08-19 | Eastman Chemical Co., Kingsport | Wasserdispergierbare Blockcopolyester |
US5498668A (en) | 1994-10-31 | 1996-03-12 | Eastman Chemical Company | Blends of certain polyesters with acrylics |
EP0714764A3 (en) | 1994-12-02 | 1997-03-05 | Gen Electric | Improved impact resistant composite |
US5534609A (en) | 1995-02-03 | 1996-07-09 | Osi Specialties, Inc. | Polysiloxane compositions |
CA2171584A1 (en) | 1995-04-11 | 1996-10-12 | James P. Mason | Compositions having low birefringence |
US5480926A (en) * | 1995-04-28 | 1996-01-02 | Eastman Chemical Company | Blends of ultraviolet absorbers and polyesters |
US5650453A (en) | 1995-04-28 | 1997-07-22 | General Electric Company | UV curable epoxysilicone blend compositions |
JP3153437B2 (ja) * | 1995-05-11 | 2001-04-09 | 電気化学工業株式会社 | ポリエステル系多層シートと容器及びその製法 |
DE69620292T2 (de) | 1995-05-31 | 2002-11-21 | Shell Int Research | Copolyester Zusammensetzung |
KR19990028290A (ko) * | 1995-06-22 | 1999-04-15 | 스프레이그 로버트 월터 | 캡슐화된 렌즈형 역반사성 시트 |
US5646237A (en) | 1995-08-15 | 1997-07-08 | Eastman Chemical Company | Water-dispersible copolyester-ether compositions |
JP3200338B2 (ja) | 1995-08-30 | 2001-08-20 | 帝人株式会社 | 芳香族ポリカーボネートの製造方法 |
US5506014A (en) | 1995-09-01 | 1996-04-09 | Eastman Chemical Company | Pet copolyesters containing succinic and naphthalenedicarboxylic acid moieties having improved barrier properties |
US5624987A (en) * | 1995-09-15 | 1997-04-29 | Brink; Andrew E. | Polyalkylene ethers as plasticizers and flow aids in poly(1,4-cyclohexanedimethylene terephthalate) resins |
US5868704A (en) | 1995-09-18 | 1999-02-09 | W. L. Gore & Associates, Inc. | Balloon catheter device |
US5633340A (en) | 1995-09-21 | 1997-05-27 | Eastman Chemical Company | Polyester molding compositions |
US5696176A (en) | 1995-09-22 | 1997-12-09 | Eastman Chemical Company | Foamable polyester compositions having a low level of unreacted branching agent |
US5552512A (en) | 1995-10-06 | 1996-09-03 | Eastman Chemical Company | Thermoplastic copolyesters having improved gas barrier properties |
AUPN605595A0 (en) | 1995-10-19 | 1995-11-09 | Amcor Limited | A hot fill container |
JPH09135896A (ja) * | 1995-11-17 | 1997-05-27 | Shimadzu Corp | 人工臓器モジュール |
US5608031A (en) | 1995-11-30 | 1997-03-04 | Eastman Chemical Company | Polyesters modified with 1,4-cyclohexaned imethanol having high clarity prepared utilizing an antimony containing catalyst/stabilizer system |
US5643666A (en) | 1995-12-20 | 1997-07-01 | Eastman Chemical Company | Solid surfaces which are prepared from copolyesters laminated onto a high resolution image |
US5688874A (en) | 1995-12-22 | 1997-11-18 | Eastman Chemical Company | Process for preparing blends of poly(ethylene terephthalate) and poly(ethylene 2,6-naphthalenedicarboxylate) |
TW381104B (en) | 1996-02-20 | 2000-02-01 | Eastman Chem Co | Process for preparing copolyesters of terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol |
US6022603A (en) | 1996-04-05 | 2000-02-08 | Teijin Limited | Ethylene terephthalate/ethylene-2,6-naphthalene-dicarboxylate copolymers for bottles |
US5656715A (en) | 1996-06-26 | 1997-08-12 | Eastman Chemical Company | Copolyesters based on 1,4-cyclohexanedimethanol having improved stability |
US5977347A (en) | 1996-07-30 | 1999-11-02 | Daicel Chemical Industries, Ltd. | Cellulose acetate propionate |
US5814679A (en) | 1996-10-18 | 1998-09-29 | General Electric Company | Premium release photo-curable silicone compositions |
US5783307A (en) | 1996-11-04 | 1998-07-21 | Eastman Chemical Company | UV stabilized multi-layer structures with detectable UV protective layers and a method of detection |
US5863622A (en) | 1996-12-05 | 1999-01-26 | Hoechst Celanese Corporation | Polarizer laminates comprising coextruded liquid crystal polymer moieties and integral thermoplastic cover layers |
US5942585A (en) | 1996-12-28 | 1999-08-24 | Eastman Chemical Company | Polycarbonate and polyester blends |
US6005059A (en) | 1996-12-28 | 1999-12-21 | Eastman Chemical Company | Clear polycarbonate and polyester blends |
US6037424A (en) * | 1996-12-28 | 2000-03-14 | Eastman Chemical Company | Clear blends of polycarbonates and polyesters |
US6011124A (en) * | 1996-12-28 | 2000-01-04 | Eastman Chemical Company | Blends of bisphenol a polycarbonate and polyesters |
US5955565A (en) | 1996-12-28 | 1999-09-21 | Eastman Chemical Company | Polyesters from terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol |
US5989663A (en) | 1996-12-30 | 1999-11-23 | Eastman Chemical Company | Blow-molding polyesters from terephthalic acid, 2, 2, 4, 4-tetramethyl-1,3-cyclobutanediol, and ethylene glycol |
US6431401B1 (en) | 1996-12-31 | 2002-08-13 | Lever Brothers Company, A Division Of Conopco, Inc. | Bottle |
US6084019A (en) * | 1996-12-31 | 2000-07-04 | Eastman Chemical Corporation | High I.V. polyester compositions containing platelet particles |
DE19701415C1 (de) * | 1997-01-17 | 1998-01-29 | Dornier Gmbh Lindauer | Vorrichtung zum Breithalten und Quetschen von Schlauch-Wirkware |
US5859116A (en) | 1997-01-21 | 1999-01-12 | Eastman Chemical Company | Clarity and adjustable shrinkage of shrink films using miscible polyester blends |
DE19711773C2 (de) | 1997-03-21 | 1999-07-29 | Hueller Hille Gmbh | Teleskopvorschubeinheit |
US6114575A (en) | 1997-03-25 | 2000-09-05 | Bp Amoco Corporation | Process for preparing 2,6-naphthalenedicarboxylic acid |
US5902631A (en) * | 1997-06-03 | 1999-05-11 | Wang; Lixiao | Lubricity gradient for medical devices |
DE19727709A1 (de) | 1997-06-30 | 1999-01-07 | Bayer Ag | Verfahren zur Herstellung von verzweigten Polycarbonaten |
US6309718B1 (en) | 1997-07-25 | 2001-10-30 | Eastman Chemical Company | Large polyester containers and method for making same |
FR2766964B1 (fr) | 1997-07-29 | 1999-10-29 | Pixtech Sa | Procede d'assemblage sous vide d'un ecran plat de visualisation |
US5942595A (en) * | 1997-08-19 | 1999-08-24 | E. I. Du Pont De Nemours And Company | Process for co-polymerization of formaldehyde with cyclic ethers in the presence of organic nitro compounds |
JP4435409B2 (ja) * | 1997-08-26 | 2010-03-17 | イーストマン ケミカル カンパニー | 高レリーフ表面を有する熱可塑性物品 |
US6025069A (en) | 1998-06-19 | 2000-02-15 | Eastman Chemical Company | Thermoplastic article having high-relief surface |
US5958539A (en) | 1997-08-26 | 1999-09-28 | Eastman Chemical Company | Thermoplastic article having textile fiber fabric embedded therein |
