WO1987004447A1

WO1987004447A1 - Elastomeric compositions

Info

Publication number: WO1987004447A1
Application number: PCT/US1986/000119
Authority: WO
Inventors: Nan-I Liu; Russell James Mc Cready
Original assignee: General Electric Company
Priority date: 1986-01-27
Filing date: 1986-01-27
Publication date: 1987-07-30
Also published as: AU584167B2; EP0258220A1; JPS63502351A; AU5394386A

Abstract

Novel thermoplastic elastomeric molding compositions comprising a blend of a thermoplastic elastomeric polymer and a high molecular weight thermoplastic polyester.

Description

ELASTOMERIC COMPOSITIONS Nan-I Liu Russel J. McCready The present invention relates to novel thermo¬ plastic elastomeric molding compositions. Depending upon their compositional makeup, these compositions have a number of excellent and highly desirable physical properties including excellent tensile elongation and/or the ability to absorb high energy and "spring back" with little or no permanent deformation upon impact. Specifically, the compositions of the instant invention comprise poly- etherimide esters or polyetherester imides having admixed therewith a high molecular weight polyester.

Polyether ester imides are well known having been described in numerous publications and patents includ¬ ing for example, Honore et al, "Synthesis and Study of Various Reactive Oligmers and of Poly(ester-imide- ether)s," European Polymer Journal Vol. 16, pp. 909-916, October 12, 1979; and in Kluiber et al, U.S. Patent No. 3,274,159 and Wolfe Jr., U.S. Patent Nos. 4,371,692 and 4,371,693, respectively. More recently, McCready in pending U.S. Patent Application Serial No. 665,277 filed October 26, 1984, disclosed a novel class of polyetherimide esters having superior elasto¬ meric and other desired characteristics.

While the foregoing polymers having ether, imide and ester units have many desired properties including good flexibility, impact strength and moldability, these compositions have very poor heat sag resistance. Thus, molded parts from these compositions severely sag upon exposure to high temperatures, eg. greater than 250^βF. Additionally, because of the high flexibility of these materials as demonstrated by their very low flexural modulus, these compositions are limited to certain applications where physical integrity or stiffness of the part is not desired.

It is an object of the present invention to provide 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.

Furthermore, it is an object of the present invention to provide thermoplastic molding composi¬ tions which have surprisingly high tensile elongation as well as excellent melt and crystallization temper¬ atures and related characteristics.

It has now been discovered that 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. SUMMARY

In accordance with the present invention there are provided novel thermoplastic compositions having good heat sag resistance and excellent tensile elong¬ ation and/or and Dynatup properties comprising an admixture of a) one or more thermoplastic elastomeric poly¬ mers characterized as having ether, ester and imide linkages and wherein the ether linkages are present as high molecular weight, ie. MW of from about 400 to about 12000, polyoxyalkylene or co- polyoxyalkylene units derived from long chain ether glycolε and/or long chain ether diamines, and b) a modifying amount of a high molecular weight thermoplastic polyester.

Detailed Description of the Invention 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. Typically these thermoplastic elastomeric polymers are referred to as poly(etherester imide)s, poly(ester imide ethers) and poly(etherimide ester)s. Suitable poly(etherester imide)s and poly(ester- imide ether)s and their manufacture are described in, for example, Honore et al "Synthesis and Study of Various Reactive Oligomers and of Poly(esterimide ethers)", European Polymer Journal, Vol. 16 pp. 909-916, October 12, 1979 and in Wolfe Jr., U.S. Patent Nos. 4,371,692 and 4,371,693, herein incorporated by reference. These are characterized as comprising units of the formulas:

and

or

-O-G-O- III

and

or mixtures thereof wherein 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.

Representative of suitable 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). 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. When used herein, the term "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. Exemplary of 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. Exemplary of these 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. Especially preferred are 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. In- eluded among the 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 %. As mentioned above, 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. Of these diamines, 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 -Q¹- 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-(β-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.

