WO1991015545A1 - Compositions de melanges de polyethylene terephthalate-polycarbonate a haute resistance a l'impact - Google Patents

Compositions de melanges de polyethylene terephthalate-polycarbonate a haute resistance a l'impact Download PDF

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Publication number
WO1991015545A1
WO1991015545A1 PCT/US1991/001347 US9101347W WO9115545A1 WO 1991015545 A1 WO1991015545 A1 WO 1991015545A1 US 9101347 W US9101347 W US 9101347W WO 9115545 A1 WO9115545 A1 WO 9115545A1
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WIPO (PCT)
Prior art keywords
polycarbonate
terpolymer
formula
poly
polyester
Prior art date
Application number
PCT/US1991/001347
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English (en)
Inventor
Murali Krishna Akkapeddi
Charles Driscoll Mason
Original Assignee
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 BR919106113A priority Critical patent/BR9106113A/pt
Publication of WO1991015545A1 publication Critical patent/WO1991015545A1/fr

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Classifications

    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08L69/005—Polyester-carbonates

Definitions

  • the present invention relates to particular polyester molding compositions which are characterized by exceptional toughness subsequent to annealing. More particularly, the present invention is directed towards a composition which comprises a polyester and
  • polycarbonate or a polyarylate which further includes a reactive impact modifier is provided.
  • the materials typically comprise one or more polymeric materials which exhibit specific properties, i.e., toughness, rigidity,
  • blended polymeric materials are rarely attained which offer the desirable characteristics of the constituents, without simultaneously suffering fro m some detrimental quality.
  • aromatic polycarbonate plastics may be easily -molded, have a high tensile and impact strength, and exhibit an excellent degree of dimensional stability in most articles formed
  • aromatic polycarbonates are unsuitable as they are also known to exhibit severe environmental stress crazing and cracking, i.e., a type of failure which is enhanced by the presence of organic solvents such as basic solvents such as many hydrocarbons, alcohols, ketones, etc which are the constituents of may common automobile fluids, gasoline, paints, and the like.
  • organic solvents such as basic solvents such as many hydrocarbons, alcohols, ketones, etc which are the constituents of may common automobile fluids, gasoline, paints, and the like.
  • polycarbonates have been devised which increase the resistance of polycarbonates to environmental stress cracking including the addition of a minor amount of a polyalkylene terephthalate such as poly(ethylene terephthalate) and ⁇ oly(butylene terephthalate).
  • poly(ethylene terephthalate), also known to the art by its acronym “PET”, and ⁇ oly(butylene terephthalate), similarly referred to as “PBT” are aromatic polyesters which enjoy frequent use either as the sole materials or as constituents in plastic products where rigidity, impact resistance, and abrasion resistance, are
  • polyalkylene terephthalates exhibit subsequent to cooling fromthe melt, and thus encourages their use in many molding operations, particularly injection molding processes.
  • these materials most particularly PET, are known to exhibit poor impact resistance properties subsequent to annealing or heat aging.
  • injection molding of PET results in a slow rate of crystallization and
  • plastic materials comprising a blend or mixture of a polycarbonate and an ⁇ oly(alkylene terephthalate)
  • improvements in the processing and the physical properties of plastic materials have included the addition of further constituents to these two polymers, or the use of specific molding processes for the production of articles formed from polycarbonate and poly(alkylene terephthalate) blends.
  • Some examples include U.S.
  • compositions Having An Enhanced Resistance to Gasoline which discloses PE and PC blended with rubbery impact modified and a blocked polyisocyanate prepolymer
  • U.S. Patent 4,764,556 to Lausberg et.al. for "Thermoplastic Molding Materials of Polyester and Polycarbonate” disclosing a thermoplastic molding material comprising polyalkylene terephthalates, polycarbonates and a rubber toughener and rubbery ethylene copolymers
  • U.S. Patent 4,897,448 for "Polyester/Polycarbonate Blends" to Romance for PE/PC blends which include core shell rubbers as impact modifiers
  • compositions having a major amount of an aromatic carbonate polymer, and a minor amount of an aromatic carbonate polymer impact modifying composition comprising a "teleblock” copolymer of a vinyl aromatic compound and an olefinic elastomer, and an olefin alkylacrylate.
  • an aromatic carbonate polymer impact modifying composition comprising a "teleblock” copolymer of a vinyl aromatic compound and an olefinic elastomer, and an olefin alkylacrylate.