US5998028A (en) | 1997-08-26 | 1999-12-07 | Eastman Chemical Company | Thermoplastic article having metallic wire, rod or bar embedded therein |
US5907026A (en) | 1997-08-27 | 1999-05-25 | General Electric Company | Polycarbonate compositions comprising polyester resins and ultraviolet light absorbers |
SG70651A1 (en) | 1997-09-15 | 2000-02-22 | Gen Electric | Aliphatic polyester-acrylic blend molding composition having good ductility and weatherability |
US6048978A (en) * | 1997-10-07 | 2000-04-11 | Merck & Co., Inc. | Process for the synthesis of carbapenem intermediates, and compounds produced |
US6030671A (en) | 1998-01-09 | 2000-02-29 | Msc Specialty Films, Inc. | Low emissivity window films |
US5925507A (en) | 1998-01-14 | 1999-07-20 | Eastman Kodak Company | Photographic film base and photographic elements |
US5954216A (en) | 1998-01-23 | 1999-09-21 | Great Spring Waters Of America, Inc. | Container with integral ergonomic handle |
CA2319261A1 (en) * | 1998-01-23 | 1999-07-29 | Pall Corporation | Biological fluid treatment system |
JP3628165B2 (ja) * | 1998-02-05 | 2005-03-09 | 三井化学株式会社 | ポリエステルおよびその用途 |
US6846440B2 (en) | 1998-03-17 | 2005-01-25 | Eastman Chemical Company | Polyester resin compositions for calendering |
US6012597A (en) | 1998-03-18 | 2000-01-11 | Mitsubishi Plastics, Inc. | Polyester bottle with a handle and method of manufacturing the same |
DE19811773A1 (de) | 1998-03-18 | 1999-09-23 | Wolff Walsrode Ag | Thermoplastische, biologisch abbaubare und kompostierbare opake Folie und Verfahren zu deren Herstellung |
US6063464A (en) | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Isosorbide containing polyesters and methods for making same |
US6025061A (en) * | 1998-04-23 | 2000-02-15 | Hna Holdings, Inc. | Sheets formed from polyesters including isosorbide |
US5958581A (en) | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyester film and methods for making same |
US6140422A (en) | 1998-04-23 | 2000-10-31 | E.I. Dupont De Nemours And Company | Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers |
US6063465A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Polyester container and method for making same |
US6126992A (en) * | 1998-04-23 | 2000-10-03 | E.I. Dupont De Nemours And Company | Optical articles comprising isosorbide polyesters and method for making same |
US5959066A (en) | 1998-04-23 | 1999-09-28 | Hna Holdings, Inc. | Polyesters including isosorbide as a comonomer and methods for making same |
US6063495A (en) | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Polyester fiber and methods for making same |
US6150494A (en) | 1998-04-30 | 2000-11-21 | Eastman Chemical Company | Polymers containing optical brightener compounds copolymerized therein and methods of making and using therefor |
GB9902808D0 (en) | 1998-05-06 | 1999-03-31 | Dow Corning Sa | Adhesive device |
TW500765B (en) | 1998-05-13 | 2002-09-01 | Sumitomo Chemical Co | Thermoplastic resin composition and heat-resistant tray for IC |
US6211309B1 (en) | 1998-06-29 | 2001-04-03 | Basf Corporation | Water-dispersable materials |
US6727294B2 (en) | 1998-07-28 | 2004-04-27 | Mitsubishi Engineering-Plastics Corporation | Thermoplastic resin composition containing a naphthalene dicarboxylic acid moiety and an aliphatic diol moiety |
US6639067B1 (en) | 1998-09-09 | 2003-10-28 | Willard C. Brinegar | Continuous process for the production of anhydrosugar alcohols |
US6255523B1 (en) * | 1998-09-18 | 2001-07-03 | Mcwhorter Technologies, Inc. | Power coatings based on branched oligoesters and non-emissive uretdione polyisocyanates |
JP4021105B2 (ja) | 1998-09-30 | 2007-12-12 | 三井化学株式会社 | ポリエステル樹脂組成物およびそれからなる中空成形容器 |
JP3583305B2 (ja) * | 1998-11-24 | 2004-11-04 | 三菱化学株式会社 | 芳香族ポリカーボネート |
JP2001066701A (ja) | 1999-08-25 | 2001-03-16 | Mitsubishi Rayon Co Ltd | 光拡散性シートおよび透過型スクリーン |
GB9902823D0 (en) | 1998-12-23 | 1999-03-31 | Dow Corning Sa | Biocompatible coatings |
US6232504B1 (en) * | 1998-12-29 | 2001-05-15 | University Of Delaware | Functionalized monolith catalyst and process for production of ketenes |
US6458468B1 (en) | 1999-01-28 | 2002-10-01 | Eastman Chemical Company | Photocurable coatings for polyester articles |
US6320042B1 (en) | 1999-03-03 | 2001-11-20 | Konica Corporation | Polarizing plate protective cellulose triacetate film |
US6221556B1 (en) | 1999-03-05 | 2001-04-24 | General Electric Company | Article for optical data storage device |
JP2000352620A (ja) | 1999-03-31 | 2000-12-19 | Konica Corp | 光学フィルム、偏光板及び液晶表示装置 |
US6001910A (en) | 1999-04-09 | 1999-12-14 | National Starch And Chemical Investment Holding Corporation | Use of anionic or cationic plasticizers with sulfonated polyesters in hot melt formulations |
US6287656B1 (en) | 1999-06-03 | 2001-09-11 | Eastman Chemical Corporation | Low melt viscosity amorphous copolyesters having improved resistance to lipids |
US6120889A (en) | 1999-06-03 | 2000-09-19 | Eastman Chemical Company | Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures |
US6183848B1 (en) * | 1999-06-03 | 2001-02-06 | Eastman Chemical Company | Low melt viscosity amorphous copolyesters with enhanced glass transition temperatures having improved gas barrier properties |
EP1066825A1 (en) | 1999-06-17 | 2001-01-10 | The Procter & Gamble Company | An anti-microbial body care product |
US6191209B1 (en) * | 1999-06-30 | 2001-02-20 | Ciba Specialty Chemicals Corporation | Polyester compositions of low residual aldehyde content |
US20030032737A1 (en) * | 1999-06-30 | 2003-02-13 | Stephen Andrews | Polyester compositions of low residual aldehyde content |
AU6025700A (en) | 1999-07-26 | 2001-02-13 | Kolon Industries, Inc. | A suckling bottle for baby, and a process of preparing the same |
US7176252B2 (en) | 1999-07-29 | 2007-02-13 | Dover Chemical Corporation | Solid melt blended phosphite composites |
MXPA02001271A (es) * | 1999-08-06 | 2002-07-22 | Eastman Chem Co | Poliesteres que tienen un punto de fusion controlado y fibras formadas de ellos. |
ES2231261T3 (es) | 1999-09-27 | 2005-05-16 | Ciba Specialty Chemicals Holding Inc. | Procedimiento para la preparacion de composiciones de poliester de bajo contenido de aldehido residual. |
JP2001098086A (ja) | 1999-09-29 | 2001-04-10 | Fuji Photo Film Co Ltd | セルロースエステルフイルムの製造方法およびセルロースエステルフイルムの複屈折率上昇方法 |
JP4373577B2 (ja) | 1999-11-25 | 2009-11-25 | 帝人化成株式会社 | 光拡散性芳香族ポリカーボネート樹脂組成物 |
US6576309B2 (en) * | 1999-12-02 | 2003-06-10 | Associated Packaging Enterprises | Thermoplastic compositions having high dimensional stability |