A second and preferred class of 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. In general, 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.

The 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. The term "dicarboxylic acids" as used here- in, includes equivalents of dicarboxylic acids having two functional carboxyl groups which perform substan¬ tially like dicarboxylic acids in reaction with gly¬ cols and diols in forming polyester polymers. These equivalents include esters and ester-forming deriva- tives, such as acid halides and anhydrides. The mol¬ ecular weight preference, mentioned above, pertains to the acid and not to its equivalent ester or ester- forming derivative. Thus, 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. Addition¬ ally, the dicarboxylic acids may contain any subεti- 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, as the term is used herein, 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, as the term is used herein, 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 -S0₂-.

Representative 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) , 3,4-furan dicarboxylic acid, and 1,1-cyclobutane dicarboxylic acid. Pre¬ ferred aliphatic acids are cyclohexane dicarboxylic acids,sebacic acid, dimer acid, glutaric acid, azelaic acid and adipic acid.

Representative 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. Among the 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.

Finally, where mixtures of dicarboxylic acids are employed in the preparation of the poly(etherimide ester), it is preferred that at least about 60 mole %, preferably at least about 80 mole %, based on 100 mole % of dicarboxylic acid (ii) be of the same dicarb¬ oxylic acid or ester derivative thereof. As mentioned above, 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.

In general, the polyoxyalkylene diimide diacids are characterized by the following formula:

wherein each R is independently a trivalent organic radical, preferably a C-, to C₂₀ 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 -

Further, while 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

- 12 - tricarboxylic anhydride; 3,3' ,4 diphenyl tricarboxylic anhydride; 3,3' ,4 benzophenone tricarboxylic anhydr¬ ide; 1,3,4 cyclopentane tricarboxylic anhydride; 2,2' ,3 diphenyl tricarboxylic anhydride; diphenyl sulfone - 3,3',4 tricarboxylic anhydride, ethylene tricarboxylic anhydride; 1,2,5 naphthalene tricarb¬ oxylic anhydride; 1,2,4 butane tricarboxylic anhyd¬ ride; diphenyl isopropylidene 3,3* ,4 tricarboxylic anhydride; 3,4 dicarboxyphenyl 3'-carboxylphenyl ether anhydride; 1,3,4 cyclohexane tricarboxylic anhydride; etc. These tricarboxylic acid materials can be characterized by the following formula:

where R is a trivalent organic radical, preferably a C« to C₂₀ 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.

In the preparation of the poly(etherimide ester)s, the diimide diacid may be preformed in a separate step prior to polymerization or they may be formed during polymerization itself. In the latter instance, 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. Alternatively, 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. to about 250°C. while drawing off water or in a solvent system at the reflux temperature of the solvent or azeotropic (solvent) mixture. Preferred 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. Especially preferred 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. In its most preferred embodiments, the diol will be 100 mole %

1,4- butanediol and the dicarboxylic acid 100 mole % dimethylterephthalate.

As mentioned, 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, iεophthalic 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:

where D is as defined above in formulas II and IV for aliphatic and cycloaliphatic diols. Most preferably D is derived from a C₂ to C, aliphatic diol. Exemplary of the preferred aromatic polyesters there may be given poly(butylene terephthalate), poly(butylene terephthalate-co-isophthalate) , poly(ethylene terephthalate) and blends thereof, most preferably poly(butylene terepthalate) . 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. Illustratively, 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^βC. - 15 -

In general, the compositions of the present invention comprise an admixture of a polyether imide ester (a) and a polyester (b) . For practical purposes, 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. As will be demonstrated in the examples below, 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.

Additionally, the 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.

The 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.

The polymer 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.

The following examples are given as exemplary of the present invention and are not to be construed as limiting thereto.

