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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters

Definitions

• the present invention relates to blends of copolyetherimide ester elastomer and a rubbery crosslinkabl alkylacrylate elastomer.
• Thermoplastic elastomers of the type known a polyetherimide esters provide a variety of unique an excellent properties and are particularly useful in extrusio and molding applications.
• Polyetherimide esters prepared from diols dicarboxylic acids and polyoxyalkylene diimide diacids ar thermoplastic elastomers having an excellent combination o stress-strain properties, low tensile set, high meltin temperatures and excellent strength, toughness and flexibilit properties. All of these properties are variously useful i many elastomer applications. Copolyetherimide ester elastomer also process well, due to their rapid crystallization rate an excellent moldability characteristics. Elastomers with the lo flexural modulus of polyetherimide esters in combination wi any of the aforementioned advantageous properties have gain wide acceptance in the field of elastomers.
• polyetherimide esters can be improved or enhanced for certa applications, especially with respect to improving t "softness" (lower durometer) of the elastomer, while retaini satisfactory tensile properties.
• the improvements a accomplished by blending a rubbery crosslinkable alkylacryla elastomer with the polyetherimide ester and dynamical crosslinking the former.
• Dynamic vulcanization has also been disclosed employing copolyesters.
• European patent, EP 0 293 821 A2 discloses a multiblock copolyester melt mixed with polychloroprene rubber which is then crosslinked during mixing.
• a segmented thermoplastic copolyester is blended with a second composition which is a blend of two partially crosslinked polymers, such as PVC or PVDC and a copolymer of ethylene and one or more ethylenically unsaturated comonomers prepared by dynamic vulcanization.
• Acrylic rubbers are also known to be employed in thermoplastic dynamic vulcanizates.
• Coran et al.. Rubber Chem. and Tech., 55, 116 (1982) disclose a matrix of polymers and rubbers used in the preparation of dynamic vulcanizate compositions in which polyacrylate rubber was used; however, not with copolyetherimide esters.
• Wolfe, United States Patent No. 4,782,110 discloses dynamically vulcanizing ethylene-alkylacrylate copolymer rubbers with crystalline polyolefins.
• Coran et al.. United States Patent No. 4,327,199 disclose employing, an ethylene-acrylic type copolymer rubber containing free carboxylic moieties in blends with polyesters such as PBT.
• a metal oxide is used as a source of metal ions to neutralize the pendant acid groups, forming an ionomeric network structure as distinguished from covalent bond formation.
• the ethylene acrylic copolymer is blended with a nylon resin and a metal oxide; and amorphous styrene based resins and a metal oxide, respectively.
• thermoplastic copolyetherimide ester None of these however disclose a polyacrylate rubber which has been dynamically vulcanized with a thermoplastic copolyetherimide ester. It has now bee discovered and is shown in the examples hereinafter tha dynamically vulcanizing a polyacrylate rubber with thermoplastic copolyetherimide ester provides an elastome composition with improved softness while retaining excellen tensile properties. This is unexpected because th copolyether esters employed in EP '010 suffer from the loss o tensile properties to a much greater extent when mixed wit crosslinkable polyacrylate rubbers and dynamically vulcanized.
• thermoplastic elastomer composition comprising: (A) a polyetherimide ester copolymer; (B) a crosslinkable rubbery alkylacrylate, and
• the polyetherimide ester copolymer can comprise the reaction product of (a) one or more low molecular weight diols; (b) one or more dicarboxylic acids; and (c) one or more polyoxyalkylene diimide diacids.
• the diol component Preferably the diol component
• (a) comprises from about 60 to about 100 mole percent
• the dicarboxylic acid component (b) comprises from about 60 to about 100 mole percent dimethyl terephthalate
• the polyoxyalkylene diimide diacid component (c) is . derived from trimellitic anhydride and a polyoxyalkyl diamine selected from the group consisting of polypropylene oxide . diamine and a copoly(ethylene oxide-propylene oxide) diamine having predominantly polyethylene oxide in the backbone.
• the preferred rubbery alkyl acrylate is based on repeating units comprising the formula:
• thermoplastic elastomer compositions further comprising a filler such as a silica and a plasticizer.
• the preferred compositions comprise component (A) in an amount ranging from about 20 to about 99 parts by weight and component (B) in an amount ranging from about 80 to about 1 part by weight based upon 100 parts by weight of (A) and (B) together.
• a process for producing a thermoplastic elastomer composition comprising: (I) mixing
• step (i) a polyetherimide ester copolymer, and (ii) a crosslinkable rubbery alkylacrylate; and (II) curing the mixture obtained in step (I) by adding a crosslinking agent.
• step (II) of the process further comprises adding an accelerator such as sulfur, sulfur donors, magnesium oxide, tertiary amines and mixtures of any of th foregoing. Most preferred are quaternary ammonium compounds.