FR2802302B1 (fr) | 1999-12-09 | 2002-02-15 | Sagem | Appareil de mesure de l'intensite du courant dans un conducteur |
US6352783B1 (en) | 1999-12-13 | 2002-03-05 | Eastman Kodak Company | Copolyester containing 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol and an ultraviolet light absorbing compound and articles made therefrom |
AU3687401A (en) | 2000-02-11 | 2001-08-20 | U S Army Inst Of Surgical Res | Pacifier pulse oximeter sensor |
US6354986B1 (en) * | 2000-02-16 | 2002-03-12 | Gambro, Inc. | Reverse-flow chamber purging during centrifugal separation |
DE10009756B4 (de) | 2000-03-01 | 2004-03-25 | Ems-Chemie Ag | Farblose, hochtransparente Polyamid-Blends mit verbesserter Spannungsrissbeständigkeit |
US6704377B1 (en) * | 2000-03-10 | 2004-03-09 | Lucent Technologies Inc. | Method of correcting frequency errors for coherently demodulated wireless communication systems |
KR20010089942A (ko) | 2000-03-15 | 2001-10-17 | 양갑석 | 고내열성 폴리에스터 병용 수지제조방법 |
JP2001273723A (ja) | 2000-03-28 | 2001-10-05 | Matsushita Electric Ind Co Ltd | ハードディスク装置、媒体及び情報集合体 |
US6225436B1 (en) | 2000-04-07 | 2001-05-01 | The Dow Chemical Company | Polycarbonate preparation process |
US6593425B2 (en) | 2000-05-31 | 2003-07-15 | General Electric Company | Data storage media containing transparent polycarbonate blends |
JP5360517B2 (ja) | 2000-06-05 | 2013-12-04 | エフテックス有限会社 | ポリエステル樹脂およびその成形体のマスターバッチ式製造方法 |
FR2810040B1 (fr) | 2000-06-09 | 2004-04-09 | Roquette Freres | Procede de purification d'une composition contenant au moins un produit de deshydratation interne d'un sucre hydrogene |
JP2002053685A (ja) * | 2000-08-08 | 2002-02-19 | Fuji Photo Film Co Ltd | ポリエステル支持体およびハロゲン化銀写真感光材料 |
DE10040178A1 (de) * | 2000-08-17 | 2002-03-07 | Wacker Chemie Gmbh | Verdickungsmittel auf der Basis von Vinylalkohol-Mischpolymerisaten |
EP1327648B1 (en) * | 2000-09-12 | 2007-06-13 | Toyo Boseki Kabushiki Kaisha | Polymerization catalyst for polyester, polyester produced with the same, and process for producing polyester |
US6458888B1 (en) * | 2000-09-15 | 2002-10-01 | Isp Investments Inc. | Rheology modifier for use in aqueous compositions |
JP3455776B2 (ja) * | 2000-09-19 | 2003-10-14 | 独立行政法人産業技術総合研究所 | 静電的手法により一方向配向させた有機繊維を鋳型にした中空セラミックスファイバー集合体の製造方法 |
US6458915B1 (en) | 2000-10-13 | 2002-10-01 | Eastman Chemical Company | Process for producing poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate) and the reactor grade polyester therefrom |
US20020082360A1 (en) * | 2000-11-03 | 2002-06-27 | Conn Roy Lee | Films and articles formed from blends of polycarbonate and polyester |
CN1281645C (zh) | 2000-11-09 | 2006-10-25 | 艾弗里丹尼森有限公司 | 具有由紫外光吸收聚合物形成的屏蔽层的荧光聚合物制品 |
US6541059B2 (en) * | 2000-12-07 | 2003-04-01 | Bestfoods | Process of making instant pasta with improved cooking quality |
US6448334B1 (en) | 2000-12-19 | 2002-09-10 | General Electric Company | Translucent polycarbonate composition, method for preparation thereof, and articles derived therefrom |
US6635698B2 (en) | 2000-12-22 | 2003-10-21 | General Electric Company | Flame retardant polycarbonate polyester composition |
ATE352583T1 (de) | 2000-12-29 | 2007-02-15 | Ciba Sc Holding Ag | Polyesterzusammensetzungen mit geringem restaldehydgehalt |
US6573328B2 (en) | 2001-01-03 | 2003-06-03 | Loctite Corporation | Low temperature, fast curing silicone compositions |
US6323304B1 (en) | 2001-01-12 | 2001-11-27 | General Electric Company | Melt polycarbonate catalyst systems |
US6551688B2 (en) | 2001-02-28 | 2003-04-22 | Eastman Chemical Company | Calendered polyester films or sheets having a haze value of less than five percent |
US20020198297A1 (en) | 2001-03-02 | 2002-12-26 | Odorisio Paul A. | Polyester and polyamide compositions of low residual aldehyde content |
US6908650B2 (en) * | 2001-03-02 | 2005-06-21 | Ciba Specialty Chemicals Corporation | Polyester and polyamide compositions of low residual aldehyde content |
MXPA03007914A (es) | 2001-03-28 | 2003-12-11 | Ciba Sc Holding Ag | Proceso para preparar un poliester estabilizado. |
US6586165B2 (en) * | 2001-04-27 | 2003-07-01 | Eastman Kodak Company | Photographic elements coated on transparent support with reflective protective overcoat |
US6733716B2 (en) * | 2001-05-21 | 2004-05-11 | Sabel Plastechs Inc. | Method of making a stretch/blow molded article (bottle) with an integral projection such as a handle |
JP2002348482A (ja) * | 2001-05-25 | 2002-12-04 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂組成物 |
US6599994B2 (en) | 2001-07-18 | 2003-07-29 | Eastman Chemical Company | Polyester blends and heat shrinkable films made therefrom |
DE10135465A1 (de) | 2001-07-20 | 2003-02-06 | Bayer Ag | Polycarbonat-Blends |
FR2827876B1 (fr) * | 2001-07-27 | 2004-06-18 | Usinor | Acier inoxydable austenitique pour deformation a froid pouvant etre suivi d'un usinage |
US20030055586A1 (en) * | 2001-08-21 | 2003-03-20 | Alstom Power N.V. | Regularization model for electrical resistance mapping |
US6740377B2 (en) | 2001-09-14 | 2004-05-25 | Eastman Chemical Company | Polyester having improved crystallization behavior and extrusion blow molded articles made therefrom |
US6669980B2 (en) | 2001-09-18 | 2003-12-30 | Scimed Life Systems, Inc. | Method for spray-coating medical devices |
US6773653B2 (en) | 2001-10-05 | 2004-08-10 | Avery Dennison Corporation | In-mold labeling method |
KR100459654B1 (ko) * | 2001-10-12 | 2004-12-03 | 에스케이케미칼주식회사 | 1,4-사이클로헥산디메탄올이 공중합된 폴리에스테르수지의 제조방법 |
US6437083B1 (en) | 2001-12-06 | 2002-08-20 | General Electric Company | Process for preparing branched aromatic polycarbonates |
EP1460106B1 (en) | 2001-12-21 | 2005-11-23 | Mitsubishi Gas Chemical Company, Inc. | Thermoplastic resin composition |
US6504002B1 (en) | 2001-12-21 | 2003-01-07 | General Electric Company | Process for the production of branched melt polycarbonate by late addition of fries-inducing catalyst |
JP3952144B2 (ja) * | 2001-12-25 | 2007-08-01 | 三菱瓦斯化学株式会社 | ポリエステル系中空成形体 |
KR20030054611A (ko) * | 2001-12-26 | 2003-07-02 | 주식회사 코오롱 | 혈액투석기용 하우징 |
DE10201354A1 (de) * | 2002-01-16 | 2003-07-24 | Cognis Deutschland Gmbh | Alkyl- und/oder Alkylenoligoglycosid-Betainesterquats |
DK1470175T3 (da) | 2002-02-01 | 2007-05-21 | Clariant Int Ltd | Oligomere kædeforlængere til behandling, efterbehandling og recirkulering af kondensationspolymerer, syntese, sammensætninger og anvendelser |
