WO1989011507A1 - Melange greffe d'un elastomere et d'un polyester thermoplastique - Google Patents

Melange greffe d'un elastomere et d'un polyester thermoplastique Download PDF

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Publication number
WO1989011507A1
WO1989011507A1 PCT/US1989/002060 US8902060W WO8911507A1 WO 1989011507 A1 WO1989011507 A1 WO 1989011507A1 US 8902060 W US8902060 W US 8902060W WO 8911507 A1 WO8911507 A1 WO 8911507A1
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Prior art keywords
elastomer
composition
poly
polycarbodiimide
parts
Prior art date
Application number
PCT/US1989/002060
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English (en)
Inventor
Murali K. Akkapeddi
Alan C. Brown
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Allied-Signal Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Allied-Signal Inc. filed Critical Allied-Signal Inc.
Priority to KR1019900700097A priority Critical patent/KR900701930A/ko
Publication of WO1989011507A1 publication Critical patent/WO1989011507A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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

Definitions

  • the present invention relates to thermoplastic polyester/elastomer grafted blends.
  • Thermoplastic polyesters such as poly(ethylene terephthalate) (hereinafter PET) and poly(butylene terephthalate) (hereinafter PBT) are widely used as engineering resins because they have high crystalline melting points. good mechanical properties, good hygrothermal dimensional stability, and good solvent resistance.
  • PET poly(ethylene terephthalate)
  • PBT poly(butylene terephthalate)
  • PET poly(ethylene terephthalate)
  • PBT poly(butylene terephthalate)
  • thermoplastic polyesters have been blended with thermoplastic polyesters in order to improve toughness.
  • thermoplastic polyesters for example, thermoplastic polyesters
  • U.S. Patent 3.435.093 teaches a blend of PET and an ionomer type hydrocarbon copolymer.
  • U.S. Patent 4,090.996 teaches a composition of PBT. a block copolymer such as styrene-butadiene, and polyamide.
  • U.S. Patent 4.096,202 teaches a blend of PBT and a core-shell rubber consisting of multiphase acrylic compositions.
  • an elastomer/PBT blend retains most of the improvement in notched impact.
  • thermoplastic polyester/elastomer blend having improved impact resistance, tensile elongation, and resistance to embrittlement upon annealing.
  • Carbodiimides or polycarbodiimides have been added to PBT to improve impact strength as taught by U.S. Patent 4,110,302; to polyesters to improve thermal stability as taught by U.S. Patent 3,975,329, to provide polyesters suitable for extrusion and blow molding as taught by Chem. Abs. 85, 178533u (1976), and to increase melt strength as taught by U.S. Patent 4,071,503; to copolyesters to improve hydrolytic stability as taught by Chem Abs. 78, 17364e (1973); and to polyphenylene ethers to functionalize them as taught by U.S. Patent 4.689,372.
  • Polycarbodiimides also have been blended with polyether-ester copolymer elastomers and ethylene/carboxylic acid copolymers to increase melt strength as taught by U.S. Patent 3,963,801 and with maleic anhydride and hydroxy compounds to produce high temperature-resistant compositions as taught by U.S. Patent 4,465,839.
  • Chem Abs. 104, 150170k a composition containing PBT, acrylate-butylene diacrylate-diallylmaleate-methacrylate copolymer rubber, glass fibers, Mark EP-17, and bis(diisopropylphenyl)carbodiimide has good impact and hydrolysis resistance.
  • PET compositions containing polycarbodiimides wherein improved toughness results.
  • European Patent Application 197789 teaches polyester compositions of PBT. butadiene-styrene-methyl methacrylate copolymer, and poly(4,4'-diphenylmethane carbodiimide); the PBT compositions have good impact resistance.
  • the reference teaches that a preferred polyester is PET, the reference does not contain Examples directed to PET compositions.
  • thermoplastic polyester/elastomer blend having better impact resistance, tensile elongation, and resistance to embrittlement upon annealing.
  • the present invention provides a polycarbodiimide functionalized elastomer or rubber.
