EP0258220A1 - Compositions elastomeres - Google Patents

Compositions elastomeres

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Publication number
EP0258220A1
EP0258220A1 EP86901176A EP86901176A EP0258220A1 EP 0258220 A1 EP0258220 A1 EP 0258220A1 EP 86901176 A EP86901176 A EP 86901176A EP 86901176 A EP86901176 A EP 86901176A EP 0258220 A1 EP0258220 A1 EP 0258220A1
Authority
EP
European Patent Office
Prior art keywords
composition
poly
molecular weight
ether
aliphatic
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.)
Withdrawn
Application number
EP86901176A
Other languages
German (de)
English (en)
Inventor
Nan-I Liu
Russell James Mc Cready
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
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Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP0258220A1 publication Critical patent/EP0258220A1/fr
Withdrawn legal-status Critical Current

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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
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • compositions of the instant invention comprise poly- etherimide esters or polyetherester imides having admixed therewith a high molecular weight polyester.
  • thermoplastic molding compositions having excellent elastomeric properties including the ability to absorb and withstand high energy impact and "spring back" to its previous state or shape upon removal of the impinging energy with little or no permanent deformation.
  • thermoplastic molding composi ⁇ tions which have surprisingly high tensile elongation as well as excellent melt and crystallization temper ⁇ atures and related characteristics.
  • thermoplastic molding compositions may be prepared which overcome the foregoing deficiencies and have good overall physical characteristics including high strength and stress-strain properties, good impact resistance and good moldability.
  • Thermoplastic elastomeric polymers (a) suitable for use in the practice of the present invention are characterized as containing imide, ester and ether linkages wherein the ether linkages are present as high molceular weight, ie. from about 400 to about 12000 MW, preferably from about 900 to about 4000, polyoxyalkylene or copolyoxyalkylene units derived from long chain ether glycols and/or long chain ether diamines.
  • these thermoplastic elastomeric polymers are referred to as poly(etherester imide)s, poly(ester imide ethers) and poly(etherimide ester)s.
  • G is a divalent radical remaining after the removal of terminal (or as nearly terminal as possible) hydroxyl groups from a long chain poly(oxyalkylene)glycol having a molecular weight of from about 400 to about 12000;
  • D is a divalent radical remaining after the removal of hydroxyl groups from a diol having a molecular weight less than about 300;
  • Q is a divalent radical remaining after removal of amino groups from an aliphatic primary diamine having a molecular weight of less than 350 and Q' is a divalent radical remaining after removal of an amino group and a carboxyl group from an aliphatic primary amino acid having a molecular weight of less than 250, with the proviso that from about 0.5 to about 10 D units are present for each G unit.
  • Each of the above esterimide units exemplified by formulas I and II and formulas III and IV contain a diimide-diacid radical or an imide-diacid radical, respectively. As described in Wolfe, these are pre ⁇ ferably prepared by reacting the respective aliphatic diamine or amino acid with trimellitic anhydride either in a separate step prior to polymerization or during the polymerization itself.
  • Long chain ether glycols which can be used to provide the -G- radicals in the thermoplastic elast ⁇ omers are preferably poly(oxyalkylene)glycols and copoly(oxyalkylene)glycols of molecular weight of from about 400 to 12000.
  • Preferred poly(oxyalkylene) units are derived from long chain ether glycols of from about 900 to about 4000 molecular weight and having a carbon-to-oxygen ratio of from about 1.8 to about 4.3, exclusive of any side chains.
  • poly(oxyalkylene)- glycols there may be given poly(ethylene ether)glycol; poly(propylene ether)glycol; poly(tetramethylene ether) glycol; random or block copolymers of ethylene oxide and propylene oxide, including ethylene oxide capped poly(propylene ether)glycol and predominately poly- (ethylene ether) backbone, copoly(propylene ether- ethylene ether)glycol and random or block copolymers of tetrahydrofuran with minor amounts of a second monomer such as ethylene oxide, propylene oxide, or methyltetrahydrofuran (used in proportions such that the carbon-to-oxygen ratio does not exceed about 4.3).
  • a second monomer such as ethylene oxide, propylene oxide, or methyltetrahydrofuran
  • Polyfor al glycols prepared by reacting formaldehyde with diols such as 1,4-butanediol and 1,5-pentanediol are also useful.