US7037576B2 (en) | 2002-02-06 | 2006-05-02 | Eastman Chemical Company | Polyester or copolyester/polyolefin laminate structures and methods of making the same |
US20040009146A1 (en) * | 2002-02-26 | 2004-01-15 | Osvaldo Podhajcer | Anti-tumor vaccine and method |
JP2003252969A (ja) * | 2002-03-05 | 2003-09-10 | Nippon Ester Co Ltd | 共重合ポリエステル及び成形品 |
US6721102B2 (en) | 2002-03-11 | 2004-04-13 | Eastman Kodak Company | Surface formed complex polymer lenses for visible light diffusion |
US6723768B2 (en) | 2002-03-27 | 2004-04-20 | Eastman Chemical Company | Polyester/polycarbonate blends with reduced yellowness |
JP4062416B2 (ja) | 2002-04-04 | 2008-03-19 | 三菱瓦斯化学株式会社 | ポリエステル樹脂 |
US20030195295A1 (en) | 2002-04-16 | 2003-10-16 | General Electric Company | Miscible blends of polyesters and polycarbonates with good thermal characteristics, and related processes and articles |
US6818730B2 (en) | 2002-04-26 | 2004-11-16 | E. I. Du Pont De Nemours And Company | Process to produce polyesters which incorporate isosorbide |
US6986864B2 (en) * | 2002-04-30 | 2006-01-17 | David Scott Porter | Polyester compositions |
US6742533B2 (en) | 2002-06-04 | 2004-06-01 | Charles J. Olson | Temporary outdoor shelter |
US6656577B1 (en) | 2002-06-14 | 2003-12-02 | E. I. Du Pont De Nemours & Company | Process for making poly(ethylene-co-isosorbide) terephthalate polymer |
EP1553992B1 (en) | 2002-07-24 | 2010-06-09 | Covidien AG | Process for lubricating hypodermic needles with radiation curable silicon material |
JP2004058565A (ja) | 2002-07-31 | 2004-02-26 | Tahara:Kk | ポリエステル系樹脂製容器の製造方法 |
JP4052055B2 (ja) | 2002-08-06 | 2008-02-27 | 東洋製罐株式会社 | プラスチックボトル容器の延伸ブロー成形方法 |
JP4123351B2 (ja) | 2002-08-09 | 2008-07-23 | 三菱瓦斯化学株式会社 | ポリエステル樹脂の製造方法 |
EP1400568B1 (en) | 2002-09-17 | 2007-11-07 | Mitsubishi Gas Chemical Company, Inc. | Polyester-based resin composition |
US6818276B2 (en) | 2002-10-24 | 2004-11-16 | Eastman Kodak Company | Light management film with colorant receiving layer |
WO2004039860A1 (ja) | 2002-10-31 | 2004-05-13 | Mitsubishi Chemical Corporation | ポリエステル樹脂、ポリエステル樹脂組成物及びこれを用いて得られるシート、フィルム並びに中空成形容器 |
US20040106707A1 (en) | 2002-11-13 | 2004-06-03 | Kai Su | Protective coatings and methods of applying and using the same |
US6914120B2 (en) | 2002-11-13 | 2005-07-05 | Eastman Chemical Company | Method for making isosorbide containing polyesters |
US6896966B2 (en) | 2002-11-22 | 2005-05-24 | Eastman Chemical Company | Articles of manufacture incorporating polyester/polycarbonate blends |
US7118799B2 (en) * | 2002-11-22 | 2006-10-10 | Eastman Chemical Company | Thermoplastic article having a decorative material embedded therein |
EP1570001B1 (en) * | 2002-12-10 | 2009-11-11 | BASF Corporation | High flow engineering thermoplastic compositions and products made therefrom |
US7285587B2 (en) * | 2002-12-20 | 2007-10-23 | Eastman Chemical Company | Flame retardant polyester compositions for calendering |
US7482397B2 (en) | 2003-01-13 | 2009-01-27 | Eastman Chemical Company | Polycarbonate compositions |
US20040143041A1 (en) | 2003-01-13 | 2004-07-22 | Pearson Jason Clay | Polyester compositions |
US7004583B2 (en) | 2003-01-29 | 2006-02-28 | East Bay Technologies | Eyewear lenses and methods of manufacturing |
JP2004244497A (ja) | 2003-02-13 | 2004-09-02 | Konica Minolta Holdings Inc | セルロースエステルフィルム、偏光板及び液晶表示装置 |
US7332227B2 (en) * | 2003-03-14 | 2008-02-19 | Becton, Dickinson And Company | Non-volatile lubricant system for medical devices |
JP2004292558A (ja) | 2003-03-26 | 2004-10-21 | Konica Minolta Holdings Inc | セルロースエステルフィルムとその製造方法および偏光板保護フィルム |
US6818293B1 (en) | 2003-04-24 | 2004-11-16 | Eastman Chemical Company | Stabilized polyester fibers and films |
JP3927585B2 (ja) | 2003-05-20 | 2007-06-13 | 三菱樹脂株式会社 | 脂肪族ポリエステル系樹脂反射フィルム及び反射板 |
US7046439B2 (en) | 2003-05-22 | 2006-05-16 | Eastman Kodak Company | Optical element with nanoparticles |
KR101050982B1 (ko) | 2003-06-17 | 2011-07-21 | 테이진 카세이 가부시키가이샤 | 직하형 백라이트식 액정 표시 장치 및 광확산판 |
JP2005008809A (ja) * | 2003-06-20 | 2005-01-13 | Mitsubishi Gas Chem Co Inc | 再生ポリエステル樹脂組成物の製造方法 |
EP1498778A1 (en) * | 2003-06-27 | 2005-01-19 | ASML Netherlands B.V. | Lithographic apparatus and device manufacturing method |
WO2005007735A2 (en) | 2003-07-11 | 2005-01-27 | Eastman Chemical Company | Addition of uv absorbers to pet process for maximum yield |
US20050010017A1 (en) | 2003-07-11 | 2005-01-13 | Blakely Dale Milton | Addition of UV inhibitors to pet process for maximum yield |
JP2005047984A (ja) * | 2003-07-30 | 2005-02-24 | Toyobo Co Ltd | 医療用具用ポリエステル系樹脂射出成形体 |
JP2005047983A (ja) * | 2003-07-30 | 2005-02-24 | Toyobo Co Ltd | 医療用具用ポリエステル系樹脂射出成形体 |
EP1666521B1 (en) | 2003-09-11 | 2014-03-26 | Teijin Dupont Films Japan Limited | Polyester film |
US7237360B2 (en) * | 2003-09-23 | 2007-07-03 | Cemusa, Inc. | Shelter |
CN100427525C (zh) | 2003-09-25 | 2008-10-22 | 大阪瓦斯株式会社 | 聚酯树脂组合物及光学材料 |
US7051892B1 (en) | 2003-10-28 | 2006-05-30 | O'day Jr William R | Water bottle for a dispenser |
US7235623B2 (en) * | 2003-11-26 | 2007-06-26 | Eastman Chemical Company | Polyester compositions for calendering |
US20050119359A1 (en) * | 2003-12-02 | 2005-06-02 | Shelby Marcus D. | Void-containing polyester shrink film |
US7169880B2 (en) * | 2003-12-04 | 2007-01-30 | Eastman Chemical Company | Shaped articles from cycloaliphatic polyester compositions |
US8192676B2 (en) | 2004-02-12 | 2012-06-05 | Valspar Sourcing, Inc. | Container having barrier properties and method of manufacturing the same |
JP4378689B2 (ja) | 2004-03-15 | 2009-12-09 | 帝人化成株式会社 | ポリエチレンナフタレート系樹脂からなる燃料タンク用容器 |
US7179869B2 (en) | 2004-03-22 | 2007-02-20 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyester resins |
USD532694S1 (en) | 2004-04-29 | 2006-11-28 | Plastipak Packaging, Inc. | Container |
US20060004151A1 (en) * | 2004-06-30 | 2006-01-05 | General Electric Company | Copolymers containing indan moieties and blends thereof |
US20060036012A1 (en) | 2004-08-10 | 2006-02-16 | Hayes Richard A | Process for producing a wollastonite containing polyester and products and articles produced therefrom |
EP1784300B1 (en) | 2004-08-31 | 2012-05-23 | INVISTA Technologies S.à.r.l. | Polyester-polyamide blends having low haze |
CN100456163C (zh) | 2004-09-08 | 2009-01-28 | 佳能株式会社 | 制造电子照相无接头环形带的方法以及电子照相设备 |
DE102004051274A1 (de) * | 2004-10-21 | 2006-04-27 | Robert Bosch Gmbh | Verfahren und Vorrichtung zum Anpassen einer Überwachungseinrichtung eines Steuergerätes für ein Rückhaltesystem eines Kraftfahrzeugs |
