WO2000015716A2 - Melanges a base de polyester a resistance elevee aux chocs - Google Patents

Melanges a base de polyester a resistance elevee aux chocs Download PDF

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Publication number
WO2000015716A2
WO2000015716A2 PCT/US1999/021068 US9921068W WO0015716A2 WO 2000015716 A2 WO2000015716 A2 WO 2000015716A2 US 9921068 W US9921068 W US 9921068W WO 0015716 A2 WO0015716 A2 WO 0015716A2
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WO
WIPO (PCT)
Prior art keywords
residues
weight percent
polyester
terpolymer
ethylene
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Application number
PCT/US1999/021068
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English (en)
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WO2000015716A3 (fr
Inventor
Thomas Joseph Pecorini
Bruce Connard Bell
Alan Joseph Oshinski
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Eastman Chemical Company
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Publication of WO2000015716A2 publication Critical patent/WO2000015716A2/fr
Publication of WO2000015716A3 publication Critical patent/WO2000015716A3/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
    • 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

  • This invention pertains to certain, novel polyester compositions which exhibit improved toughness. More specifically, this invention pertains to novel polyester compositions comprising (i) at least one polyester containing diol residues comprising ethylene glycol residues, diacid residues comprising terephthalic acid residues, 2,6-naphthalenedicarboxylic acid resides or a mixture thereof, and titanium and/or germanium residues but essentially no antimony residues and (ii) certain epoxy-containing impact modifiers.
  • Polyesters such as poly(ethylene terephthalate) (PET) are engineering thermoplastics used in a wide variety of end use applications such as fibers, films, automotive parts, food and beverage containers and the like. They can be processed by a variety of techniques including injection molding, compression molding, extrusion, thermoforming, blow molding, and combinations thereof. Sometimes, it is desirable to add impact modifiers to improve the toughness of polyesters used in the manufacture of molded parts such as those used in automotive, appliance, cookware or food storage applications.
  • PTT poly(ethylene terephthalate)
  • Patent 4,172,859 discloses that polymeric materials that serve well as impact modifiers should (i) possess a modulus 1/10 that of the polyester matrix material, (ii) be well dispersed within the matrix material in discrete phases of 0.01 micron to 3.0 micron in size, and (iii) be well bonded to the matrix.
  • Low modulus polymers commonly used as impact modifiers fall into several general classes.
  • the first class comprises rubbers based on butadiene or isoprene, e.g., polybutadiene, polyisoprene, natural rubber, styrene-butadiene (SBR), acrylonytrile-butadiene (ABN or nitrile rubber), styrene-butatene-styrene (SBS) or hydrogenated SBS (styrene-ethylene- butene-styrene) block copolymers (SEBS), or acrylonytrile-butadiene- styrene (ABS) polymers containing high levels of butadiene.
  • SBR styrene-butadiene
  • ABS acrylonytrile-butadiene
  • SEBS acrylonytrile-butadiene- styrene
  • Butadiene- based rubbers generally have lower glass transition temperatures (Tg's) which help to improve low temperature toughness, but they may not be stable under the high temperatures at which polyesters are processed.
  • the second major class of impact modifiers comprise elastomers based on polyethylene, e.g., ethylene-propylene rubbers (EPR) or EPRs with a small amount of side chain diene moiety (EPDM), ethylene-acrylate copolymers such as ethylene/methyl acrylate, ethylene/ethyl acrylate, ethylene/butyl acrylate and ethylene/methylacrylate/glycidyl methacrylate, or ethylene- vinyl acetate copolymers (EVA).
  • EPR ethylene-propylene rubbers
  • EPDM side chain diene moiety
  • EVA ethylene-acrylate copolymers
  • a third group of impact modifiers consists of core-shell impact modifiers such as those that contain a poly(methyl methacrylate) (PMMA) hard shell with either a butadiene methacrylate- butadiene-styrene (MBS) or butyl acrylate (acrylic) core, e.g., PARALOID manufactured by Rohm & Haas Company.
  • Core-shell impact modifiers based on acrylonitrile-butadiene-styrene) (ABS) also are commercially available, e.g., BLENDEX manufactured by GE Specialty Chemicals).