  • Especially preferred poly(oxyalkyl ⁇ ene)glycols are poly(propylene ether)glycol, poly- (tetramethylene ether)glycol and predominately poly ⁇ ethylene ether) backbone copoly(propylene ether- ethylene ether)glycol.
  • Low molecular weight diols which can be used to provide the -D- radicals are saturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds. These diols are preferably of a low molecular weight, ie. having a molecular weight of about 300 or less.
  • diols and low molecular weight diols should be construed to include equivalent ester forming derivatives thereof, provided, however, that the molecular weight requirement pertains to the diol only and not to its derivatives.
  • ester forming derivatives there may be given the acetates of the diols as well as, for example, ethylene oxide or ethylene carbonate for ethylene glycol.
  • Preferred saturated and unsaturated aliphatic and cycloaliphatic diols are those having from about 2 to 19 carbon atoms.
  • diols there may be given ethylene glycol; propanediol; butanediol; pentanediol; 2-methyl propanediol; 2,2-dimethyl propane ⁇ diol; hexanediol; decanediol; 2-octyl undecanediol; 1,2-, 1,3- and 1,4- dihydroxy cyclohexane; 1,2-, 1,3- and 1,4-cyclohexane dimethanol; butenediol; hexene diol, etc.
  • 1,4-butanediol and mixtures thereof with hexanediol or butenediol most preferably 1,4-butanediol.
  • Aromatic diols suitable for use in the prepara ⁇ tion of the thermoplastic elastomers are generally those having from 6 to about 19 carbon atoms.
  • aromatic dihydroxy compounds are resorcinol; hydroquinone; 1,5-dihydroxy naphthalene; 4,4'-dihydroxy diphenyl; bis(p-hydroxy phenyl)methane and 2,2-bis(p-hydroxy phenyl) propane.
  • Especially preferred diols are the saturated ali- phatic diols, mixtures thereof and mixtures of a satur ⁇ ated diol(s) with an unsaturated diol(s), wherein each diol contains from 2 to about 8 carbon atoms. Where more than one diol is employed, it is preferred that at least about 60 mole %, based on the total diol con- tent, be the same diol, most preferably at least 80 mole %.
  • the preferred thermo ⁇ plastic elastomers are those in which 1,4- butanediol is present in a predominant amount, most preferably when 1,4-butanediol is the only diol.
  • Diamines which can be used to provide the -Q- radicals in the polymers of this invention are ali ⁇ phatic (including cycloaliphatic) primary diamines having a molecular weight of less than about 350, pre ⁇ ferably below about 250.
  • Diamines containing aromatic rings in which both amino groups are attached to ali ⁇ phatic carbons, such as p-xylylene diamine, are also meant to be included.
  • Representative aliphatic (and cycloaliphatic) primary diamines are ethylene diamine, 1,2-propylene diamine, methylene diamine, 1,3- and 1,4-diaminocyclohexane, 2,4- and 2,6-diaminomethyl- cyclohexane, - and p-xylylene diamine and bis(4-a_nino- cyclohexyl)methane.
  • ethylene diamine and bis(4-aminocyclohexyl)methane are pre ⁇ ferred because they are readily available and yield polymers having excellent physical properties.
  • Amino acids which can be used to provide the -Q 1 - radicals in the polymers of this invention are ali ⁇ phatic (including cycloaliphatic) primary amino acids having a molecular weight of less than about 250.
  • Amino acids containing aromatic rings in which the amino group is attached to aliphatic carbon such as phenylalanine or 4-( ⁇ -aminoethyl)benzoic acid, are also meant to be included.
  • Representative aliphatic and cycloaliphatic primary amino acids are glycine, alanine, JB-alanine, phenylalanine, 6-aminohexanoic acid, 11-aminoundecanoic acid and 4-aminocyclohexanoic acid. Of these amino acids, glycine and JB-alanine are preferred because they are readily available and yield polymers having excellent physical properties.
  • thermoplastic elastomers (a) suitable for use in the practice of the present invention are the poly(etherimide esters) as described in McCready, copending U.S Patent Applic ⁇ ation Serial No. 665,277 filed October 26, 1984, and cofiled, copending U.S. Patent application entitled "Thermoplastic Polyetherimide Ester Elastomers", both incorporated herein by reference.