  • rubber and “elastomer” are used interchangeably throughout this application.
  • This compos ition comprises the reaction product of (a) an elastomer having reactive groups thereon wherein the reactive groups are selected from the group consisting of carboxylic acids, acid anhydrides. acid amides, alcohols, amines, and the like; and (b) a polycarbodiimide.
  • This reaction product which is a polycarbodiimide functionalized elastomer, can be used alone as a molding composition or because the resulting reaction product is so reactive, the product is useful in the preparation of further products.
  • the present invention provides a composition of polycarbodiimide functionalized elastomer and thermoplastic polyester.
  • the composition has improved impact resistance, tensile elongation, and resistance to embrittlement upon annealing.
  • the present invention fulfills the need in the art for a thermoplastic polyester/elastomer blend having improved properties.
  • the present invention provides a melt-blended composition
  • a melt-blended composition comprising, based on the total composition: about 30 to 95 parts by weight PET; about 0.1 to 10 parts by weight polycarbodiimide; and about 1 to 70 parts by weight elastomer having reactive groups thereon wherein the reactive groups are selected from the group consisting of carboxylic acids, acid anhydrides, acid amides, alcohols, amines, and the like.
  • thermoplastic PET/modified elastomer composition having polycarbodiimide as a graft-linking agent has improved impact resistance, tensile elongation, and resistance to embrittlement upon annealing compared to a composition of PET, polycarbodiimide. and unmodified elastomer.
  • Such compositions are useful in any application where enhanced impact resistance and tensile elongation of PET are required. Typical applications include automotive exterior parts including bumpers, fascia, and grill panels, and a variety of tubing and jacketing applications.
  • the reaction product of the present invention has an elastomer.
  • the elastomer has a Mooney viscosity of about 10 to 70 ML 1+8@ 127°C units. More particularly, the elastomer has a Mooney viscosity of about 15 to 50 units, and preferably, about 25 to 50 units.
  • the elastomer is defined as having an ASTM D-638 tensile modulus of generally less than about 40,000, more particularly less than about 25,000, and preferably less than about 20,000. It can be a block or graft copolymer.
  • Useful elastomeric polymers can be made from reactive monomers which can be part of the polymer chains or branches, or grafted onto the polymer.
  • Useful elastomeric polymers may be produced by any well-known method including emulsion or solution polymerization.
  • Such elastomeric polymers include homopolymers, such as polybutadiene and polyisoprene, and random or block copolymers, such as butadiene/styrene copolymers, acrylonitrile/butadiene copolymers, isobutylene/butadiene copolymers, ethylene/propylene copolymers, ethylene/propylene/diene copolymers. and ethylene alkyl acrylate copolymers.
  • Useful elastomeric polymers can include aromatic vinyl monomers, olefins, and acrylic acid and methacrylic acid and their derivatives.
  • Some preferred elastomers are butadiene/acrylonitrile copolymers, ethylene/propylene copolymers. ethylene alkyl acrylate copolymers, and styrene/butadiene block copolymers and their hydrogenated derivatives.
  • the elastomer is modified by copolymerization or post-reaction with modifiers such as unsaturated carboxylic acids and derivatives thereof such as amides and anhydrides, and unsaturated alcohols, and unsaturated amines.
  • modifiers such as unsaturated carboxylic acids and derivatives thereof such as amides and anhydrides, and unsaturated alcohols, and unsaturated amines.
  • carboxylated polymers such as carboxylated nitrile rubbers and ethylene-ethyl acrylate-acrylic acid polymer may be employed.
  • the reactive groups may be randomly distributed along the length of the polymer chain or at the ends of the polymer chain.
  • the carboxyl or carboxylate functionality can be supplied by reacting the elastomer with a modifier taken from the class consisting of ⁇ , B-ethylenically unsaturated monocarboxylic acids such as acrylic and methacrylic acids as well as dicarboxylic acids having from 4 to 8 carbon atoms, or derivatives thereof.