• polyetherimide esters useful in the practic of the present invention may be prepared from one or mor diols, one or more dicarboxylic acids and one or more hig molecular weight polyoxyalkylene diimide diacids.
• G is a divalent radical remaining after removal of th amino groups of a high molecular weight polyalkylene ethe diamine;
• R is a trivalent organic radical;
• R is the divalen radical remaining after the removal of the hydroxyl groups o a diol;
• x is a whole number having a value of from 2 t about 40.
• poly(etherimide esters) used herein may b prepared by conventional processes, such as esterification an condensation reactions for the production of polyesters, t provide random or block copolymers.
• polyetherimide esters may be generally characterized as the reaction product of the aforementioned diols and acids.
• compositions encompassed by the present invention may be prepared from (a) one or more C 2 *-C 15 aliphatic or cycloaliphatic diols, (b) one or more C 4 -C 15 aliphatic, cycloaliphatic or aromatic dicarboxylic acids or ester derivatives thereof and (c) one or more polyoxyalkylene diimide diacids.
• the amount of polyoxyalkylene diimide diacid employed is generally dependent upon the desired properties of the resultant polyetherimide ester.
• the weight ratio of polyoxyalkylene diimide diacid (c) to dicarboxylic acid (b) is from about 0.25 to 2.0, preferably from about 0.4 to about 1.4.
• Suitable diols (a) for use in preparing the compositions of the present invention include saturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds as well as aromatic dihydroxy compounds. These diols are preferably of a low molecular weight, i.e. having a molecular weight of about 250 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. 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 2 to 19 carbon atoms. Exemplary of these diols there may be given ethylene glycol; propane diol; butane diol; pentane diol; 2-methyl propane diol; 2,2-dimethyl propane diol; hexane diol; decane diol; 2-octyl undecane diol; 1,2-, 1,3-, and 1,4-cyclohexane dimethanol; 1,2-, 1,3-, and 1,4-dihydroxy cyclohexane; butene diol; and hexene diol.
• Aromatic diols suitable for use in the practice of the present invention are generally those having from 6 to about 19 carbon atoms. Included 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.
• diols are the saturated aliphatic diols, mixtures thereof and mixtures of a saturated 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 content, be the same diol, most preferably at least 80 mole %.
• the preferred compositions are those in which 1,4-butanediol is present in a predominant amount, most preferably when 1,4-butanediol is the only diol.
• Dicarboxylic acids (b) which are suitable for use in the practice of the present invention are aliphatic, cycloaliphatic, and/or aromatic dicarboxylic acids. These acids are preferably of a low molecular weight, i.e., having a molecular weight of less than about 300; however, higher molecular weight dicarboxylic acids, especially dimer acids, which are fully described in Kirk-Othmer,Encyclopedia of Chemical Technology/ 3rd Edition, vol. 7, John Wiley & Sons, N.Y., pp. 768-782, may also be used.
• dicarboxylic acids includes equivalents of dicarboxylic acids having two functional carboxyl groups which perform substantially like dicarboxylic acids in reaction with glycols and diols in forming polyester polymers. These equivalents include esters and ester-forming derivatives, such as acid halides and anhydrides. The molecular weight preference, mentioned above, pertains to the acid and not to its equivalent ester or ester-forming derivative.
• 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 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 such as -0- or -S0 2 ⁇ .
• Representative aliphatic and cycloaliphatic acids which can be used for this invention include sebacic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, adipic acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, diethylmalonic acid, allylmalonic acid, 4-cyclohexane-l,2- dicarboxylic acid, 2-ethylsuberic acid, tetramethylsuccinic acid, cyclopentanedicarboxylic 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 di
• aromatic dicarboxylic acids which can be used include terephthalic acid, isophthalic acid, phthalic acid, bi-benzoic acid, substituted dicarboxy compounds with two benzene nuclei such as bis(p- carboxyphenyl)methane, oxybis(benzoic acid) , ethylene 1,2-bis- (p-oxybenzoic acid), 1,5-naphth ⁇ lene dicarboxylic acid, 2,6- naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid, and halo and C 1 ⁇ C 12 alkyl, alkoxy, and aryl ring substitution derivatives thereof. Hydroxy acids such as p-(beta-hydroxyethoxy)benzoic acid can also be used provided an aromatic dicarboxylic acid is also present.
• Preferred dicarboxylic acids for the preparation of the polyetherimide esters of the present invention are the aromatic dicarboxylic acids, mixtures thereof and mixtures of one or more dicarboxylic acids with an aliphatic or cycloaliphatic dicarboxylic acid, most preferably the aromatic dicarboxylic acids.
• aromatic acids ' those with 8-16 carbon atoms are preferred, particularly the benzene dicarboxylic acids, i.e., phthalic, terephthalic and isophthalic acids and their dimethyl derivatives.