Detailed Description of the Preferred Embodiments The following ASTM methods were used in determining the physical characteristics of the compositions:

Flexural Modulus ASTM D790 Tensile Elongation ASTM D638 Shore D Hardness ASTM D2240 Notched Izod ASTM D256 Unnotched Izod ASTM D256

All compositions were prepared by melt blending the thermoplastic elastomer with the thermoplastic polyester in a Prodex single screw extruder. PEIE A-C

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 A 15,000 psi

PEIE B 25,000 psi

PEIE C 50,000 psi - 17 -

PEIE D 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.

Examples 1-5, 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.

As is evident from 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.

Additionally, these compositions manifested some very unexpected and surprising results. For example, Dynatup properties increased with increased loadings of PBT, as compared to the unmodified PEIE, up through an 83 weight percent loading. A similar trend was apparent with respect to Heat Sag at 290°F, which also Table 1

A J, 2 3_ 4_ 5_

PEIE A" 100 90 80 50 15 10 PBT^b - 10 20 50 75 90

NI 1/4", ft lb/in NB NB NB 4.6 4.3 1.6

NI 1/4", -30°C, ft lb/in 8 2.7 3.1 1.7 1.4 1.2

3 Flexural Modulus xlO psi 14.8 20.8 33.6 123 205 307

Tensile Elongation, % 240 233 228 395 457 357

Dynatup -30-C_f E_maχ E_total 20/32 21/34 23/35 24/39 27/45 11/11

Heat Sag 290^βF, 30 min, mm 43 27 26 17 24

a. All compositions contained 0.7 parts by weight stabilizer. b. Poly(butylene terephthalate) iv. approx. 1.2dl/g from General Electric Company as VALOX® 315.

- 19 - improved up through the 83 weight percent loading. However, the most surprising result was the effect on tensile elongation. After an initial drop upon the addition of polyester (about 20 weight percent) , there was a tremendous increase in elongation up through the 80 weight percent loading. This increase in elongation was even far superior to the unmodified elastomer.

Examples 6-10, Comparative Example B

A second series of examples were prepared this time blending the poly(ether imide ester) with poly(ethylene terephthalate) (PET). The composition of the examples and the physical properties there of were as shown in Table 2.

From Table 2 it is apparent that compositions having a number of desirable properties making them suitable for various molding applications were obtained. Once again the level of incorporation of the polyester dramatically affected the physical properties of the resultant composition. In these blend compositions, 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. Finally, once again after an initial loss of tensile elongation, tensile elongation increased dramatically with increased loading of PET.

Table 2

!_ __ I I __ i_-

PEIE A* 100 85 70 50 15 10

PET^D - 15 30 50 85 90

NI 1/4" ft lb/in NB 5.3 4.6 2.9 1.2 1.05

NI 1/4", -30°C ft lb/in 6.7(NB) 1.35 1.4 1.0 0.6 0.75

UNI 1/4", -30°C ft lb NB 13.4(2NB) 14.8(3NB) 21.6(3NB) 15.3 11.6

Flexural Modulus xlO³ psi 12.9 27.5 53.7 132.2 306.9 330.5

Tensile Elongation psi 243 109 190 400 466

Heat Sag _ 290°F, 30 min mm 45 53 62 74 47 52

Dynatup, -30^βC 17/26 4/4 15/17 21/28 4/4 3/3

ro o a. See Table 1 above b. Poly(ethylene terephthalate) available under the trademark Vituf from Goodyear.

- 21 -

Examples 11-15, Comparative Example C

An additional series of examples were run further demonstrating the scope of the present invention. In these examples various polyetherimide esters were exemplified with two different poly(butylene terephthalates) . Once again, it is evident that the blend compositions have improved tensile elongation as compared to the unmodified poly(etherimide ester). Further comparison of examples 11 and 14 demonstrate the differences obtained by utilizing a lower intrinsic viscosity polyester. Finally, a comparison of examples 12 through 15 demonstrates the impact of utilizing various poly(ether imide esters), wherein the poly(ether imide esters) vary in initial flexural modulus or in actual monomer chemistry.