  • a modifier taken from the class consisting of ⁇ , B-ethylenically unsaturated monocarboxylic acids such as acrylic and methacrylic acids as well as dicarboxylic acids having from 4 to 8 carbon atoms, or derivatives thereof.
  • Such derivatives include anhydrides of the dicarboxylic acids, or the metal salts of the acids.
  • maleic acid maleic anhydride, maleic acid amide, fumaric acid, fumaric acid amide, itaconic acid, itaconi ⁇ anhydride.
  • vinyl benzoic acid vinyl phthalic acid.
  • unsaturated alcohols include 2-propen-1-ol, 2-buten-1-ol, 3-buten-1-ol, 3-buten-2-ol.
  • Illustrative unsaturated amines include p-aminostyrene and 2-aminopropylacrylamide.
  • Preferred modifiers are acrylic acid, fumaric acid, and maleic anhydride.
  • the modifier can be grafted to the copolymer by any well-known grafting process.
  • the elastomer is modified to provide a greater improvement in composition properties when compared to an unfunctionalized elastomer.
  • the elastomer contains based on the weight of the elastomer, about 0.1 to 9 percent, preferably about 0.1 to 4 percent, and more preferably about 0.1 to 2.0 percent by weight of the modifier.
  • the modified elastomer has a number average molecular weight of from about 2,000 to 100,000; preferably about 2,000 to 65,000; more preferably about 5,000 to 35,000; and most preferably about 5,000 to 20,000.
  • a preferred elastomer is maleated ethylene propylene rubber which is 45% by weight ethylene and 54.6% by weight propylene.
  • the elastomer has a 25 Mooney viscosity and is modified with 0.4% maleic anhydride; the elastomer is available in commercial quantities.
  • Based on the total reaction product generally about 90 to 99.5 parts by weight modified elastomer are used. Preferably, about 95 to 99.5 parts, and more preferably, about 97 to 99 parts by weight modified elastomer are used.
  • the reaction product of the present invention has a polycarbodiimide.
  • useful polycarbodiimides have average molecular weights of about 1,000 to 15,000. If the polycarbodiimide is to be blended with a thermoplastic polyester, the polycarbodiimide should be dispersible with the molten thermoplastic polyester. Polycarbodiimides having molecular weights greater than about 15,000 may not be dispersible in the thermoplastic polyester.
  • Useful polycarbodiimides have the following repeating unit wherein
  • X represents a hydrocarbon radical which may be an aliphatic radical containing from 1 to 20 carbon atoms, a cycloaliphatic radical containing from 5 to 12 carbon atoms, an aromatic radical containing from 6 to 16 carbon atoms , or an aromatic or cycloaliphatic C 5 -C 12 radical containing one or more heteroatoms such as N, O, or S.
  • the polycarbodiimides may be formed in any manner known to those skilled in the art. for example, by heating diisocyanate compounds in the presence or absence of solvent. The formation of the polycarbodiimide is accompanied by the evolution of carbon dioxide gas. Although the polycarbodiimides useful in the present invention may be prepared without the use of a catalyst, much higher temperatures are needed in the absence of a catalyst. For certain polycarbodiimides, the use of such high temperatures may result in the formation of large quantities of side products and discolored products. Thus, the polycarbodiimides may be typically prepared by heating the isocyanates in the presence of a catalyst such as the phosphorus containing catalysts described in U.S. Patent 2,853,473 and Monagle, J.J., "Carbodiimides. III. Conversion of Isocyanates to Carbodiimides, Catalyst Studies.” J. Org. Chem. 27, 3851 (1962).
  • a catalyst such as the phosphorus containing catalysts described in U.S.
  • polycarbodiimides include poly (2,4,6-triisopropyl-1,3-phenylene carbodiimide); poly(tolyl carbodiimide); poly(4,4'-diphenylmethane carbodiimide); poly(3,3'-dimethyl-4,4'-biphenylene carbodiimide); poly(p-phenylene carbodiimide); poly(m-phenylene carbodiimide); poly
  • a preferred polycarbodiimide is poly(2,4,6-triisopropyl-1,3-phenylene carbodiimide) which is commercially available as Stabaxol P-100 from Rhein-Chemie.