  • Polyester Acrylate Elastomeric Copolymer and a Phenoxy Resin
  • a polymer composition which comprises a PC, polyalkylene terephthalate and an elastomeric acrylate copolymer, and of particular note is U.S.
  • compositions which include a polyester resin, which may be a poly(alkylene terephthalate) polymer, such as PET or ⁇ oly(butylene terephthalate), which is commonly known as "PBT” either as a homopolymer or a copolymer, or mixtures of PET and PBT, and an ethylene terpolymer such as ethylene/methacrylate/glycidyl methacrylate.
  • a polyester resin which may be a poly(alkylene terephthalate) polymer, such as PET or ⁇ oly(butylene terephthalate), which is commonly known as "PBT” either as a homopolymer or a copolymer, or mixtures of PET and PBT, and an ethylene terpolymer such as ethylene/methacrylate/glycidyl methacrylate.
  • compositions which exhibit further improvements in properties, and processability
  • an impact modified polyester-polycarbonate composition comprising:
  • A is a divalent aromatic radical derived from a dihydric aromatic compound, and a reactive terpolymer constituent (hereinafter interchangeably referred to as "graft terpolymer") which comprises a compound having the formula:
  • a reactive functionality "P” which is selected from epoxide, isocyanate, 1,3-oxazoline, or acyllactam functionalities, where the terpolymer forms graft linked bonds with other polymeric materials in a composition, particularly with polycarbonates and the poly(ethylene terephthalates).
  • a polymer composition having improved properties may be produced wherein the inventive polymer composition comprises a polycarbonate and a poly(ethylene
  • the polycarbonates which may be used are the carbonate polymers of dihydric phenols.
  • Such polycarbonates may be prepared by reacting a dihydric phenol with a carbonate
  • the resulting polycarbonate may be represented by recurring
  • A is a divalent aromatic radical derived from a dihydric aromatic compound, preferably bisphenol A.
  • dihydroxy aromatic compounds are defined as 4,4'- dihydroxydi(mononuclear aryl)A compounds where the mononuclear aryl may be phenyl, tolyl, xylyl,
  • ethylphenyl isopropylphenyl, etc.
  • the connecting A groups may be -CH 2 -, -C-H 4 -, -C 3 H 6 ,
  • Typical dihydric phenols are
  • aromatic polycarbonates can be manufacture by known processes, such as noted above, by reacting a dihydric phenol with a carbonate precursor, such as a phosgene with the methods set forth, and disclosed in U.S. Patent 4,018,750, or by transesterification processes disclosed in U.S. Patent 3,153,008, as well as other processes well known to the art.
  • a carbonate precursor such as a phosgene
  • two or more different dihydric phenols may be utilized, as well as a
  • blends of a linear polycarbonate and a branched polycarbonate may also be used.
  • blends of any of the above materials may be employed in the practice of this invention to provide the aromatic polycarbonate.
  • the above materials may be employed in the practice of this invention to provide the aromatic polycarbonate.
  • preferred aromatic polycarbonates are those selected from the group consisting of:
  • poly(2,2-bis(4-hydroxypehyl)alkane) carbonates The most preferred of these polycarbonates is a
  • Polycarbonates utilizable with the invention should have a number-average molecular weight of 10,000 to 80,000.
  • the range of the number-average molecular weight is in the range of 15,000 to 40,000. While the specific number-average molecular weight of the polycarbonate is recognized not to be detrimental to the operation of the novel graft terpolymer which provides improved properties in polymer compositions within which it is utilized, it has been observed that when the number-average molecular weight of the
  • polycarbonate is less than about 10,000 or more than about 80,000, the resultant product polymer composition has been observed to be inferior in molding and
  • the polycarbonates should preferably exhibit an intrinsic or inherent viscosity of about 0.2 to 1.2 dl/g, (deciliters/gram) more preferably of about 0.3 to 0.9 dl/g in dichloromethane by standard Ubbehlohde viscometry at room temperature.
  • the polycarbonates should preferably contain hydroxyl end groups.
  • Suitable polyesters include polymers which exhibit an inherent viscosity of 0.3 dl/g or greater and which generally are the linear saturated
  • condensation products of glycols and dicarboxylic acids, or reactive derivates thereof Preferably, they will comprise condensation products of aromatic
  • dicarboxylic acids having 8 to 14 carbon atoms and at least one glycol selected from the group consisting of cyclohexane dimethanol, neopentyl glycol, and aliphatic glycols of the formula HO(CH 2 ) n OH where the letter "n" may be any integer of 2 to 10.
  • n may be any integer of 2 to 10.