  • the poly(etherimide esters) of McCready are random and block copolymers prepared by conventional processes from (i) one or more diols, (ii) one or more dicar- boxylic acids and (iii) one or more polyoxyalkylene diimide diacids or the reactants therefore.
  • the pre- ferred poly(etherimide esters) are prepared from (i) a C- to C. Q aliphatic and/or cycloaliphatic diol, (ii) a C. to C.g aliphatic, cycloaliphatic and/or aromatic dicarboxylic acid or ester derivative thereof and (iii) a polyoxyalkylene diimide diacid wherein the weight ratio of the diimide diacid (iii) to dicarb ⁇ oxylic acid (ii) is from about 0.25 to 2.0, preferably from about 0.4 to 1.4.
  • diols (i) suitable for use herein are essen- tially the same as those used to provide the -D- rad ⁇ ical in formulas II and IV as described above.
  • Dicarboxylic acids (ii) which are suitable for use in the preparation of the poly(etherimide esters) are aliphatic, cycloaliphatic, and/or aromatic dicar- boxylic acids. These acids are preferably of a low molecular weight, i.e., having a molecular weight of less than about 350; however, higher molecular weight dicarboxylic acids, especially dimer acids, may also be used.
  • esters and ester-forming deriva- tives such as acid halides and anhydrides.
  • the mol ⁇ ecular weight preference pertains to the acid and not to its equivalent ester or ester- forming derivative.
  • an ester of a dicarboxylic acid having a molecular weight greater than 350 or an acid equivalent of a dicarboxylic acid having a molec ⁇ ular weight greater than 350 are included provided the acid has a molecular weight below about 350.
  • the dicarboxylic acids may contain any sub ⁇ ti- tuent group(s) or combinations which do not substan- tially interfere with the polymer formation and use of the polymer of this invention.
  • Aliphatic dicarboxylic acids refers to carboxylic acids having two carboxyl groups each of which is attached to a saturated carbon atom. If the carbon atom to which the carboxyl group is attached is saturated and is in a ring, the acid is cycloaliphatic.
  • Aromatic dicarboxylic acids are dicarboxylic acids having two carboxyl groups each of which is attached to a carbon atom in an isolated or fused benzene ring system. It is not necessary that both functional carboxyl groups be attached to the same aromatic ring and where more than one ring is present, they can be joined by aliphatic or aromatic divalent radicals or divalent radicals such as -O- or -S0 2 -.
  • aliphatic and cycloaliphatic acids which can be used are sebacic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, glut- aric acid, succinic acid, oxalic acid, azelaic acid, diethylmalonic acid, allyl alonic acid, di er acid, 4-cyclohexene-l,2- dicarboxylic acid, 2-ethylsuberic acid, tetramethylsuccinic acid, cyclopentane dicar ⁇ boxylic acid, decahydro-l,5-naphthalene dicarboxylic acid, 4,4'- bicyclohexyl dicarboxylic acid, decahydro- 2,6-naphthalene dicarboxylic acid, 4,4 methylenebis- (cyclohexane carboxylic acid) ,
  • aromatic dicarboxylic acids which can be used include terephthalic, phthalic and iso- phthalic acids, bi-benzoic acid, substituted dicarboxy compounds with two benzene nuclei such as bis(p-carb- oxyphenyl) methane, oxybis(benzoic acid), ethylene- 1,2- bis-(p-oxybenzoic acid), 1,5-naphthalene dicarb ⁇ oxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7- naphthalene dicarboxylic acid, phenanthrene dicarb ⁇ oxylic acid, anthracene dicarboxylic acid, 4,4'- sulfonyl dibenzoic acid, and halo and C.-C.- alkyl, alkoxy, and aryl ring substitution derivatives thereof.
  • Hydroxy acids such as p( ⁇ -hydroxyethoxy)- benzoic acid can also be used provided an aromatic dicarboxylic acid is also present.
  • Preferred dicarboxylic acids for the preparation of the polyetheri ide esters are the aromatic dicarb ⁇ oxylic acids, mixtures thereof and mixtures of one or more dicarboxylic acid with an aliphatic and/or cyclo ⁇ aliphatic dicarboxylic acid, most preferably the aro- atic dicarboxylic acids.