US20060094858A1 (en) | 2004-10-28 | 2006-05-04 | Turner Sam R | Novel copolyester compositions with improved impact strength at low temperatures |
US8071695B2 (en) | 2004-11-12 | 2011-12-06 | Eastman Chemical Company | Polyeste blends with improved stress whitening for film and sheet applications |
US7582690B2 (en) | 2004-11-19 | 2009-09-01 | Eastman Chemical Company | Stabilized aliphatic polyester compositions |
US7375154B2 (en) | 2004-12-06 | 2008-05-20 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
CN101084250B (zh) | 2004-12-21 | 2011-06-15 | 三井化学株式会社 | 改性酚树脂、含有它的环氧树脂组合物及使用该组合物的预浸料坯 |
US20060135668A1 (en) | 2004-12-21 | 2006-06-22 | Hayes Richard A | Polyesters containing natural mineral materials, processes for producing such polyesters, and shaped articles produced therefrom |
US7114623B2 (en) | 2005-02-04 | 2006-10-03 | John Robinson | Point of purchase display with interchangeable placards |
US7955533B2 (en) | 2005-03-02 | 2011-06-07 | Eastman Chemical Company | Process for the preparation of transparent shaped articles |
US7959998B2 (en) | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
US20060199871A1 (en) | 2005-03-02 | 2006-09-07 | Hale Wesley R | Multilayered, transparent articles and a process for their preparation |
WO2007126855A1 (en) | 2006-03-28 | 2007-11-08 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof |
US7959836B2 (en) | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
WO2007053549A1 (en) | 2005-10-28 | 2007-05-10 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US7842776B2 (en) * | 2005-06-17 | 2010-11-30 | Eastman Chemical Company | Appliance parts comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US7968164B2 (en) | 2005-03-02 | 2011-06-28 | Eastman Chemical Company | Transparent polymer blends and articles prepared therefrom |
US7964258B2 (en) | 2005-03-02 | 2011-06-21 | Eastman Chemical Company | Transparent, oxygen-scavenging compositions and articles prepared therefrom |
US7955674B2 (en) | 2005-03-02 | 2011-06-07 | Eastman Chemical Company | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
ES2297803T3 (es) | 2005-03-15 | 2008-05-01 | Techne Technipack Engineering Italia S.P.A. | Botella fabricada en material plastico con fondo reforzado. |
JP4830410B2 (ja) | 2005-09-05 | 2011-12-07 | 東洋製罐株式会社 | 延伸成形容器及びその製造方法 |
US20060270806A1 (en) | 2005-05-26 | 2006-11-30 | Hale Wesley R | Miscible high Tg polyester/polymer blend compositions and films formed therefrom |
US20060270773A1 (en) | 2005-05-26 | 2006-11-30 | Hale Wesley R | Polyester-polycarbonate blends for diffuser sheets with improved luminance |
US20130072628A1 (en) | 2005-06-17 | 2013-03-21 | Eastman Chemical Company | Coating compositions containing cyclobutanediol |
CN101203541B (zh) | 2005-06-17 | 2012-10-10 | 伊士曼化工公司 | 含有环丁二醇并具有比浓对数粘度和高玻璃化转变温度特定组合的聚酯组合物和由其生产的制品 |
US7825176B2 (en) | 2005-08-31 | 2010-11-02 | Sabic Innovative Plastics Ip B.V. | High flow polyester composition |
ATE505500T1 (de) * | 2005-10-28 | 2011-04-15 | Eastman Chem Co | Polyesterzusammensetzungen mit cyclobutandiol mit hoher glasübergangstemperatur und daraus hergestellte artikel |
US20100096589A1 (en) | 2005-10-28 | 2010-04-22 | Emmett Dudley Crawford | Polyester compositions containing low amounts of cyclobutanediol and articles made therefrom |
CA2565003A1 (en) | 2005-11-09 | 2007-05-09 | Dan Loebach | Water bottle |
US7427430B2 (en) | 2005-12-29 | 2008-09-23 | Honeywell International Inc. | Polyamide blend composition having excellent gas barrier performance |
JP2007253491A (ja) | 2006-03-24 | 2007-10-04 | Nippon Zeon Co Ltd | ブロー成形容器 |
US20080092776A1 (en) | 2006-10-19 | 2008-04-24 | Rebecca Reid Stockl | Low-VOC additives for extending wet edge and open times of coatings |
CN101868340B (zh) * | 2007-11-21 | 2016-04-20 | 伊士曼化工公司 | 塑料乳瓶、其它吹塑物品及其制备方法 |
TWI455967B (zh) | 2008-04-24 | 2014-10-11 | Saudi Basic Ind Corp | 不透明聚酯薄膜的製造方法 |
ES2534436T3 (es) | 2008-09-30 | 2015-04-22 | The Procter & Gamble Company | Proceso de moldeo por soplado con estirado y recipiente |
US8324316B2 (en) | 2009-02-06 | 2012-12-04 | Eastman Chemical Company | Unsaturated polyester resin compositions containing 2,2,2,4-tetramethyl-1,3-cyclobutanediol and articles made therefrom |
US20100252570A1 (en) | 2009-04-01 | 2010-10-07 | Yui George M | Bottom loading water cooler |
WO2011017481A2 (en) | 2009-08-06 | 2011-02-10 | Robert Priessnitz | Bottle with handle |
-
2006
- 2006-03-28 US US11/391,485 patent/US7842776B2/en active Active
- 2006-03-28 US US11/391,642 patent/US7510768B2/en active Active
- 2006-03-28 US US11/390,853 patent/US20070270569A1/en not_active Abandoned
- 2006-03-28 US US11/391,137 patent/US7985827B2/en active Active
- 2006-03-28 US US11/390,655 patent/US8067525B2/en not_active Expired - Fee Related
- 2006-03-28 US US11/390,631 patent/US7855267B2/en active Active
- 2006-03-28 US US11/390,722 patent/US7893187B2/en not_active Expired - Fee Related
- 2006-03-28 US US11/390,672 patent/US20060287479A1/en not_active Abandoned
- 2006-03-28 US US11/390,630 patent/US7807774B2/en not_active Expired - Fee Related
- 2006-03-28 US US11/391,125 patent/US20070010650A1/en not_active Abandoned
- 2006-03-28 US US11/390,794 patent/US8119761B2/en active Active
- 2006-03-28 US US11/391,495 patent/US7807775B2/en not_active Expired - Fee Related
- 2006-03-28 US US11/390,882 patent/US20060287486A1/en not_active Abandoned
- 2006-03-28 US US11/390,858 patent/US7951900B2/en active Active
- 2006-03-28 US US11/390,811 patent/US7868128B2/en not_active Expired - Fee Related
- 2006-03-28 US US11/391,571 patent/US20060287494A1/en not_active Abandoned
- 2006-03-28 US US11/390,826 patent/US7906610B2/en active Active
- 2006-03-28 US US11/390,836 patent/US20060286330A1/en not_active Abandoned
- 2006-03-28 US US11/390,955 patent/US7915376B2/en active Active
- 2006-03-28 US US11/391,063 patent/US7576171B2/en not_active Expired - Fee Related
- 2006-03-28 US US11/391,659 patent/US20060287496A1/en not_active Abandoned
- 2006-03-28 US US11/391,156 patent/US7812112B2/en active Active
- 2006-03-28 US US11/390,671 patent/US8063172B2/en active Active
- 2006-03-28 US US11/390,847 patent/US20060287484A1/en not_active Abandoned
- 2006-03-28 US US11/390,883 patent/US7834129B2/en active Active
- 2006-03-28 US US11/391,576 patent/US7803441B2/en active Active
- 2006-03-28 US US11/390,827 patent/US7893188B2/en active Active