  • Up to 50 mole percent of the aromatic dicarboxylic acids can be replaced by at least one different aromatic
  • dicarboxylic acid having from 8 to 14 carbon atoms, and/or up to 20 mole percent can be replaced by an aliphatic dicarboxylic acid having from 2 to 12 carbon atoms.
  • Suitable oolyesters include : poly(ethylene terephthalate);
  • terephthalate/isophthalate copolymer and other linear homopolymer esters derived from aromatic dicarboxylic acids including but not limited to isophthalic, bibenzoic, naphthalene-dicarboxylic including
  • glycols selected from but not limited to
  • 1,4-butylene glycol Up to 20 mole percent, as indicated above, or one or more aliphatic acid may be included.
  • suitable aliphatic acids include adipic, sebacic, azzelaic dodeandioic and
  • the polyester is one or more of the poly(alkylene terephthalates), either as a homopolymer or as a copolymer of two or more poly(alkylene
  • compositions include PET
  • PET in finished articles is known to the art to account for the different impact strengths of these materials subsequent to an annealing operation, or subsequent to any extended exposure to heat.
  • PET's relatively rigid non-uniform crystalline morphology is known to cause more brittleness, and is thus less desirable as a material for use in forming articles, particularly in the absence of fillers and reinforcing agents.
  • the polyester should preferably have an
  • polyesters should preferably have active chain end groups viz., carboxylic acid and/or hydroxyl end groups in a concentration of at least 0.01 meq/g.
  • the end groups are determined by standard titrametric methods for carboxyl or hydroxyl determination.
  • the compositions in accordance with the present invention based on the total weight percentage of the composition, includes relative weight ratios of the polycarbonate in the range of about 30 to about 60 percent; the polyester in the range of about 30 to about 60 percent; and the graft terpolymer more fully discussed below in a range of weight ratios of between about 2 and about 30 percent.
  • the polyester should comprise about 40 percent of the composition, with the polycarbonate and the graft terpolymer comprising the remaining amount of the composition, as it has been observed that favorable impact properties subsequent to heat aging have has not been realized where the polyester is present in less than such a proportion.
  • compositions will further include a terpolymer constituent, or as interchangeably referenced above, a "graft terpolymer” comprising a compound having the formula:
  • X has a moiety derived from acrylic and methacrylic acid or allyl alcohol, e.g., glycidyl acrylates, glycidyl methacrylates, or glycidyl allyl ether.
  • the terpolymer forms graft type bonds with other polymeric materials in a composition, particularly with polycarbonates and the poly(ethylene terephthalates).
  • X having epoxide isocyanate, acyllactam or oxazoline. Accordingly, X having epoxide
  • X may be derived from glycidyl acrylate, glycidyl methcrylate, glycidyl allyl ether, and other glycidyl containing compounds.
  • X may be derived from glycidyl acrylate, glycidyl methcrylate, glycidyl allyl ether, and other glycidyl containing compounds.
  • X may be derived from glycidyl acrylate, glycidyl methcrylate, glycidyl allyl ether, and other glycidyl containing compounds.
  • X may be derived from glycidyl acrylate, glycidyl methcrylate, glycidyl allyl ether, and other glycidyl containing compounds.
  • X may be derived from glycidyl acrylate, glycidyl methcrylate, glycidy
  • X may be derived from 2-isopropenyl-1,3-oxazoline, 2-(p-vinyl phenyl)-1,3-oxazoline, and the like.
  • acyllactam functionality is desired, X may be derived from
  • methacryloyl caprolactam methacryloyllaurolactam, compounds of the general formula:
  • the grafted terpolymer may be synthesized by copolymerization of E, A or X in bulk or solution phase, catalyzed by free radical initiators or other types of initiators.
  • the relative weight ratios of the constituents comprising the graft terpolymer may be present in proportions which, relative to the total weight of the terpolymer of between about 98.9 and 45 weight percent E, between about 1 and 40 weight percent A, and between about 0.1 and about 15 weight percent X. It is to be noted that the relative proportions of the constituents relative to the total weight are subject to a great deal of variation and are dependent upon the weight of the individual constituents.
  • poly(ethylene terephthalate) may act to remove free water molecules from the polymer melt.
  • Such a feature eliminates the necessity of drying the poly(ethylene terephthalate) before it is melted during processing, which is a feature especially advantageous when