  • Other elastomers that may serve as impact modifiers include polyesters, e.g., HYTREL manufactured by E.I. duPont de Nemours Company and
  • ECDEL manufactured by Eastman Chemical Company
  • polyurethanes e.g., PELLETHANE manufactured by Dow Chemical Company
  • silicone rubbers e.g., silicone rubber
  • a fine discrete impact modifier phase can be created by the shearing forces obtained during melt processing.
  • a mixing screw must be designed properly to create the appropriate shear fields during a compounding/extrusion process.
  • impact modifiers dispersed by purely mechanical action may re- coalesce during a later stage of processing where shear may be reduced.
  • impact modifiers can be manufactured to an inherently small size using latex or other polymerization processes. Impact modifiers manufactured in this way often contain a stiff shell of harder polymer and are, therefore, often referred to as core-shell impact modifiers.
  • impact modifiers can be made in 0.2 - 0.5 micron sizes ideally suited for impact modification of nylons, polycarbonates and polyesters. Nonetheless, these core-shell impact modifiers also must be dispersed by shearing action during melt processing, and are prone to re-coalesce during later stages of molding or compounding.
  • One way to enhance dispersion and prevent coalescence is to introduce functional groups into the impact modifier that either are highly soluble in the matrix polymer or will react with the matrix polymer. Interaction between these functional groups and the matrix during compounding creates a thin interlayer of material that make the impact modifier and matrix more energetically compatible. Compatibility related to these functional groups leads to good mixing and good dispersion of the impact modifier.
  • Impact modifiers can be functionalized with a variety of reactive or non- reactive monomers. These functional monomers can be incorporated into the impact modifier directly during preparation of the impact modifier or subsequently by means of a grafting polymerization step.
  • Non-reactive impact modifiers for example an EPDM-grafted-SAN
  • the reactive groups of reactive impact modifiers chemically bond to the matrix polymer but, to be effective, they must do so in the limited time available in the extruder during compounding.
  • U.S. Patent 4,172,859 lists a variety of functional groups which can be grafted or copolymerized onto ethylene-based elastomers for use with polyesters and nylons.
  • maleic anhydride (MAH) functionalized impact modifiers work well for nylons, and there are many commercial products available, e.g., EPR-MAH, EVA-MAH, and SEBS-MAH.
  • EPR-MAH EVA-MAH
  • SEBS-MAH SEBS-MAH
  • a functional group that reacts particularly well with polyesters is the monosubstituted oxirane, or epoxy, group such as is present in glycidyl methacrylate (GMA), glycidyl acrylate, allyl glycidyl ether, and 3,4-epoxy-1- butene (EpB).
  • polyester compositions which contain epoxy-containing, ethylene-based polymeric materials.
  • U.S. Patent 4,172,859 describes thermoplastic compositions comprising blends of polyesters and epoxy-functionalized, random ethylene copolymers. This patent makes no reference to catalyst residues present in the polyesters.
  • U.S. Patent 4,284,540 describes the use of ethylene/GMA copolymers as a toughening agent for polyesters when combined with 0.1 to 5 weight percent of an added barium catalyst. This patent also notes that ethylene/GMA copolymers increases the crystallization rate of PET and that PET containing antimony catalyst residues are preferable for promoting a reaction with epoxy-containing olefinic materials. The patent does not, however, provide any data that show any toughness enhancement due to these catalyst residues.
  • U.S. Patent 4,753,980 discloses that polyester compositions containing 3-40 weight percent of either ethylene/ethyl acrylate/GMA terpolymer or ethylene/butyl acrylate/GMA terpolymer possess superior low temperature toughness when compared to analogous polyester compositions which contain an ethylene/methyl acrylate/GMA terpolymer. There is no reference to catalyst residues in this patent.
  • Patents 5,098,953, 5,086,119, 5,086,118, 5,086,116, and 5,068,283 disclose that the toughness of polyester compositions containing ethylene/GMA copolymers or ethylene/alkyl acrylate/GMA terpolymers can be improved by adding a functional crosslinking agent to the compositions.
  • the functional crosslinking agent contains, in one molecule, at least two functional groups having reactivity with epoxy group, carboxyl group or hydroxyl group.
  • U.S. Patent 5,206,291 describes compositions comprising a polyester containing 1 ,4-cyclohexanedimethanol residues and an ethylene/GMA copolymer.