  • the reaction product of modified elastomer and polycarbodiimide is made by melt blending the modified elastomer and polycarbodiimide above the melting temperature of the elastomer.
  • the reaction product is prepared by melt-blending the modified elastomer with polycarbodiimide using conditions which are severe enough for a satisfactory reaction to occur. Typical reaction temperatures range from about 240 to 300°C.
  • the reaction product does not have to be the complete reaction of the modified elastomer and polycarbodiimide; it is only necessary that a sufficient amount of reaction occur between the modified elastomer and polycarbodiimide so that the reactive groups of the polycarbodiimide can react with another component to form a graft-linked blend.
  • the polycarbodiimide functionalizes the elastomer by a bond through a double bond of the polycarbodiimide. This bond forms a graft to the modified elastomer.
  • reaction product itself is useful in that it can be used as a molding compound or independently kept for later blending with other materials.
  • thermoplastic polyester which is terminally-reactive is useful in the present invention.
  • Such terminal reactivity is provided by groups such as carboxyl, anhydride, hydroxyl, amino, epoxy, and the like.
  • thermoplastic polyesters may be prepared by known techniques such as by alcoholysis of esters of terephthalic acid with ethylene glycol or butanediol and subsequent polymerization or by heating the glycols with the free acids or with halide derivatives thereof.
  • the thermoplastic polyesters have an intrinsic viscosity of about 0.3 to 1.0, and preferably 0.5 to 0.9.
  • Intrinsic viscosity is obtained by extrapolation of viscosity values to zero concentration of solutions of poly(ethylene terephthalate) in 60 to 40 weight/weight ratio of phenol and tetrachloroethane. The measurements are normalized to 25°C.
  • thermoplastic polyesters examples include poly(ethylene terephthalate); poly(propylene terephthalate); poly(butylene terephthalate); poly(pentylene terephthalate); and poly(cyclohexene terephthalate).
  • Preferred thermoplastic polyesters are poly(ethylene terephthalate) and poly(butylene terephthalate).
  • the more preferred thermoplastic polyester is poly(ethylene terephthalate).
  • Scrap or recycled thermoplastic polyester resin may also be used.
  • the reaction product is preferably melt blended with the thermoplastic polyester.
  • Conventional melt-blending techniques can be used, and advantageously, a closed mixing device such as an extruder is used.
  • Typical extrusion temperatures are above the melting point of the thermoplastic polyester but below the degradation point of the components.
  • the melt temperature of the final composition should exceed about 245°C.
  • Typical reaction temperatures range from about 250 to 280°C.
  • the polycarbodiimide and modified elastomer can be fed together at the throat and the thermoplastic polyester fed into the system downstream.
  • the composition comprises generally about 5 to 70 parts by weight, preferably about 10 to 40 parts by weight, and more preferably about 10 to 30 parts by weight reaction product; and generally about 30 to 95 parts by weight, preferably about 60 to 90 parts by weight, and more preferably about 70 to 90 parts by weight thermoplastic polyester.
  • the reactive groups of the polycarbodiimide react with the terminal groups on the thermoplastic polyester.
  • the polycarbodiimide forms a linkage between the modified elastomer and thermoplastic polyester.
  • the composition has improved impact resistance, tensile elongation, and resistance to embrittlement upon annealing.
  • the PET, polycarbodiimide, and modified elastomer are melt blended together.
  • about 30 to 95 parts by weight thermoplastic polyester, about 0.1 to 10 parts by weight polycarbodiimide, and about 1 to 70 parts by weight modified elastomer are used.
  • about 60 to 90 parts by weight thermoplastic polyester, about 0.5 to 5 parts by weight polycarbodiimide, and about 10 to 40 parts by weight modified elastomer are used.
  • More preferably based on the total composition about 70 to 90 parts by weight thermoplastic polyester, about 1 to 3 parts by weight polycarbodiimide, and about 10 to 30 parts by weight modified elastomer are used.