  • Examples of such typical modifiers include heat stabilizers, flame retardants, pigments and coloring agents, nucleators, lubricants and flow modifiers, especially ethylene copolymers which are frequently used additives for improving the melt flowcharacteristics of many polymer materials. Also, the use of in-organic materials as in-organic
  • modifiers such as fillers, and reinforcing agents
  • glass fibers including glass fibers, talc carbon fibers, and the like
  • talc carbon fibers may be included in any suitable amount, which is preferably in a range typically used in the art, between about 40 and 50%.
  • compositions in the Examples were generally prepared by one of two methods.
  • the melt blend is prepared by first dry blending the constituents in their appropriate weight percentages by tumble blending or in a rotary drum, then feeding in the blended constituents into the hopper of a single screw extruder which was heated so to form a melt of the constituents and then extruding it through a die to form strands.
  • the extrudate was rapidly passed through a water bath in order to quench and cool the strands.
  • the strands were then passed through a pelletizing machine and the pellets were collected and dried.
  • the polycarbonate utilized and the terpolymer are first preblended before combining them with the PET of any desired composition. This second method is the
  • preblending allows for a more homogeneous phase distribution of the terpolymer and the polycarbonate, which being preblended, improves the distribution of the terpolymer within the polycarbonate and PET, increasing the amount of grafting in the final composition and thereby enhancing the improved
  • the polycarbonate and the termpolymer are first preblended via a melt extrusion before blending with the PET by another melt extrusion
  • the melt blend may be prepared by use of a 2-stage, single pass extrusion process.
  • a dry blend of the polycarbonate and the terpolymer in their appropriate weight percentages is introduced into a first hopper of a single screw extruder.
  • PET is introduce into a second hopper of the extruder at location downstream
  • the extrudate was rapidly passed through a water bath in order to quench and cool the strands which were then pelletized, and collected, and when necessary, dried.
  • pellets were utilized to mold test specimens which were 1/8 inch test bars which are a standardized sample size well known to the art by use of an
  • test bars were annealed in an annealing oven at a temperature of about 150 deg.C where they were retained for periods of either 16 hours or 72 hours in accordance with testing parameters well known to the art.
  • Example 1 is a melt blend composition consisting essentially of 40% PET, 40% of a polycarbonate and 20% of an ethylene/ethyl acrylate/glycidyl methacrylate terpolymer.
  • the PET used was a bottle grade resin with 0.67 I.v. ( as determined in phenol/TCE) and typically containing between about 0.035-0.04 meg/g of carboxyl chain ends.
  • the polycarbonate used was commercially available from the under the trade name "Lexan", a name used for a family of polycarbonate materials. The particular polycarbonate used was "Lexan 101".
  • the ethylene/ethyl acrylate/glycidyl terpolymer was
  • the melt blend was prepared by first dry
  • the dry blended constituents were then fed into the hopper of a Killion 1 inch single screw extruder with a L/D ratio of 30/1 using a feed screw equipped with a Maddox mixing head.
  • the extruder barrel temperatures for each zone were kept at the following approximate temperatures of: Zone 1, 205 deg.C; Zone 2, 250 deg.C; Zone 3, 270 deg.C; Zone 4, 250 deg.C.
  • the temperature of the flange was kept at approximately 250 deg.C and the temperature of the dies was kept at approximately 210 deg.C.
  • the extruder screw rotational speed was maintained at about 60 rpm.
  • the extrudate was rapidly passed through a water bath in order to quench and cool the strands.
  • the cooled strands were then passed through a pelletizing machine and the pellets formed were collected and dried.
  • the pellets were molded into test specimens by injection molding using an injection molding machine.
  • the barrel temperature of the machine during the injection process was maintained within a temperature range of about 280 - 287 deg.C and the mold was kept at a temperature of about 50 deg.C.
  • the cycle time was approximately 10 seconds during the injection step, and approximately 20 second during cooling.
  • test bars were annealed, or heat aged in a circulating hot air oven at about 150 deg.C for periods of either 16 hours or 72 hours.
  • the comparative examples A, B, C, D and E are compositions comprising PET, PC and various impact modifiers. Each of these examples was prepared in the same manner as the composition of Example 1, and consisted essentially of 40% PET, 40% of a
  • Comparative Example A used an methyl
  • methacrylate-butadiene-styrene (which is frequently catergorized in the art as an "interpolymer") or "MBS" core shell rubber as its impact modifier.