  • U.S. Patents 5,483,001 , 5,407,999, and 5,208,292 and Die Angewandte Makromolekulare Chemie, p. 89 disclose polyester compositions having improved toughness which contain an ethylene/alkyl acrylate/GMA terpolymer, an ethylene/alkyl acrylate/maleic anhydride terpolymer, and a catalyst such as dimethylstearylamine which accelerates the reaction between the functional groups of the two terpolymers.
  • U.S. Patent 5,652,306 and European Patent Publication EP 737,715 A2 disclose polyester compositions containing MBS or acrylic-type core-shell impact modifiers combined with small amounts of an ethylene/alkyl acrylate/GMA terpolymer.
  • torque rheometry provides a simple and straightforward method for monitoring the viscosity of polymer blends as a function of blending time.
  • the rheometer continuously measures the torque required to turn the rotor blades that shear and mix the sample within the mixing bowl. For a given material and set of processing conditions, the torque measured is approximately a linear function of the viscosity of the sample.
  • any change in viscosity with time is in turn related to such effects as changes in molecular weight of the sample (for example, an increase due to a reaction or a decrease due to degradation) or the formation of grafts, branches or crosslinks in the sample.
  • the work by Stewart et al. shows that mixtures of E/GMA with PET containing antimony catalyst residues gives rise to significant increases in torque with mixing time. This led to the conclusion that PET containing antimony catalyst residues accelerated the reaction between the PET and the E/GMA. PET containing residual antimony catalyst was found to produce a more rapid increase in torque than PET containing other residual catalysts.
  • compositions comprising certain polyesters and certain epoxy- containing impact modifiers exhibit improved toughness when the polyester utilized contains no, or essentially no, antimony residues but rather contains titanium and/or germanium metal residues, e.g., residues resulting from the use of a titanium catalyst in the manufacture of the polyester.
  • polyesters containing titanium and/or germanium residues are preferred to those containing antimony residues.
  • the polyester compositions provided by the present invention comprise: I. about 75 to 98 weight percent of a thermoplastic polyester comprised of:
  • (A) diacid residues comprising at least 85 mole percent terephthalic acid residues, 2,6-naphthalenedicarboxylic acid residues or a mixture of terephthalic acid and 2,6-naphthalenedicarboxylic acid residues;
  • polyester compositions comprising 50/50 blends of (i) PET containing titanium residues and (ii) an ethylene/glycidyl methacrylate copolymer. These compositions of Stewart et al. actually contain more E/GMA than PET on a volume basis whereby they are very low modulus materials, suitable for torque rheometry studies but unsuitable for the types of applications prepared for by the manufacture of molded articles or extruded sheet or film material.
  • polyester component of our novel compositions are commercially available and/or may be prepared by batch or continuous processes using conventional melt phase or solid state condensation procedures well known in the art. Also, the polyester component may be obtained from post consumer waste, e.g., recycled polyester.
  • Polyesters useful in the present invention are comprised of diacid residues comprising at least 85 mole percent terephthalic acid residues, 2,6-naphthalenedicar- boxylic acid residues or a mixture of terephthalic acid and 2,6-naphthalene- dicarboxylic acid residues; (B) diol residues comprising at least 85 mole percent ethylene glycol residues; and (C) at least 25 ppmw Ti, Ge or a mixture thereof; wherein the polyester is made up of 100 mole percent diacid residues and 100 mole percent diol residues.
  • Up to 15 mole percent of the diacid component of the polyesters may be derived from diacids other than terephthalic and 2,6-naphthalenedicarboxylic acid residues.
  • diacid residues may be residues derived from dicarboxylic acids containing about 4 to about 40 carbon atoms such as succinic, glutaric, adipic, pimelic, suberic, azaieic, sebacic, terephthalic, isophthalic, sulfodibenzoic, sulphoisophthalic, maleic, fumaric, 1 ,4-cyclohexanedicarboxylic (cis-, trans-, or cis/trans mixtures), and the like.
  • dicarboxylic acids containing about 4 to about 40 carbon atoms such as succinic, glutaric, adipic, pimelic, suberic, azaieic, sebacic, terephthalic, isophthalic, sul
  • the diacid residues may be derived from the dicarboxylic acids, esters and acid chlorides thereof, and, in some cases, anhydrides thereof. Similarly, up to 15 mole percent of the diol residues may be derived from diols other than ethylene glycol.