  • aromatic acids those with 8-16 carbon atoms are preferred, particu ⁇ larly the benzene dicarboxylic acids, i.e., phthalic, terephthalic and isophthalic acids and their dimethyl derivatives. Especially preferred is dimethyl terephthalate.
  • the preferred poly(etherimide esters) are those in which dimethylterephthalate is the predominant dicarboxylic acid, most preferably when dimethyl- terephthalate is the only dicarboxylic acid.
  • Polyoxyalkylene diimide diacids (iii) are high molecular weight diimide diacids wherein the average molecular weight is greater than about 700, most pref ⁇ erably greater than about 900. They may be prepared by the imidization reaction of one or more tricarb- oxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl group, which must be esterifiable and pref ⁇ erably is nonimidizable, with a high molecular weight polyoxylalkylene diamine. These polyoxyalkylene diimide diacids and processes for their preparation are more fully disclosed in McCready, pending U.S. Patent Application Ser. No. 665,192 filed October 26, 1984, incorporated herein by reference.
  • polyoxyalkylene diimide diacids are characterized by the following formula:
  • each R is independently a trivalent organic radical, preferably a C-, to C 20 aliphatic, aromatic or cycloaliphatic trivalent organic radical; each R" is independently hydrogen or a monovalent organic radical preferably selected from the group consisting of C.. to C- aliphatic and cycloaliphatic radicals and C ⁇ to C « 2 aromatic radicals, e.g. benzyl, most preferably hydro ⁇ gen; and G is the radical remaining after removal of the terminal amino groups of a long chain poly(oxy alkylene)diamine equivalent to the long chain poly(oxy alkylene)glycol as described above in formulas I and III above.
  • the tricarboxylic component may be almost any carboxylic acid anhydride containing an additional carboxylic group or the corresponding acid thereof containing two imide-forming vicinal carboxyl groups in lieu of the anhydride group. Mixtures thereof are also suitable.
  • the additional carboxylic group must be esterifiable and preferably is substantially non ⁇ imidizable. - 11.1 -
  • trimellitic anhydride is preferred as the tricarboxylic component
  • any of a number of suitable tricarboxylic acid constituents will occur to those skilled in the art including 2,6,7 naphthalene
  • R is a trivalent organic radical, preferably a C « to C 20 aliphatic, aromatic, or cycloaliphatic tri ⁇ valent organic radical and R' is preferably hydrogen or a monovalent organic radical preferably selected from the group consisting of C. to C ⁇ aliphatic and/or cycloaliphatic radicals and C, to C- 2 aromatic radi- cals, e.g. benzy; most preferably hydrogen.
  • the diimide diacid may be preformed in a separate step prior to polymerization or they may be formed during polymerization itself.
  • the polyoxyalkylene diamine and tricar ⁇ boxylic acid component may be directly added to the reactor together with the diol and dicarboxylic acid, whereupon imidization occurs concurrently with ester- ification.
  • the polyoxyalkylene diimide diacids may be preformed prior to polymerization by known imidization reactions including melt synthesis or by synthesizing in a solvent system. Such reac- - 13 - tions will generally occur at temperatures of from 100°C. to 300°C, preferably at from about 150°C.
  • polyetherimide esters are those in which the weight ratio of the polyoxyalkylene diimide diacid (iii) to dicarboxylic acid (ii) is from about 0.25 to about 2, preferably from about 0.4 to about 1.4.
  • polyetherimide esters com ⁇ prise the reaction product of di ethylterephthalate, optionally with up to 40 mole % of another dicarboxylic acid; 1,4-butanediol, optionally with up to 40 mole % of another saturated or unsaturated aliphatic and/or cycloaliphatic diol; and a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene diamine of molecular weight of from about 400 to about 12000, preferably from about 900 to about 4000, and trimellitic anhydride.
  • the diol will be 100 mole %
  • 1,4- butanediol and the dicarboxylic acid 100 mole % dimethylterephthalate.
  • the polyetherimide esters may be prepared by conventional esterification/condensation reactions for the production of polyesters.
  • Exemplary of the processes that may be practiced are as set forth in, for example, U.S. Pat. Nos. 3,023,192; 3,763,109; 3,651,014; 3,663,653 and 3,801,547, herein incorporated by reference.
  • the foregoing thermoplastic elastomers (a) are modified in accordance with the teachings of the in ⁇ stant invention by admixing therewith a modifying amount of a high molecular weight thermoplastic polyester derived from one or more diols and one or more dicarboxylic acids.