Additionally, a comparison of examples 14 and 15 wherein each elastomer has an initial modulus of 15,000 psi, demonstrates markedly improved heat sag resistance and tensile elongation when utilizing an elastomer prepared from copoly(propylene ether- ethylene ether) iamine as compared to one prepared from poly(propylene ether) iamine.

Examples 16-17

A final set of examples within the scope of the present invention were prepared utilizing both the polyetherimide esters of McCready, above, and the polyether ester imides of Wolfe, Jr., above. The makeup of these compositions and the physical properties thereof were as shown in Table 4. These examples further demonstrate the breadth and utility of the present invention.

Obviously, other modifications will suggest themselves to those skilled in the art in light of the above, detailed description. All such modifications are within the full intended scope of the present invention as defined by the appended claims. Table 3

C j_l 12 13 15

PEIE A: 100 65 65 PEIE B[ 65

PEIE c: 70

PEIE p 65 PBT 1*T 35 30 35 35 PBT 2 35

NI 1/4" ft lb/in NB 5.6 NB 3.3 NB NB

NI 1/4", -30^βC, ft lb/in 8(NB) 2.8 - - - -

UNI 1/4:, -30°C, ft lb/in - - NB NB 18.8(4NB) 15 .2(2NB)

Flexural Modulus xlO psi 14.8 77 99 120 69.8 52.7

Tensile Elongation % 243 300 260 300 208 289

Shore D Hardness 47 60

Heat Sag -9 290°F, 30 min, mm - 23 15 32 19

Dynatup, -30°C 28/46 11/15 22/40 6/6 a. 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. VALOXΦ 295 poly(1,4 butylene terephthalate)resin from General Electric Company, iv. approx. 0.83 dl/g.

- 23 -

Table 4

__i 17

PEIE A 65

PEEI 65

PBT^a 35 35

NI ft lb/in

NI, -30°C ft lb/in

Flexural Modulus

Heat Sag

Dynatup, -30' ^»C

a. See note c Table 3,

Claims

- 24 -CLAIMS:

1. A thermoplastic molding composition comprising: a) one or more thermoplastic elastomeric polymers characterized as having ether, ester and imide linkages and wherein the ether linkages are present as high molecular weight polyoxyalkylene or copolyoxyalkylene units derived from long chain ether glycols and long chain ether diamines, and b) a modifying amount of a high molecular weight thermoplastic polyester.

2. The composition of Claim 1 wherein the thermoplastic elastomeric polymer is a polyetherimide ester derived from (i) one or more diols (ii) one or more dicarboxylic acids or the ester derivative thereof and (iii) one or more poly(oxyalkylene) diimide diacids or the reactants therefore.

3. The composition of Claim 2 wherein the diols are selected from the group consisting of C₂ to C.₉ aliphatic and cycloaliphatic diols and at least 60 mole percent of the diols are the same.

4. The composition of Claim 2 wherein the diols are selected from the group consisting of C₂ to C_g aliphatic and cycloaliphatic diols and at least 80 mole percent of the diols are the same.

5. The composition of Claim 2 wherein the diol is 1,4 butanediol.

6. The composition of Claim 2 wherein at least 60 mole percent of the dicarboxylic acids are the same and are selected from the group consisting of C. to C₁₉ aliphatic, cycloaliphatic and aromatic dicarboxylic acids and the ester derivatives thereof. - 25 -

7. The composition of Claim 2 wherein at least 80 mole percent of the dicarboxylic acids are the same and are selected from the group consisting of C. to C.g aliphatic, cycloaliphatic or aromatic dicarboxylic acids and the ester derivatives thereof.

8. The composition of Claim 6 wherein the predominant dicarboxylic acid is a C_g to C._fi aromatic dicarboxylic acid or the ester derivative thereof.

9. The composition of Claim 7 wherein the predominant dicarboxylic acid is a C_g to C^ ~ aromatic dicarboxylic acid or the ester derivative thereof.