  • propylene glycol 1 ,3- propanediol, 1 ,4-butanediol, 1,6-hexanediol, 1 ,8-octanediol, neopentyl glycol, 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, diethylene
  • a branching agent such as trimellitic anhydride, pyromellitic dianhydride, glycerol, pentaerythritol, polyvinyl alcohol, styrene-maleic anhydride (SMA) and the like may be included in the polyester if desired.
  • a branching agent such as trimellitic anhydride, pyromellitic dianhydride, glycerol, pentaerythritol, polyvinyl alcohol, styrene-maleic anhydride (SMA) and the like may be included in the polyester if desired.
  • the polyester component of the compositions of the present invention should have an inherent viscosity (IV) in the range of about 0.4 to about 1.4 dL/g, preferably about 0.55 to 0.95 dL/g, measured at 25°C using 0.50 g of polyester per 100 mL of a solvent consisting of 60 weight percent phenol and 40 weight percent tetrachloroethane.
  • the polyester component preferably is unmodified PET having an IV of about 0.55 to 0.95 dL/g.
  • the polyester component of our novel compositions contains at least 25 ppmw of a metal selected from Ti, Ge or a mixture thereof, typically about 25 to 200 ppmw and preferably about 50 to 100 ppmw Ti, Ge or a mixture thereof.
  • the metal preferably is titanium.
  • the titanium and germanium may be introduced to the polyester by using a titanium and/or germanium compound as a catalyst in the preparation of the polyester. It is also possible to introduce the titanium and/or germanium into the polyester subsequent to the preparation of the polyester.
  • the polyester compositions of the present invention are substantially and essentially free of antimony, e.g., the polyester compositions contain less than 20 ppmw antimony, preferably no detectable antimony.
  • the second component of the compositions of the present invention is an impact modifying polymer comprised of about 0.5 to 15 weight percent of epoxy-containing residues derived from monomers selected from glycidyl methacrylate, glycidyl acrylate, allyl gycidyl ether, 3,4-epoxy-1-butene, or a mixture of any two or more of such monomers.
  • epoxy-containing monomers may be introduced into the impact modifier during polymerization, or they may be subsequently grafted onto the impact modifier.
  • Such epoxy-containing, impact modifier polymers are well known in the art and are available from a plurality of manufactures.
  • Impact modifiers that may be modified with a functional epoxy group include, but are not restricted to, polyethylene; polypropylene; po ybutene; ethylene based copolymers and terpolymers containing vinyl acetate, alkyl acrylate, alkyl methacrylate where the alkyl group could be methyl, ethyl, butyl or ethylhexyl; ethylene-propylene copolymers (EPR); ethylene- propylene-diene (EPDM); natural rubber; polybutadiene; polyisoprene; acrylonitrile-butadiene (nitrile rubber); styrene-butadiene (SBR); styrene- butadiene-styrene (SBS); styrene-ethylene-butene-styrene (SEBS); acrylonitrile-butadiene-styrene (ABS); methyl methacrylate-butyl acrylate (acryl
  • X represents residues derived from
  • R 1 is alkyl of up to about 8 carbon atoms, preferably alkyl of
  • R 2 is hydrogen, methyl or ethyl, preferably hydrogen or methyl
  • X constitutes about 10 to 40 weight percent, preferably 15 to 35 weight percent, and most preferably 20 to 35 weight percent, of terpolymer E/X/Y;
  • Y represents residues derived from glycidyl methacrylate, glycidyl acrylate, aliyl glycidyl ether or 3,4-epoxy-1-butene which constitute about 0.5 to 20 weight percent, preferably about 2 to 10 weight percent, of copolymer E/Y or terpolymer E/X/Y; and E represents ethylene residues that constitute the remainder of the copolymer or terpolymer composition.
  • copolymers based on ethylene-GMA containing about 2 to 10 weight percent GMA residues
  • terpolymers based on ethylene-methyl acrylate-GMA, ethylene-ethyl acrylate-GMA and ethylene-butyl acrylate-GMA containing about 20 to 35 weight percent alkyl acrylate residues and about 2 to 10 weight percent GMA residues are particularly preferred.
  • the concentration of the epoxy- containing impact modifiers in the compositions of the present invention preferably is about 10 to 25 weight percent, based on the total weight of components I and II, for injection molding uses and about 2 to 15 weight percent, based on the total weight of components I and II, for compositions intended for extrusion into sheet or film or for use in thermoforming applications.