  • the components may be fed into an extruder in a variety of ways. All components may be fed into the throat and extruded with a mixing screw.
  • the polycarbodiimide and the thermoplastic polyester may be fed in at the throat and the modified elastomer fed downstream.
  • the compositions may also include materials to insure uniform crystallinity after molding. These materials may include nucleating agents and plasticizers. Representative nucleating agents include ethylene based ionomers.
  • plasticizers include lactams such as caprolactam and lauryl lactam, sulfonai ⁇ ides such as o,p-toluenesulfonamide and N-ethyl, o,p-toluenesulfonamide and other plasticizers known in the art.
  • compositions of the present invention have improved toughness even after crystallization due to the nucleating agent and/or annealing, and are particularly useful in automotive applications where enhanced impact resistance and tensile elongation are advantageous.
  • Typical annealing conditions for compositions of the present invention include heating at 70 to 160°C for 1 to 24 hours.
  • Polymer blends were extruded on a Leistritz 1.1 inches (28 mm) co-rotating extruder using an intensive mixing screw and an L/D ratio of 40 using conditions in the Example. All test bars were injection molded on an Arburg All Rounder model number 221E/150 with a 35 ton clamp force. Flex bars for testing flexural properties were 0.1875 inches (0.476 cm) thick and tensile bars were 0.125 inch (0.3175 cm) thick. Izod testing was conducted on the flex bars. Typical molding conditions follow: Zone temperatures 250°C, 255°C, 260°C; mold temperature 95°C, with 600 psi (4.1 MPa) and 400 psi (2.8 MPa) pressures and cycle times of 9, 16, 3 seconds.
  • Carboxyl titrations were performed on the solution of thermoplastic polyester in o-cresol/chloroform (70:30 ratio) with dilute sodium hydroxide in benzyl alcohol.
  • Viscosities were performed on a 0.5% solution of the thermoplastic polyester in phenol/trichloroethane (60:40 ratio) at 25°C.
  • This example illustrates the preparation of a reaction product, and then the addition of PET to the reaction product.
  • This example demonstrates that a PET/polycarbodiimide functionalized rubber blend has improved impact resistance and elongation to break compared to a PET/non-polycarbodiimide functionalized rubber blend.
  • This example also illustrates the preparation of a reaction product, and then the addition of PET to the reaction product.
  • This example also illustrates that a PET/polycarbodiimide functionalized rubber blend has improved impact resistance and elongation to break compared to a PET/non-polycarbodiimide functionalized rubber blend.
  • This example illustrates one possible order for feeding the components into the extruder wherein all components together were fed into an extruder.
  • the conditions of the extrusion were as follows: Temperatures (Zones 1-6, die) 180°C, 200°C, 230°C, 240°C, 250°C; melt temperature 255°C, 15 amperes generated at 200 rpm with 750 psi (5 MPa) die pressure and 10 pounds/hour. After cooling, pelletizing. drying at 120°C for 12 hrs, and molding into standard test bars, the blend showed the following properties compared to a control (Comparative 3) run under the same conditions but without the polycarbodiimide:
  • PET/EPR weight ratio 3:1 3:1
  • This example illustrates another order for feeding the components into the extruder wherein PET and polycarbodiimide were fed in at the throat and the modified elastomer was fed into the system downstream.
  • polyester was fed with the carbodiimide down the throat and the elastomer was fed at Zone 5.
  • This example illustrates the effects of annealing a composition formed by feeding all components together into an extruder.
  • An intimate mixture of 80 parts PET, 20 parts Exxon's EX 1601 mEPR, 1.4 parts Rhein-Chemie's Stabaxol P-100 polycarbodiimide, and 0.1 part paraffin oil was fed together and extruded on a Leistritz co-rotating, twin screw extruder under the following conditions: Temperatures (Zone 1-9, die) 250°C across; melt temp 265°C at 150 rpm; 1120 psi (8 MPa) die pressure, 16 amps generated at 22 pounds per hour.
  • the blend, after making standard test bars. showed the following physical properties before and after annealing 15 hours at 150°C.