• dimethyl terephthalate is especially preferred.
• dicarboxylic acids are employed in the practice of the present invention, it is preferred that at least about 60 mole %, preferably at least about 80 mole %, based on 100 mole % of dicarboxylic acid (b) be of the same dicarboxylic acid or ester derivative thereof.
• the preferred compositions are those in which dimethyl terephthalate is the predominant dicarboxylic acid, most preferably when dimethyl terephthalate is the only dicarboxylic acid.
• Polyoxyalkylene diimide diacids (c) suitable for use herein are high molecular weight diimide diacids wherein the average molecular weight is greater than about 700, most preferably greater than about 900. They may be prepared by the imidization reaction of one or more tricarboxylic acid compounds containing two vicinal carboxyl groups or an anhydride group and an additional carboxyl group which must be esterifiable and preferably is nonimidizable with a high molecular weight polyoxyalkylene diamine. The polyoxyalkylene diimide diacids and processes for their preparation are more fully disclosed in McCready, European Patent No.
• polyoxyalkylene diimide diacids useful herein may be characterized by the following formula:
• each R is independently a trivalent organic radical, preferably a C 2 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 g aliphatic and cycloaliphatic radicals and C 6 to C 12 aromatic radicals, e.g. phenyl, most preferably hydrogen; and G is the radical remaining after the removal of the terminal (or as nearly terminal as possible) hydroxy groups of a long chain ether glycol having an average molecular weight of from about 600 to about 12000, preferably from about 900 to about 4000, and a carbon-to-oxygen ratio of about 1.8 to about 4.3.
• Representative long chain ether glycols from which the polyoxyalkylene diamine is prepared include poly(ethylene ether)glycol; poly(propylene ether) glycol; poly(tetramethylene ether)glycol; random or block copolymers of ethylene oxide and propylene oxide, including propylene oxide terminated poly(ethylene ether)glycol; and random ' or block copolymers of tetrahydrofuran with minor amounts of a second monomer such as methyl tetrahydrofuran (used in proportion such that the carbon-to-oxygen mole ratio in the glycol does not exceed about 4.3).
• Especially preferred poly(alkylene ether)glycols are poly(propylene ether)glycol and poly(ethylene ether)glycols end capped with poly(propylene ether)glycol or propylene oxide.
• the polyoxyalkylf ⁇ -C 8 Jene diamines useful within the scope of the present invention will have an average molecular weight of from about 600 to 12000, preferably from about 900 to 4000.
• These may be characterized by the following general formula: H 2 N-G-NH 2 wherein G is the radical remaining after the removal of the amino groups of a long chain alkylene ether diamine.
• G is the radical remaining after the removal of the amino groups of a long chain alkylene ether diamine.
• These polyether diprimary diamines are available commercially from Texaco Chemical Company under the trademark "JEFFAMINE".
• they are prepared by known processes for the amination of glycols. For example, they may be prepared by aminating the glycol in the presence of ammonia, Raney nickel catalyst, and hydrogen as set forth in Belgium Patent No. 634,741.
• they may be prepared by treating the glycol with ammonia and hydrogen over a nickel-copper-chromium catalyst as taught by United States Patent No. 3,654,370.
• Other methods for the production thereof include those taught in United States Patent Nos. 3,155,728 and 3,236,895 and French Patent Nos. 1,551,605 and 1,446,708. All of the foregoing patents are incorporated herein by reference.
• 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 noni idizable.
• the tricarboxylic acid materials can be characterized by the following formula: 0
• R is a trivalent organic radical, preferably a C 2 to C 20 aliphatic, aromatic, or cycloaliphatic trivalent organic radical and R' is preferably hydrogen or a monovalent organic radical preferably selected from.the group consisting of C ⁇ to C 6 aliphatic or cycloaliphatic radicals and C g to C 12 aromatic radicals, e.g. phenyl; most preferably hydrogen.
• a preferred tricarboxylic component is trimellitic anhydride.
• these polyoxyalkylene diimide diacids may be prepared by known imidization reactions including melt synthesis or by synthesizing in a solvent system. Such reactions will generally occur at temperatures of from 100 degrees C to 300 degrees C, preferably at from about 150 degrees C to about 250 degrees C while drawing off water or in a solvent system at the reflux temperature of the solvent or azeotropic (solvent) mixture.
• the diol be present in at least a molar equivalent amount, preferably a molar excess, most preferably at least 150 mole % based on the moles of dicarboxylic acid (b) and polyoxyalkylene diimide diacid (c) combined.
• molar excess of diol will allow for optimal yields, based on the amount of acids, while accounting for the loss of diol during esterification/condensation.