  • the impact modifier -and polyester may be pellet blended before extrusion or they may be fed from separate streams. These reactive impact modifiers also may be combined with non-reactive impact modifiers of similar composition.
  • the polyester compositions of this invention can be readily prepared by conventional compounding technology, such as the use of single or twin screw extruders. The resultant blends are readily extruded into film or sheeting and injection molded, compression molded or thermoformed into desired shapes or objects.
  • polyesters such as stabilizers, antioxidants, pigments, colorants, plasticizers, flame retardants, mold release agents, slip agents and the like may be used as desired.
  • Glass fibers or other inorganic fillers can also be included.
  • nucleating agents such as polyethylene, polypropylene, talc and the like may be used.
  • a particularly preferred embodiment of the invention consists of a polyester composition
  • a polyester composition comprising: I. about 75 to 98 weight percent of a thermoplastic polyester comprising poly(ethylene terephthalate) having an inherent viscosity of about 0.55 to 0.95 dL/g, measured at 25°C using 0.50 g of polyester per 100 mL of a solvent consisting of 60 weight percent phenol and 40 weight percent tetrachloroethane, containing about 50 to 100 ppmw Ti; and II.
  • an impact modifying polymer selected from ethylene/methyl acrylate/glycidyl methacrylate copolymers containing about 20 to 35 weight percent methyl acrylate residues and about 2 to 10 weight percent glycidyl methacrylate residues.
  • an impact modifying polymer selected from ethylene/methyl acrylate/glycidyl methacrylate copolymers containing about 20 to 35 weight percent methyl acrylate residues and about 2 to 10 weight percent glycidyl methacrylate residues.
  • up to 50% of the amount of component II may consist of an ethylene/methyl acrylate copolymer containing about 20 to 35 weight percent methyl acrylate residues.
  • novel polyester compositions provided by the present invention are further illustrated by the following examples wherein all percentages given are by weight unless otherwise specified.
  • Polyester A Poly(ethylene terephthalate) having an IV of 0.70 prepared from ethylene glycol and terephthalic acid using 100 ppmw titanium catalyst provided as titanium tetraisopropoxide.
  • Polyester B Poly(ethylene terephthalate) having an IV of 0.72 prepared from ethylene glycol and terephthalic acid using 200 ppmw antimony catalyst provided as antimony triacetate.
  • Impact Modified 1 An ethylene/methyl acrylate/glycidyl methacrylate terpolymer containing 24% methyl acrylate residues and 8% glycidyl methacrylate residues, available from Elf Atochem under the name "Lotader AX8900" and having a melt flow of 6.5 g/10 minutes measured by ASTM D1238 at 190°C using a 2.16 kg weight.
  • Impact Modifier 2 An ethylene/glycidyl methacrylate copolymer containing 8% glycidyl methacrylate residues, available from Elf Atochem under the name "Lotader AX8840" and having a melt flow of 5 g/10 minutes measured by ASTM D1238 at 190°C using a 2.16 kg weight.
  • the polyester compositions of the examples were prepared by feeding the polyester and impact modifier through separate feeders into the main hopper of a 30 mm twin-screw, compounding extruder.
  • the extruder barrel temperatures was set at 290°C (554°F), screw speed was 300 revolutions per minute and the throughput rate was 11.4 kg (25 pounds) per hour.
  • Test bars 3.2 mm thick by 12.8 mm wide by 125 mm long were molded on a ToyoA molding machine using a chilled -4°C (25°F) mold.
  • the test bars thus prepared contained essentially amorphous polyester.
  • the test bars then were crystallized in an air oven at 120°C for 3 hours. Test bars were machined into notched Izod test coupons and tested in accordance with ASTM D256.
  • Morphology was examined using either TEM (transmission electron microscopy) or SEM (scanning electron microscopy). Specimens for TEM examination were cut using a cryomicrotome. Specimens for SEM examination were freeze fractured in liquid nitrogen. The particle sizes listed represent the diameters of the most common large particles of the impact modifier phases present in the SEM or TEM photo.
  • the polyester composition of Example 1 consisted of 80% Polyester A containing about 100 ppmw titanium and 20% Impact Modifier 1. This composition has a 23°C (72°F) Notched Izod value of 616 Joules per meter (11.52 foot-pounds per inch). The TEM particle size of the impact modifier was 0.2 microns.