  • This rubber enjoys significant usage in the art as an impact modifier as this material exhibits good elasticity and provides good impact absorption.
  • the impact modifier used in the composition of Comparative Example B was an
  • ABS acrylonitrile-butadiene-styrene
  • the formulation B was commercially obtained from Mobay Chemical Co. under the trade designation "Makroblend UT1018".
  • C is an all-acrylate core shell rubber, which is marketed under the trademark "Paraloid KM 330" by Rohm & Haas, and consists of a cross linked
  • Comparative Example E utilizes an ethyl/glycidyl methacrylate copolymer as the impact modifier.
  • the particular copolymer is commercially marketed under the tradename "Bondfast 2C" and is available from the
  • the relative weight ratios of the ethyl to the glycidyl methacrylate in the copolymer is 94/6.
  • compositions of examples A, B, C, D and E were all produced, molded and subsequently tested in the manner utilized in the production of example 1, so to more clearly illustrate the distinct advantage of compositions made in accordance with the invention.
  • testing of the samples included impact testing, tensile elongation, tensile modulus and yield stress according to the same testing procedures
  • Example 1 utilized in testing the composition of Example 1.
  • the physical properties measured for these Comparative Examples indicate the marked reduction in the toughness of the material subsequent to annealing, or heat aging at 150 deg.C. Results of the tests are also summarized under the appropriate headings and listed on Tables 1 and 2 below.
  • compositions of the present invention namely, the compositions which include a reactive graft-terpolymer show the unexpected
  • annealing and superior impact strength retention This is attributed to the functionality of the terpolymer in its ability to form a graft copolymer through reaction with the terminal end groups, carboxyl and hydroxyl, of PET and PC. Further, the excellent elasticity of the terpolymer imparts good impact energy absorption qualities to the molded composition, and which is further believed to act as a compatibilizing agent for the PET and PC used.
  • Examples 2,3,4,5 and 6 are further embodiments of the invention which utilized the constituents as used to formulate Example 1, but varies the relative proportions of the PET, PC and the reactive terpolymer used in Example 1.
  • the range of variation for the respective components based on the total weight of the composition was: 30% to 80% PET, 0% to 50% PC, and a constant 20% of the terpolymer.
  • compositions of Examples 2-6 were produced in the same manner as that used for the production of Example 1.
  • Example 5 As may be determined from Tables 3 and 4, the composition of Example 5 exhibited
  • Examples 7-12 exemplify the second, alternative method of preparing the compositions.
  • an additional step, "preblending" of the polycarbonate and the reactive terpolymer may be accomplished by methods known to the art, including a two-step process, or a two-stage, single pass extrusion process. This latter process was used for the formation of the compositions of Examples 7-12.
  • Table 5 indicates the various ratios of constituents utilized in the compositions of Examples 7-12 which were produced using a preblending step. The percentages shown are percent by weight of the
  • compositions showed good retention of impact strength throughout, especially for Examples 7-10. It may further be observed that the second method of forming compositions, where there is preblending may be advantageous to the first method without preblending of the constitutents by a
  • compositions produced by processes including no preblending with processes including preblending are compositions produced by processes including no preblending with processes including preblending.
  • Example 5 and Example 7 Example 4 and 10.
  • impact test values (notched Izod) indicate improved
  • Example 13 was a composition consisting essentially of 40% PET, 40% PC and 20% ethylene/ethyl acrylate/glycidyl methacrylate
  • Comparative Example E was a composition of PET, PC and an
  • Example 13 The composition of Example 13 was noted to be completely ductile before heat-aging, and the
  • composition of Comparative Example E was noted to be completely brittle after heat aging, and showed poor strength retention.
  • compositions comprising the terpolymer of the present invention by melt blending the constituents in accordance with the method
  • compositions containing an amount of an ethylene copolymer such as E/EA noted above, but not to be limited solely to E/EA, may be included in compositions, generally in amounts of up to about 10% so to replace up to about half of the reactive
  • terpolymer may be used without detracting from the beneficial qualities of the present invention.