  • Suitable diols and dicarboxylic acids useful in the preparation of the polyester component include those diols(i) and dicarboxylic acids(ii) mentioned above for use in the - 14 - preparation of the polyetherimide esters of McCready.
  • Preferred polyesters are the aromatic polyesters derived from one or more aliphatic and/or cyclo ⁇ aliphatic diols and an aromatic dicarboxylic acid.
  • Aromatic dicarboxylic acids from which the aromatic polyesters may be derived include for example the phthalic, i ⁇ ophthalic and terephthalic acids; naphthalene 2,6-dicarboxylic acid and the ester derivatives there of as well as other aromatic dicarboxylic acids mentioned above. Additionally, these polyesters may also contain minor amounts of other units such as aliphatic dicarboxylic acids and aliphatic polyols and/or polyacids.
  • Preferred aromatic polyesters will generally have repeating units of the following formula:
  • D is as defined above in formulas II and IV for aliphatic and cycloaliphatic diols. Most preferably D is derived from a C 2 to C, aliphatic diol.
  • the polyesters described above are either commer ⁇ cially available or can be produced by methods well known in the art, such as those set forth in 2,465,319; 3,047,539 and 2,910,466, herein incorporated by reference.
  • the high molecular weight thermoplastic polyesters (b) will have an intrinsic viscosity of at least about 0.4 decilliters/gram and, preferably, at least about 0.7 decilliters/gram as measured in a 60:40 phenol/tetrachloroethane mixture at 30 ⁇ C. - 15 -
  • compositions of the present invention comprise an admixture of a polyether imide ester (a) and a polyester (b) .
  • these compositions comprise from about 1-99 percent by weight of (a) to from about 99-1 percent by weight of (b) .
  • the specific amount by which each polymer is incorporated is dependent upon the physical properties desired in the resultant polymer composition.
  • different compositional makeup will provide different physical characteristics. For example, about an 80:20 mixture of poly(butylene tere ⁇ phthalate) / polyetherimide ester provides optimal tensile elongation, whereas a 20:80 mixture provides optimal low temperature impact.
  • compositions of the present invention may be suitably admixed with other additives including for example antioxidants plasticizers, pig ⁇ ments, flame retardants, fillers and the like as necessary.
  • compositions of the present invention may be prepared by any of the well known techniques for pre ⁇ paring polymer blends or admixtures, with extrusion blending being preferred.
  • Suitable devices for the blending include single screw extruders, twin screw extruders, internal mixers such as the Bambury Mixer, heated rubber mills (electric or oil heat) or Farrell continuous mixers.
  • Injection molding equipment can also be used to accomplish blending just prior to molding, but care must be taken to provide sufficient time and aggitation to insure uniform blending prior to molding.
  • Alternative methods include dry blending prior to extrusion or injection molding.
  • compositions prepared in accordance with the present invention are suitable for a broad range of applications. Depending upon the compositional makeup, these compositions will have - 16 - excellent heat sag resistance so as to allow for their use in painted articles which must be baked in ovens. Additionally, these compositions have excellent Dynatup properties such that when struck, they "give” to the impinging energy and “spring back” after the energy is removed. Thus, these compositions are especially suitable for use in automotive applica ⁇ tions, as for example, in fenders or bumpers.
  • thermoplastic elastomer elastomer with the thermoplastic polyester in a Prodex single screw extruder.
  • PEIE A-C are polyether imide esters prepared from butanediol, dimethylterephtlalate, poly(propylene ether) diamine (ave MW 2000) and trimellitic anhydride, wherein the weight ratio of dimethylterephthalate to diimide diacid was such as to produce polymers of flexural modulus as follows:
  • PEIE D is a polyetherimide ester prepared from butanediol, dimethylterephthalate and copoly(propylene ether-ethylene ether) diamine (ave MW 900) and trjmellitic anhydride, wherein the weight ratio of dimethylterephthalate to diimide diacid was such as to provide a polymer of 15,000 psi.
  • PEEI PEEI is a polyetherester imide prepared in accordance with Wolfe, Jr., above, from 32.5 parts by weight trimellitic anhydride, 13 parts by weight glycine, 23 parts by weight poly(tetramethylene ether)glycol (ave MW 1000), 31 parts by weight butanediol and 0.5 parts by weight of a phenolic stabilizer with a titanate ester catalyst.