  • a control (Comparative 5) without the Stabaxol P-100 was run.
  • This example uses a commercially available ethylene-butyl acrylate-maleic anhydride terpolymer (Lotador AX 8040) as a reactive impact modifier for the PET.
  • PET master batch pellets containing 4% AClyn ionomer (of the type used in Example 6) as nucleator were mixed with 20.5 parts of Lotador AX 8040. 2 parts of a sulfonamide plasticizer, and 1.5 parts of Rhein Chemie's Stabaxol P-100 polycarbodiimide. The mixture was then extruded on a 1.1 inches (28 mm) co-rotating, twin-screw extruder at 250°C and 28 Ibs/hr throughput rate. The extrudate was cooled, pel-letized. and dried. The pellets were then injection molded at 250°C into standard ASTM test specimens using a mold temperature of 80°C.
  • This example illustrates the use of the impact modified PET composition of this invention in tubing applications.
  • the blend composition from Example 7 was extruded into 0.25 "(0.635 cm) tubing of several different width thicknesses ranging from 20 mil to 40 mil.
  • the extruder was a 1 1/2" (3.81 cm) NRM machine with 24/1 (L/D) screw with 3:1 compression ratio.
  • the barrel and die temperatures were maintained at 260°C.
  • the tubing was extruded at approximately 19 ft/min (5.8 m/min) with draw ratios ranging from 3:1 to 5:1.
  • the tubing was heated at 180°C for 3 hours to see if any embrittlement which normally occurs with PET due to crystallization (with or without nucleator) occurred.
  • the tubing made from the material of the current invention retained its flexibility even after the heat treatment.
  • Tubings of impact modified PET can be potentially used in a variety of applications such as fuel lines, optical fiber, encasement, etc.
  • a PBT/polycarbodiimide functionalized rubber blend is prepared by following Example 1.
  • This example illustrates the effect of a multiphase, acrylic impact modifier as in U.S. Pat. 4.096,202 for PET.
  • the properties, particularly notched lzod and elongation, are inferior to those obtained with the PET/polycarbodiimide/rubber compositions of the present invention.
  • thermoplastic polyurethane elastomer As impact modifier for PET.
  • This example illustrates the effect of blending a commercial, unmodified EP rubber with PET.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un produit de réaction de (a) un élastomère ayant des groupes réactifs et (b) un polycarbodiimide. Le produit de réaction peut être utilisé seul ou avec un polyester thermoplastique pour former des compositions ayant des caractéristiques améliorées de résistance aux impacts et d'allongement à la traction.
PCT/US1989/002060 1988-05-26 1989-05-12 Melange greffe d'un elastomere et d'un polyester thermoplastique WO1989011507A1 (fr)

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Application Number Priority Date Filing Date Title
KR1019900700097A KR900701930A (ko) 1988-05-26 1989-05-12 열가소성 폴리에스테르/탄성체 조성물

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US19890788A 1988-05-26 1988-05-26
US198,907 1988-05-26

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994022956A1 (fr) * 1993-04-05 1994-10-13 Alliedsignal Inc. Compositions a base de polyester a haute resistance a l'impact
WO1994022955A1 (fr) * 1993-04-05 1994-10-13 Alliedsignal Inc. Melange de polyesters et de polycarbonates a haute resistance a l'impact
WO1999010442A1 (fr) * 1997-08-27 1999-03-04 Reichhold, Inc. Resines servant a effectuer la doublure de surfaces
US6692802B1 (en) 1997-08-27 2004-02-17 Reichhold, Inc. Resins for lining surfaces
DE102007056631A1 (de) * 2007-11-24 2009-05-28 Teijin Monofilament Germany Gmbh Hydrolysebeständig ausgerüstete Fäden, Verfahren zu deren Herstellung und deren Verwendung