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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

Compositions polymères comprenant du poly(éthylène téréphthalate), du polycarbonate et un constituant de therpolymère présentant des propriétés de résistance à l'impact améliorées, notamment après un vieillissement thermique.
PCT/US1991/001347 1990-04-04 1991-02-26 Compositions de melanges de polyethylene terephthalate-polycarbonate a haute resistance a l'impact WO1991015545A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BR919106113A BR9106113A (pt) 1990-04-04 1991-02-26 Composicao de poliester-policarbonato modificada por impacto

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US50445690A 1990-04-04 1990-04-04
US504,456 1990-04-04

Publications (1)

Publication Number Publication Date
WO1991015545A1 true WO1991015545A1 (fr) 1991-10-17

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PCT/US1991/001347 WO1991015545A1 (fr) 1990-04-04 1991-02-26 Compositions de melanges de polyethylene terephthalate-polycarbonate a haute resistance a l'impact

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EP (1) EP0523087A1 (fr)
JP (1) JPH05501128A (fr)
BR (1) BR9106113A (fr)
CA (1) CA2075910A1 (fr)
WO (1) WO1991015545A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0528462A1 (fr) * 1991-07-31 1993-02-24 ENICHEM S.p.A. Mélanges de polycarbonate et de polyester ayant des propriétés de résistance au choc améliorées
EP0803537A2 (fr) * 1996-04-25 1997-10-29 General Electric Company Compositions à mouler polyester-polycarbonate résistantes aux chocs
EP0902055A2 (fr) * 1997-09-10 1999-03-17 Basf Aktiengesellschaft Compositions de moulage thermoplastiques à base de polyesters et de polycarbonates

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0180648A1 (fr) * 1984-05-01 1986-05-14 Toray Industries, Inc. Composition de polyester et ses moulages
EP0206267A2 (fr) * 1985-06-20 1986-12-30 BASF Aktiengesellschaft Masses à mouler thermoplastiques de polyester et de polycarbonate résistant au choc à froid
EP0233473A2 (fr) * 1986-01-20 1987-08-26 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polycarbonates et de polyesters
US4753980A (en) * 1984-02-24 1988-06-28 E. I. Du Pont De Nemours & Company Toughened thermoplastic polyester compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4753980A (en) * 1984-02-24 1988-06-28 E. I. Du Pont De Nemours & Company Toughened thermoplastic polyester compositions
EP0180648A1 (fr) * 1984-05-01 1986-05-14 Toray Industries, Inc. Composition de polyester et ses moulages
EP0206267A2 (fr) * 1985-06-20 1986-12-30 BASF Aktiengesellschaft Masses à mouler thermoplastiques de polyester et de polycarbonate résistant au choc à froid
EP0233473A2 (fr) * 1986-01-20 1987-08-26 BASF Aktiengesellschaft Masses à mouler thermoplastiques à base de polycarbonates et de polyesters

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0528462A1 (fr) * 1991-07-31 1993-02-24 ENICHEM S.p.A. Mélanges de polycarbonate et de polyester ayant des propriétés de résistance au choc améliorées
EP0803537A2 (fr) * 1996-04-25 1997-10-29 General Electric Company Compositions à mouler polyester-polycarbonate résistantes aux chocs
EP0803537A3 (fr) * 1996-04-25 1998-08-12 General Electric Company Compositions à mouler polyester-polycarbonate résistantes aux chocs
EP0902055A2 (fr) * 1997-09-10 1999-03-17 Basf Aktiengesellschaft Compositions de moulage thermoplastiques à base de polyesters et de polycarbonates
EP0902055A3 (fr) * 1997-09-10 2000-05-17 Basf Aktiengesellschaft Compositions de moulage thermoplastiques à base de polyesters et de polycarbonates

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CA2075910A1 (fr) 1991-10-05
EP0523087A1 (fr) 1993-01-20
BR9106113A (pt) 1993-02-24
JPH05501128A (ja) 1993-03-04

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