  • Comparative Example A Compositions were prepared demonstrating blends of poly(butylene terephthalate) (PBT) with polyether ⁇ imide ester (PEIE) across a broad range of weight ratios. The specific compositions and the physical properties thereof were as presented in Table 1.
  • the physical properties of the blend varies widely depending upon the specific mixture employed. For example, optimum low temperature notched izod impact strength was achieved at about an 80:20 blend of PEIE to PBT; whereas the low temperature Dynatup was optimal at about 15:75 level of PEIE to PBT. Overall, the composition of the present invention had excellent stress strain and elastomeric characteristics.
  • PEIE A 100 90 80 50 15 10 PBT b - 10 20 50 75 90
  • compositions contained 0.7 parts by weight stabilizer.
  • compositions having a number of desirable properties making them suitable for various molding applications were obtained.
  • level of incorporation of the polyester dramatically affected the physical properties of the resultant composition.
  • optimum Dynatup properties were achieved at about a 50:50 mixture, with good properties found at from about a 30 weight percent to less than an 85 weight percent loading of PET.
  • tensile elongation increased dramatically with increased loading of PET.
  • PEIE A 100 65 65 PEIE B[ 65
  • PEIE compositions of examples C and 11 contain 1.1 parts by weight ri stabilizer, example 14 contains 0.7 parts by weight stabilizer. ro b. Each PEIE composition contains 0.7 parts by weight stabilizer. c. VALOX® 315 poly(1,4 butylene terephthalate)resin from General Electric Company iv. approx. 1.2 dl/g. d. VALOX ⁇ 295 poly(1,4 butylene terephthalate)resin from General Electric Company, iv. approx. 0.83 dl/g.

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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)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Les nouvelles compositions élastomères thermoplastiques de moulage ci-décrites consistent en un mélange d'un polymère élastomère thermoplastique et d'un polyester thermoplastique de poids moléculaire élevé.
EP86901176A 1986-01-27 1986-01-27 Compositions elastomeres Withdrawn EP0258220A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1986/000119 WO1987004447A1 (fr) 1986-01-27 1986-01-27 Compositions elastomeres

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EP0258220A1 true EP0258220A1 (fr) 1988-03-09

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EP (1) EP0258220A1 (fr)
JP (1) JPS63502351A (fr)
AU (1) AU584167B2 (fr)
WO (1) WO1987004447A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4598117A (en) * 1985-01-11 1986-07-01 General Electric Company Elastomeric compositions comprising a combination of (a) an aromatic thermoplastic polyester and (b) clay/syenite
US4659765A (en) * 1985-02-19 1987-04-21 General Electric Company Elastomeric compositions
US4891397A (en) * 1987-12-02 1990-01-02 General Electric Company Nucleated thermoplastic polyetherimide ester elastomer molding compositions
AU631582B2 (en) * 1989-02-23 1992-12-03 General Electric Company Blends of polyesters and high flow polycarbonate
EP0491986A1 (fr) * 1990-12-24 1992-07-01 General Electric Company Compositions ignifuges de polymères contenant du poly(téréphtalate de butylène) et des esters oligomères d'acide phosphorique ou phosphonique
US5260387A (en) * 1992-01-09 1993-11-09 W. L. Gore & Associates, Inc. Copolyester elastomer blends

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4141927A (en) * 1975-05-22 1979-02-27 General Electric Company Novel polyetherimide-polyester blends
EP0117326A1 (fr) * 1983-02-25 1984-09-05 General Electric Company Mélanges de polyétherimides et de polyarylates
US4556688A (en) * 1984-10-26 1985-12-03 General Electric Company Thermoplastic polyetherimide ester elastomers
US4598117A (en) * 1985-01-11 1986-07-01 General Electric Company Elastomeric compositions comprising a combination of (a) an aromatic thermoplastic polyester and (b) clay/syenite
US4659765A (en) * 1985-02-19 1987-04-21 General Electric Company Elastomeric compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8704447A1 *

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JPS63502351A (ja) 1988-09-08
WO1987004447A1 (fr) 1987-07-30
AU5394386A (en) 1987-08-14
AU584167B2 (en) 1989-05-18

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