- 2006-03-28 US US11/390,752 patent/US8063173B2/en active Active
- 2006-03-28 US US11/390,654 patent/US20060287477A1/en not_active Abandoned
- 2006-03-28 US US11/390,751 patent/US7803440B2/en active Active
- 2006-03-28 US US11/390,865 patent/US20060287485A1/en not_active Abandoned
- 2006-03-28 US US11/390,864 patent/US7812111B2/en not_active Expired - Fee Related
- 2006-03-28 US US11/390,563 patent/US7902320B2/en not_active Expired - Fee Related
- 2006-03-28 US US11/390,629 patent/US7803439B2/en active Active
- 2006-03-28 US US11/390,750 patent/US20060287480A1/en not_active Abandoned
- 2006-03-28 US US11/390,814 patent/US20060286327A1/en not_active Abandoned
- 2006-03-28 US US11/390,793 patent/US20060286389A1/en not_active Abandoned
- 2006-03-28 US US11/391,505 patent/US7838620B2/en active Active
- 2006-03-28 US US11/391,565 patent/US7781562B2/en active Active
- 2006-03-30 KR KR1020077028806A patent/KR20080019218A/ko not_active Application Discontinuation
- 2006-03-30 EP EP20090012051 patent/EP2156934B1/en active Active
- 2006-03-30 KR KR1020077028802A patent/KR20080019217A/ko not_active Application Discontinuation
- 2006-03-30 JP JP2008516841A patent/JP2008546603A/ja active Pending
- 2006-03-30 JP JP2008516855A patent/JP2008544035A/ja active Pending
- 2006-03-30 AU AU2006262854A patent/AU2006262854A1/en not_active Abandoned
- 2006-03-30 JP JP2008516854A patent/JP5139274B2/ja active Active
- 2006-03-30 WO PCT/US2006/011594 patent/WO2007001529A1/en active Application Filing
- 2006-03-30 TW TW095111258A patent/TW200700456A/zh unknown
- 2006-03-30 JP JP2008516852A patent/JP2008544033A/ja not_active Withdrawn
- 2006-03-30 EP EP06740280A patent/EP1910441B1/en active Active
- 2006-03-30 TW TW095111208A patent/TW200700454A/zh unknown
- 2006-03-30 JP JP2008516842A patent/JP2008544026A/ja not_active Withdrawn
- 2006-03-30 KR KR1020077028797A patent/KR20080019216A/ko not_active Application Discontinuation
- 2006-03-30 EP EP06749030A patent/EP1907441A1/en not_active Withdrawn
- 2006-03-30 MY MYPI20061422A patent/MY145986A/en unknown
- 2006-03-30 PL PL06749034T patent/PL1907442T3/pl unknown
- 2006-03-30 CN CN201310616094.0A patent/CN103755930A/zh active Pending
- 2006-03-30 JP JP2008516845A patent/JP5408467B2/ja active Active
- 2006-03-30 EP EP06749044A patent/EP1904549B1/en not_active Not-in-force
- 2006-03-30 AT AT06740273T patent/ATE475683T1/de not_active IP Right Cessation
- 2006-03-30 EP EP06740055A patent/EP1899400B1/en not_active Not-in-force
- 2006-03-30 EP EP06749007A patent/EP1891135B1/en not_active Not-in-force
- 2006-03-30 AT AT06740272T patent/ATE458772T1/de not_active IP Right Cessation
- 2006-03-30 WO PCT/US2006/011940 patent/WO2007001564A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/011926 patent/WO2007001559A1/en active Application Filing
- 2006-03-30 EP EP10014298.3A patent/EP2277935B1/en active Active
- 2006-03-30 EP EP20090012339 patent/EP2138524A1/en not_active Withdrawn
- 2006-03-30 EP EP06749145.6A patent/EP1913054B1/en active Active
- 2006-03-30 DE DE602006012319T patent/DE602006012319D1/de active Active
- 2006-03-30 EP EP06740206A patent/EP1891133A1/en not_active Withdrawn
- 2006-03-30 MX MX2007015664A patent/MX2007015664A/es active IP Right Grant
- 2006-03-30 WO PCT/US2006/011966 patent/WO2007001566A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/012065 patent/WO2007001572A1/en active Application Filing
- 2006-03-30 EP EP06740273A patent/EP1907439B1/en active Active
- 2006-03-30 JP JP2008516857A patent/JP2008547046A/ja active Pending
- 2006-03-30 JP JP2008516835A patent/JP5431725B2/ja active Active
- 2006-03-30 JP JP2008516838A patent/JP2008546866A/ja not_active Withdrawn
- 2006-03-30 WO PCT/US2006/011892 patent/WO2007001549A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/011593 patent/WO2007001528A1/en active Application Filing
- 2006-03-30 KR KR1020077028804A patent/KR101274908B1/ko active IP Right Grant
- 2006-03-30 AR ARP060101261 patent/AR055897A1/es not_active Application Discontinuation
- 2006-03-30 TW TW095111210A patent/TW200700455A/zh unknown
- 2006-03-30 JP JP2008516831A patent/JP2008546865A/ja not_active Withdrawn
- 2006-03-30 WO PCT/US2006/011687 patent/WO2007001533A1/en active Application Filing
- 2006-03-30 EP EP06740272A patent/EP1913051B1/en active Active
- 2006-03-30 EP EP06749020.1A patent/EP1891131B1/en active Active
- 2006-03-30 WO PCT/US2006/011873 patent/WO2007001544A1/en active Application Filing
- 2006-03-30 DE DE602006009519T patent/DE602006009519D1/de active Active
- 2006-03-30 TW TW095111213A patent/TW200700494A/zh unknown
- 2006-03-30 KR KR1020077028792A patent/KR101249552B1/ko active IP Right Grant
- 2006-03-30 MX MX2007015667A patent/MX2007015667A/es active IP Right Grant
- 2006-03-30 PL PL06758235T patent/PL1891138T3/pl unknown
- 2006-03-30 WO PCT/US2006/012066 patent/WO2007001573A1/en active Application Filing
- 2006-03-30 EP EP15002089.9A patent/EP2954910B1/en active Active
- 2006-03-30 KR KR1020077028809A patent/KR101249616B1/ko active IP Right Grant
- 2006-03-30 KR KR1020077028827A patent/KR101238995B1/ko active IP Right Grant
- 2006-03-30 WO PCT/US2006/011890 patent/WO2007001547A1/en active Application Filing
- 2006-03-30 JP JP2008516853A patent/JP2008546561A/ja not_active Withdrawn
- 2006-03-30 AT AT06740055T patent/ATE444325T1/de not_active IP Right Cessation
- 2006-03-30 EP EP20090012338 patent/EP2138523B1/en not_active Not-in-force
- 2006-03-30 WO PCT/US2006/011962 patent/WO2007001565A1/en active Application Filing
- 2006-03-30 AT AT06749007T patent/ATE434009T1/de not_active IP Right Cessation
- 2006-03-30 AT AT06758239T patent/ATE452925T1/de not_active IP Right Cessation
- 2006-03-30 TW TW095111285A patent/TW200700497A/zh unknown
- 2006-03-30 EP EP06758239A patent/EP1913056B1/en not_active Not-in-force
- 2006-03-30 DE DE602006011332T patent/DE602006011332D1/de active Active
- 2006-03-30 DE DE602006020720T patent/DE602006020720D1/de active Active
- 2006-03-30 EP EP20100012570 patent/EP2272888B1/en active Active
- 2006-03-30 EP EP14001923.3A patent/EP2865398B1/en active Active
- 2006-03-30 WO PCT/US2006/011891 patent/WO2007001548A1/en active Application Filing
- 2006-03-30 EP EP06749015A patent/EP1891136B1/en not_active Not-in-force
- 2006-03-30 EP EP06748952A patent/EP1898972B1/en not_active Not-in-force
- 2006-03-30 DE DE602006007346T patent/DE602006007346D1/de active Active
- 2006-03-30 EP EP06784333A patent/EP1907443A1/en not_active Withdrawn