EP2484725A1 (fr) * 2009-09-30 2012-08-08 Adeka Corporation Composition de résine polyester, fibre de polyester, article moulé de résine polyester et procédé de production d'agent de nucléation pour une résine polyester
WO2013028695A3 (fr) * 2011-08-22 2013-04-25 E. I. Du Pont De Nemours And Company Thermoplastique recyclé comprenant un élastomère fonctionnalisé
WO2013028707A3 (fr) * 2011-08-22 2013-06-27 E. I. Du Pont De Nemours And Company Thermoplastique recyclé comprenant un durcisseur
WO2023229131A1 (fr) * 2022-05-23 2023-11-30 (주) 엘지화학 Composition d'élastomère de polyester thermoplastique, procédé de préparation associé et article moulé la comprenant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963801A (en) * 1975-05-23 1976-06-15 E. I. Du Pont De Nemours And Company Blends of copolyesters, ethylene/carboxylic acid copolymers and a polycarbodiimide
FR2311808A1 (fr) * 1975-05-23 1976-12-17 Du Pont Compositions de polyesters thermoplastiques tenaces et leur preparation
DE3525253A1 (de) * 1984-07-16 1986-01-16 Mitsubishi Chemical Industries Ltd., Tokio/Tokyo Polyesterharzmasse
EP0197789A2 (fr) * 1985-04-10 1986-10-15 Polyplastics Co. Ltd. Composition de polyester

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963801A (en) * 1975-05-23 1976-06-15 E. I. Du Pont De Nemours And Company Blends of copolyesters, ethylene/carboxylic acid copolymers and a polycarbodiimide
FR2311808A1 (fr) * 1975-05-23 1976-12-17 Du Pont Compositions de polyesters thermoplastiques tenaces et leur preparation
DE3525253A1 (de) * 1984-07-16 1986-01-16 Mitsubishi Chemical Industries Ltd., Tokio/Tokyo Polyesterharzmasse
EP0197789A2 (fr) * 1985-04-10 1986-10-15 Polyplastics Co. Ltd. Composition de polyester

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994022956A1 (fr) * 1993-04-05 1994-10-13 Alliedsignal Inc. Compositions a base de polyester a haute resistance a l'impact
WO1994022955A1 (fr) * 1993-04-05 1994-10-13 Alliedsignal Inc. Melange de polyesters et de polycarbonates a haute resistance a l'impact
US5621040A (en) * 1993-04-05 1997-04-15 Alliedsignal Inc. High impact polyester compositions
WO1999010442A1 (fr) * 1997-08-27 1999-03-04 Reichhold, Inc. Resines servant a effectuer la doublure de surfaces
US5925409A (en) * 1997-08-27 1999-07-20 Reichhold, Inc. Resins for lining surfaces
US6692802B1 (en) 1997-08-27 2004-02-17 Reichhold, Inc. Resins for lining surfaces
DE102007056631A1 (de) * 2007-11-24 2009-05-28 Teijin Monofilament Germany Gmbh Hydrolysebeständig ausgerüstete Fäden, Verfahren zu deren Herstellung und deren Verwendung
EP2484725A1 (fr) * 2009-09-30 2012-08-08 Adeka Corporation Composition de résine polyester, fibre de polyester, article moulé de résine polyester et procédé de production d'agent de nucléation pour une résine polyester
EP2484725A4 (fr) * 2009-09-30 2013-03-13 Adeka Corp Composition de résine polyester, fibre de polyester, article moulé de résine polyester et procédé de production d'agent de nucléation pour une résine polyester
WO2013028695A3 (fr) * 2011-08-22 2013-04-25 E. I. Du Pont De Nemours And Company Thermoplastique recyclé comprenant un élastomère fonctionnalisé
WO2013028707A3 (fr) * 2011-08-22 2013-06-27 E. I. Du Pont De Nemours And Company Thermoplastique recyclé comprenant un durcisseur
US8889781B2 (en) 2011-08-22 2014-11-18 E I Du Pont De Nemours And Company Recycled thermoplastic with toughener
WO2023229131A1 (fr) * 2022-05-23 2023-11-30 (주) 엘지화학 Composition d'élastomère de polyester thermoplastique, procédé de préparation associé et article moulé la comprenant

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