10. The composition of Claim 2 wherein the dicarboxylic acid is an aromatic dicarboxylic acid selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid and the ester derivatives thereof.

11. The composition of Claim 2 wherein the dicarboxylic acid is dimethyl terephthalate.

- 26 -

12. The composition of Claim 2 wherein the polyetherimide ester is prepared from a preformed poly(oxyalkylene) diimide diacid characterized as having the following formula:

or the reactants therefor comprising monomers of the following formulas:

H₂ - G - NH₂ and

wherein each R is independently a C₂ to C_2Q aliphatic, cycloaliphatic or aromatic trivalent organic radical; each R" is independently hydrogen or a C- to C, monovalent organic radical, and G is the radical remaining after removal of the terminal amino groups of a long chain ether diamine having a molecular weight of from about 400 to about 12,000.

13. The composition of Claim 12 wherein R is a C~ to C_2Q aromatic trivalent organic radical, R' is hydrogen or methyl and G is derived from a long chain ether diamine having a molecular weight of from about 900 to about 4000.

14. The composition of Claim 12 wherein the long chain ether diamine is selected from the group consisting of poly(ethylene ether)diamine, poly(propylene ether) diamine, poly(tetramethylene ether) diamine and copoly(ethylene ether-propylene ether) diamine. - 27 -

15. The composition of Claim 12 wherein the long chain ether diamine is poly(propylene ether) diamine.

16. The composition of Claim 12 wherein R is a C~ aromatic trivalent radical derived from trimellitic anhydride.

17. The composition of Claim 12 wherein the polyetherimide ester is derived from a preformed poly(oxyalkylene) diimide diacid which is the reaction product of trimellitic anhydride and poly(propylene ether) diamine having a molecular weight of from about 900 to about 4000.

- 28 -

18. The composition of Claim 1 wherein the thermoplastic elastomeric polymer is selected from elastomeric polymers characterized as comprising units of the formulas:

and 0 0 II II

0 . - -C-O-D-O- IV

II 0 or mixtures thereof wherein 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 12,000; 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 - 29 - an amino group and a carboxyl group from an 25 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.

19. The composition of Claim 1 wherein the high molecular weight thermoplastic polyester (b) is selected from the group consisting of homopolyesters, copolyesters and blends of i homopolyesters, copolyesters or both, derived from (i) one or more C₂ to C._g aliphatic, cycloaliphatic or aromatic diols and (ii) one or more C. to C._g aliphatic, cycloaliphatic or aromatic dicarboxylic acids.

20. The composition of Claim 1 wherein the high molecular weight thermoplastic polyester (b) is selected from the group consisting of aromatic homopolyesters, aromatic copolyesters and

, mixtures of said homopolyesters, copolyesters or both which are characterized as comprising repeating units of the following formula:

wherein D is the radical remaining after removal of the hydroxy groups of a C₂ to C_g aliphatic or cycloaliphatic diol, with the proviso that at least about 80 mole percent.of the units in the copolyesters are of the aromatic ester units.

21. The composition of Claim 20 wherein D is the radical remaining after removal of the hydroxy groups of a C₂ to C~ aliphatic diol. - 30 -

22. The composition of Claim 20 wherein the high molecular weight thermoplastic polyester is selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), poly(butylene terephthalate - co-isophthalate) and blends thereof.

23. The composition of Claim 22 wherein the high molecular weight thermoplastic polyester (b) is poly(butylene terephthalate).

24. The composition of Claim 1 comprising from about 1 to about 99 weight percent thermoplastic elactomeric polymer (a) and from about 99 to about 1 weight percent high molecular weight thermoplastic polyester (b) .

25. The composition of Claim 1 comprising from about 10 to about 90 weight percent thermoplastic elastomeric polymer (a) and from about 90 to about 10 weight percent high molecular weight thermoplastic polyester (b) .