- 2006-03-30 AT AT06749015T patent/ATE466039T1/de not_active IP Right Cessation
- 2006-03-30 DE DE602006018314T patent/DE602006018314D1/de active Active
- 2006-03-30 EP EP20090015897 patent/EP2159029A3/en not_active Withdrawn
- 2006-03-30 PL PL06749020T patent/PL1891131T3/pl unknown
- 2006-03-30 WO PCT/US2006/011927 patent/WO2007001560A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/011910 patent/WO2007001552A1/en active Application Filing
- 2006-03-30 JP JP2008516839A patent/JP2008544024A/ja active Pending
- 2006-03-30 EP EP06749034A patent/EP1907442B9/en active Active
- 2006-03-30 DE DE602006010552T patent/DE602006010552D1/de active Active
- 2006-03-30 AT AT06749034T patent/ATE488541T1/de not_active IP Right Cessation
- 2006-03-30 JP JP2008516833A patent/JP2008544121A/ja active Pending
- 2006-03-30 DE DE602006013971T patent/DE602006013971D1/de active Active
- 2006-03-30 JP JP2008516850A patent/JP5683786B2/ja active Active
- 2006-03-30 MX MX2007015662A patent/MX2007015662A/es active IP Right Grant
- 2006-03-30 WO PCT/US2006/011660 patent/WO2007001530A1/en active Application Filing
- 2006-03-30 TW TW095111234A patent/TW200700495A/zh unknown
- 2006-03-30 WO PCT/US2006/012268 patent/WO2006137954A1/en active Application Filing
- 2006-03-30 ES ES06748952T patent/ES2341482T3/es active Active
- 2006-03-30 JP JP2008516847A patent/JP5290754B2/ja active Active
- 2006-03-30 AT AT06740270T patent/ATE466898T1/de not_active IP Right Cessation
- 2006-03-30 JP JP2008516832A patent/JP2008543425A/ja active Pending
- 2006-03-30 WO PCT/US2006/011796 patent/WO2007001541A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/011893 patent/WO2007001550A1/en active Application Filing
- 2006-03-30 EP EP06749014A patent/EP1891157B1/en not_active Not-in-force
- 2006-03-30 WO PCT/US2006/011937 patent/WO2007001563A1/en active Application Filing
- 2006-03-30 BR BRPI0613698A patent/BRPI0613698A2/pt not_active IP Right Cessation
- 2006-03-30 WO PCT/US2006/011912 patent/WO2007001554A1/en active Application Filing
- 2006-03-30 JP JP2008516827A patent/JP2008543424A/ja active Pending
- 2006-03-30 MY MYPI20061425A patent/MY148507A/en unknown
- 2006-03-30 AT AT06748952T patent/ATE457754T1/de not_active IP Right Cessation
- 2006-03-30 TW TW095111286A patent/TW200700498A/zh unknown
- 2006-03-30 MX MX2007015687A patent/MX2007015687A/es not_active Application Discontinuation
- 2006-03-30 WO PCT/US2006/011662 patent/WO2007001531A1/en active Application Filing
- 2006-03-30 DE DE602006015813T patent/DE602006015813D1/de active Active
- 2006-03-30 DE DE602006009396T patent/DE602006009396D1/de active Active
- 2006-03-30 KR KR1020077028803A patent/KR101249550B1/ko active IP Right Grant
- 2006-03-30 WO PCT/US2006/011967 patent/WO2007001567A1/en active Application Filing
- 2006-03-30 EP EP06758235A patent/EP1891138B1/en active Active
- 2006-03-30 BR BRPI0611900A patent/BRPI0611900A2/pt not_active IP Right Cessation
- 2006-03-30 EP EP15000775.5A patent/EP2907640A1/en not_active Withdrawn
- 2006-03-30 WO PCT/US2006/011915 patent/WO2007001557A1/en active Application Filing
- 2006-03-30 EP EP06749073A patent/EP1913053B1/en active Active
- 2006-03-30 WO PCT/US2006/012063 patent/WO2007001571A1/en active Application Filing
- 2006-03-30 AT AT06749073T patent/ATE445659T1/de not_active IP Right Cessation
- 2006-03-30 KR KR1020077028795A patent/KR20080031672A/ko not_active Application Discontinuation
- 2006-03-30 EP EP06758238A patent/EP1913055A1/en not_active Withdrawn
- 2006-03-30 EP EP20110000363 patent/EP2305732A3/en not_active Withdrawn
- 2006-03-30 KR KR1020077028799A patent/KR20080018998A/ko not_active Application Discontinuation
- 2006-03-30 AT AT06749029T patent/ATE444326T1/de not_active IP Right Cessation
- 2006-03-30 BR BRPI0613645A patent/BRPI0613645A2/pt not_active IP Right Cessation
- 2006-03-30 WO PCT/US2006/011913 patent/WO2007001555A1/en active Application Filing
- 2006-03-30 JP JP2008516851A patent/JP2008546868A/ja not_active Withdrawn
- 2006-03-30 AT AT06749045T patent/ATE495211T1/de not_active IP Right Cessation
- 2006-03-30 EP EP06749019A patent/EP1891137B1/en active Active
- 2006-03-30 EP EP20163621.4A patent/EP3686233A1/en active Pending
- 2006-03-30 DE DE602006019597T patent/DE602006019597D1/de active Active
- 2006-03-30 JP JP2008516840A patent/JP5384936B2/ja active Active
- 2006-03-30 AT AT06740053T patent/ATE449121T1/de not_active IP Right Cessation
- 2006-03-30 JP JP2008516848A patent/JP2008544030A/ja active Pending
- 2006-03-30 JP JP2008516826A patent/JP2008544019A/ja not_active Withdrawn
- 2006-03-30 WO PCT/US2006/011968 patent/WO2007001568A1/en active Application Filing
- 2006-03-30 EP EP09012868.7A patent/EP2192140B1/en active Active
- 2006-03-30 WO PCT/US2006/012075 patent/WO2007001575A1/en active Application Filing
- 2006-03-30 AT AT06749044T patent/ATE443095T1/de not_active IP Right Cessation
- 2006-03-30 WO PCT/US2006/011935 patent/WO2007001562A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/011701 patent/WO2007001536A1/en unknown
- 2006-03-30 EP EP20100004446 patent/EP2233657A3/en not_active Withdrawn
- 2006-03-30 WO PCT/US2006/011808 patent/WO2007001542A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/011704 patent/WO2007001537A1/en active Application Filing
- 2006-03-30 KR KR1020077028793A patent/KR101280717B1/ko active IP Right Grant
- 2006-03-30 EP EP06740053A patent/EP1899399B1/en active Active
- 2006-03-30 JP JP2008516836A patent/JP2008544023A/ja active Pending
- 2006-03-30 WO PCT/US2006/011970 patent/WO2007001569A1/en active Application Filing
- 2006-03-30 MX MX2007015663A patent/MX2007015663A/es unknown
- 2006-03-30 EP EP06784332.6A patent/EP1899401B1/en active Active
- 2006-03-30 DE DE602006014160T patent/DE602006014160D1/de active Active
- 2006-03-30 JP JP2008516846A patent/JP2008544028A/ja active Pending
- 2006-03-30 WO PCT/US2006/011877 patent/WO2007001545A1/en active Application Filing
- 2006-03-30 DE DE602006009816T patent/DE602006009816D1/de active Active
- 2006-03-30 DE DE602006013146T patent/DE602006013146D1/de active Active
- 2006-03-30 EP EP06749046A patent/EP1913052A1/en not_active Withdrawn
- 2006-03-30 EP EP06740210A patent/EP1891134A1/en not_active Withdrawn
- 2006-03-30 DE DE602006009514T patent/DE602006009514D1/de active Active
- 2006-03-30 TW TW095111241A patent/TW200700496A/zh unknown
- 2006-03-30 KR KR1020077028811A patent/KR20080016841A/ko not_active Application Discontinuation