  • the polyester composition of Example 2 consisted of 80% Polyester A containing about 100 ppmw titanium and 20% Impact Modifier 2. This composition has a 23°C (72°F) Notched Izod value of "No Break”. A "No Break” result indicates that the material did not completely fracture under the indicated conditions with an Izod value of greater than 1000 Joules per meter (53.5 foot-pounds per inch). The TEM particle size of the impact modifier was 0.2 microns.

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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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne de nouvelles compositions à base de polyester qui comprennent (i) des résidus de diol avec au moins un polyester qui contiennent des résidus d'éthylèneglycol, et des résidus de diacide comprenant des résidus d'acide téréphtalique, des résidus d'acide 2,6-naphthalène-dicarboxylique ou leur mélange; (ii) quelques modificateurs de la résistance aux chocs contenant certains époxydes et (iii); des résidus de titane et/ou de germanium. Les compositions à base de polyester manifestent une plus grande dureté et peuvent servir à la fabrication d'articles façonnés obtenus au moyen du moulage par injection ainsi qu'à l'extrusion de matières en film ou en feuille.
PCT/US1999/021068 1998-09-14 1999-09-13 Melanges a base de polyester a resistance elevee aux chocs WO2000015716A2 (fr)

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US15266198A 1998-09-14 1998-09-14
US152,661 1998-09-14

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WO2000015716A2 true WO2000015716A2 (fr) 2000-03-23
WO2000015716A3 WO2000015716A3 (fr) 2000-07-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8058360B2 (en) 2007-06-01 2011-11-15 Grupo Petrotemex, S.A. De C.V. Polyester blends exhibiting low temperature toughness

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4284540A (en) * 1979-04-17 1981-08-18 Toray Industries, Inc. Polyethylene terephthalate molding compositions
EP0838501A2 (fr) * 1996-10-23 1998-04-29 Hoechst Celanese Corporation Procédé et compositions pour modifier la tenacité de résines de polyester

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0670171B2 (ja) * 1985-12-23 1994-09-07 東レ株式会社 成形用ポリエチレンテレフタレ−ト系樹脂組成物
JPS62146949A (ja) * 1985-12-23 1987-06-30 Toray Ind Inc 成形用ポリエチレンテレフタレ−ト系組成物
JPH10158490A (ja) * 1996-12-03 1998-06-16 Kanegafuchi Chem Ind Co Ltd ポリエチレンテレフタレート系樹脂組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4284540A (en) * 1979-04-17 1981-08-18 Toray Industries, Inc. Polyethylene terephthalate molding compositions
EP0838501A2 (fr) * 1996-10-23 1998-04-29 Hoechst Celanese Corporation Procédé et compositions pour modifier la tenacité de résines de polyester

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 379 (C-463), 10 December 1987 (1987-12-10) & JP 62 146948 A (TORAY IND INC), 30 June 1987 (1987-06-30) & DATABASE WPI Derwent Publications Ltd., London, GB; AN 1987-237564 [34] *
PATENT ABSTRACTS OF JAPAN vol. 011, no. 379 (C-463), 10 December 1987 (1987-12-10) & JP 62 146949 A (TORAY IND INC), 30 June 1987 (1987-06-30) & DATABASE WPI Derwent Publications Ltd., London, GB; AN 1987-237565 [34] *
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 11, 30 September 1998 (1998-09-30) & JP 10 158490 A (KANEGAFUCHI CHEM IND CO LTD), 16 June 1998 (1998-06-16) & DATABASE WPI Derwent Publications Ltd., London, GB; AN 1998-393634 *
STEWART ET AL.: "Effect of catalyst on the reactive processing of polyesters with epoxy-functional polymers" POLYMER ENGINEERING AND SCIENCE, vol. 33, no. 11, June 1993 (1993-06), pages 675-685, XP002127429 cited in the application *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8058360B2 (en) 2007-06-01 2011-11-15 Grupo Petrotemex, S.A. De C.V. Polyester blends exhibiting low temperature toughness
US8859681B2 (en) 2007-06-01 2014-10-14 Grupo Petrotemex, S.A. De C.V. Polyester blends exhibiting low temperature toughness
US9062200B2 (en) 2007-06-01 2015-06-23 Grupo Petrotemex, S.A. De C.V. Polyester blends exhibiting low temperature toughness

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