- 2006-03-30 EP EP16000036.0A patent/EP3031481B1/en active Active
- 2006-03-30 EP EP20100007798 patent/EP2260887A1/en not_active Withdrawn
- 2006-03-30 JP JP2008516829A patent/JP2008544020A/ja not_active Withdrawn
- 2006-03-30 EP EP06749045A patent/EP1904550B1/en active Active
- 2006-03-30 JP JP2008516858A patent/JP5616581B2/ja active Active
- 2006-03-30 KR KR1020077028796A patent/KR101249595B1/ko active IP Right Grant
- 2006-03-30 AT AT06749014T patent/ATE434020T1/de not_active IP Right Cessation
- 2006-03-30 DE DE602006009268T patent/DE602006009268D1/de active Active
- 2006-03-30 DE DE602006012496T patent/DE602006012496D1/de active Active
- 2006-03-30 WO PCT/US2006/011914 patent/WO2007001556A1/en active Application Filing
- 2006-03-30 AT AT09012338T patent/ATE522560T1/de not_active IP Right Cessation
- 2006-03-30 EP EP17163415.7A patent/EP3246055B1/en active Active
- 2006-03-30 WO PCT/US2006/011686 patent/WO2007001532A1/en active Application Filing
- 2006-03-30 AU AU2006262852A patent/AU2006262852A1/en not_active Abandoned
- 2006-03-30 JP JP2008516849A patent/JP2008544031A/ja active Pending
- 2006-03-30 DE DE602006018945T patent/DE602006018945D1/de active Active
- 2006-03-30 JP JP2008516837A patent/JP2008547143A/ja active Pending
- 2006-03-30 AT AT06758240T patent/ATE491737T1/de not_active IP Right Cessation
- 2006-03-30 WO PCT/US2006/011911 patent/WO2007001553A1/en active Application Filing
- 2006-03-30 WO PCT/US2006/011700 patent/WO2007001535A1/en active Application Filing
- 2006-03-30 DE DE602006007345T patent/DE602006007345D1/de active Active
- 2006-03-30 KR KR1020077028818A patent/KR101249547B1/ko active IP Right Grant
- 2006-03-30 EP EP20090014313 patent/EP2147763A1/en not_active Withdrawn
- 2006-03-30 EP EP10001838.1A patent/EP2192141B1/en active Active
- 2006-03-30 EP EP06740024A patent/EP1891132A1/en not_active Withdrawn
- 2006-03-30 AT AT06758235T patent/ATE443728T1/de not_active IP Right Cessation
- 2006-03-30 EP EP06749029A patent/EP1907440B1/en not_active Not-in-force
- 2006-03-30 EP EP06758241A patent/EP1904551A1/en not_active Withdrawn
- 2006-03-30 JP JP2008516825A patent/JP2008546442A/ja active Pending
- 2006-03-30 AT AT06740280T patent/ATE461956T1/de not_active IP Right Cessation
- 2006-03-30 EP EP06758240A patent/EP1913057B1/en not_active Not-in-force
- 2006-03-30 EP EP06740270A patent/EP1910442B1/en active Active
- 2006-03-30 EP EP15003262.1A patent/EP3017834A1/en not_active Withdrawn
- 2006-03-30 JP JP2008516844A patent/JP2008544027A/ja not_active Withdrawn
- 2006-03-30 TW TW095111204A patent/TW200700493A/zh unknown
- 2006-03-30 WO PCT/US2006/012062 patent/WO2007001570A1/en active Application Filing
- 2006-03-30 AT AT06749019T patent/ATE502068T1/de not_active IP Right Cessation
- 2006-03-30 JP JP2008516830A patent/JP2008546560A/ja active Pending
- 2006-10-27 US US12/091,568 patent/US20090093574A1/en not_active Abandoned
- 2006-10-27 US US12/091,572 patent/US20090093573A1/en not_active Abandoned
-
2007
- 2007-12-10 IL IL188026A patent/IL188026A0/en unknown
- 2007-12-10 IL IL188025A patent/IL188025A0/en unknown
- 2007-12-10 IL IL188024A patent/IL188024A0/en unknown
-
2008
- 2008-05-14 HK HK08105340.8A patent/HK1115398A1/xx not_active IP Right Cessation
- 2008-05-14 HK HK08105336.4A patent/HK1115396A1/xx not_active IP Right Cessation
- 2008-06-19 HK HK08106817.0A patent/HK1116810A1/xx not_active IP Right Cessation
- 2008-09-05 HK HK08109889.7A patent/HK1118843A1/xx not_active IP Right Cessation
-
2009
- 2009-01-29 US US12/361,779 patent/US7740941B2/en active Active
- 2009-06-08 US US12/479,893 patent/US20100092705A1/en not_active Abandoned
-
2010
- 2010-03-16 US US12/724,480 patent/US7906212B2/en active Active
- 2010-03-16 US US12/724,492 patent/US20100174030A1/en not_active Abandoned
- 2010-05-20 US US12/784,193 patent/US8101705B2/en active Active
- 2010-10-07 US US12/900,060 patent/US8133967B2/en not_active Expired - Fee Related
- 2010-11-10 US US12/943,217 patent/US8119762B2/en active Active
-
2011
- 2011-01-17 US US13/007,838 patent/US9169348B2/en active Active
- 2011-01-28 US US13/016,147 patent/US8354491B2/en active Active
- 2011-01-31 US US13/017,352 patent/US20110189415A1/en not_active Abandoned
- 2011-06-17 US US13/162,870 patent/US9181387B2/en active Active
- 2011-08-23 US US13/215,511 patent/US8507638B2/en active Active
-
2012
- 2012-01-12 US US13/348,677 patent/US8415450B2/en active Active
- 2012-03-21 JP JP2012064353A patent/JP5437424B2/ja active Active
- 2012-03-21 JP JP2012064378A patent/JP5437425B2/ja active Active
- 2012-10-12 JP JP2012227374A patent/JP5773966B2/ja active Active
- 2012-11-22 JP JP2012256682A patent/JP5685240B2/ja active Active
- 2012-12-10 US US13/709,097 patent/US9175134B2/en active Active
-
2013
- 2013-02-25 US US13/776,038 patent/US9181388B2/en active Active
- 2013-02-28 JP JP2013039677A patent/JP2013100557A/ja active Pending
- 2013-07-12 JP JP2013146759A patent/JP5767671B2/ja active Active
- 2013-08-28 JP JP2013176918A patent/JP5647311B2/ja active Active
- 2013-10-16 JP JP2013215301A patent/JP5795615B2/ja active Active
-
2015
- 2015-09-25 US US14/865,714 patent/US9534079B2/en active Active
- 2015-09-25 US US14/865,681 patent/US20160009857A1/en not_active Abandoned
- 2015-09-25 US US14/865,705 patent/US9765181B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3313777A (en) * | 1959-12-18 | 1967-04-11 | Eastman Kodak Co | Linear polyesters and polyester-amides from 2, 2, 4, 4-tetraalkyl-1, 3-cyclobutanediols |
US6043322A (en) * | 1996-12-28 | 2000-03-28 | Eastman Chemical Company | Clear polycarbonate and polyester blends |
CN1293696A (zh) * | 1998-03-17 | 2001-05-02 | 伊斯曼化学公司 | 用于压延的聚酯树脂组合物 |
US5962625A (en) * | 1998-06-24 | 1999-10-05 | Eastman Chemical Company | High clarity polyester containing sub-visual antimony phosphate derivatives particles |
CN1501954A (zh) * | 2001-04-11 | 2004-06-02 | �Ϻ���ͨ��ѧ | 由增塑聚酯制备的薄膜 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114206615A (zh) * | 2019-08-02 | 2022-03-18 | 伊士曼化工公司 | 多层片材 |
WO2023206073A1 (en) * | 2022-04-26 | 2023-11-02 | Eastman Chemical (China) Co., Ltd. | Flame retardant copolyester compositions |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101193936B (zh) | 含有少量环丁二醇的聚酯组合物和由其生产的制品 | |
CN103755930A (zh) | 含有少量环丁二醇的聚酯组合物制成的膜和/或片材 | |
CN101296992B (zh) | 含有环丁烷二醇和某些热稳定剂和/或它们的反应产物的聚酯组合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140430 |
|
RJ01 | Rejection of invention patent application after publication |