• weight ratio of dicarboxylic acid (b) to polyoxyalkylene diimide diacid (c) is not critical to form the polyetherimide esters used in the present invention
• preferred compositions are those in which the weight ratio of the polyoxyalkylene diimide diacid (c) to dicarboxylic acid (b) is from about 0.25 to about 2 , preferably from about 0.4 to about 1.4.
• the actual weight ratio employed will be dependent upon the specific polyoxyalkylene diimide diacid used and more importantly, the desired physical and chemical properties of the resultant polyetherimide ester. In general, the lower the ratio of polyoxyalkylene diimide diester to dicarboxylic acid the better strength, crystallization and heat distortion properties of the polymer.
• the polyetherimide ester product will comprise the reaction product of dimethyl terephthalate, most preferably, with up to 40 mole % of another dicarboxylic acid; 1,4-butanediol, optionally with up to 40 mole % of another saturated or unsaturated aliphatic or cycloaliphatic diol; and a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene diimine of molecular weight of from about 600 to about 12000, preferably from about 900 to 4000, and trimellitic anhydride.
• the diol will be 100 mole % 1,4-butanediol and the dicarboxylic acid 100 mole % dimethyl terephthalate.
• polyetherimide esters described herein 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. Additionally, these compositions may be prepared by such processes and other known processes to effect random copolymers, block copolymers or hybrids thereof wherein both random and block units are present.
• a catalyst in the process for the production c the polyetherimide esters of the present invention.
• any of the known ester-interchange and polycondensation catalysts may be used.
• two separate catalysts or catalyst systems may be used, one for ester interchange and one for polycondensation, it is preferred, where appro 1 —iate, to use one catalyst or catalyst system for both.
• ester-interchange catalyst ineffective following the completion of the precondensation reaction by means of known catalyst inhibitors or quenchers, in particular, phosphorus compounds such as phosphoric acid, phosphenic acid, phosphonic acid and the alkyl or aryl esters of salts thereof, in order to increas the thermal stability of the resultant polymer.
• catalyst inhibitors or quenchers in particular, phosphorus compounds such as phosphoric acid, phosphenic acid, phosphonic acid and the alkyl or aryl esters of salts thereof, in order to increas the thermal stability of the resultant polymer.
• phosphorus compounds such as phosphoric acid, phosphenic acid, phosphonic acid and the alkyl or aryl esters of salts thereof.
• phosphorus compounds such as phosphoric acid, phosphenic acid, phosphonic acid and the alkyl or aryl esters of salts thereof
• titanium catalysts including the inorganic and organic titanium containing catalysts, such as those described in, for example, U.S. Pat. Nos.
• organic titanates such as tetra-butyl titanate, tetra-isopropyl titanate and tetra-octyl titanate and the complex titanates derived from alkali or alkaline earth metal alkoxides and titanate esters, most preferably the organic titanates.
• these too may be used alone or in combination with other catalysts such as for example, zinc acetate, manganese acetate or antimony trioxide, and/or with a catalyst quencher as described above.
• polyetherimide esters possess many desirable properties, it is often preferred to stabilize the compositions to heat, oxidation, radiation by UV light and the like, as described in the aforementioned U.S. Patent No. 4,556,705.
• the polyacrylate elastomers or rubbery alkylacrylates are generally copolymers having two major components: the backbone, comprising from about 95 to about 99 weight percent of the polymer; and the reactive cure site, comprising from about 1 to about 5 weight percent of the polymer.
• the copolymers Preferably have high molecular weights, typically around 100,000 Mv (viscosity average molecular weight).
• the backbones are made from monomeric aci esters to form repeating units of primarily two types:
• n 2 or 4 and m is 1 or 2.
• the most common cure sit monomers are described in the below referenced Starmer et al. article. Especially preferred are 2-chloroethyl vinyl ethe and allyl glycidyl ether.
• polyacrylate elastomer are inherently soft and tacky. They commonly have relativel low Mooney viscosities (ML-1+4 @ 100° C) in the 25 to 6 range. These elastomers are more fully described in P.H. Starmer and F.R. Wolf, Encyclopedia of Polymer Science an Engineering, 2d Ed., 306-325 (1985), incorporated herein b reference.
• the mixing of the polyetherimide esters an polyacrylate elastomers may be carried out in any device know to those skilled in the art.
• the components ar melt mixed in a compounding device such as an internal mixe (Brabender or Banbury type) and extruders (twin screw o kneading) .
• the polyetherimide esters and polyacrylat elastomers are typically combinable in proportions rangin from about 20 to about 99 parts by weight polyetherimide este and from about 80 to about 1 part by weight polyacrylat elastomer based upon 100 parts by weight of the two resin combined.
• the polyetherimide ester is present i an amount ranging from 20 to about 80 parts by weight, mos preferably from about 40 to about 60 parts by weight; an correspondingly the polyacrylate elastomer is present in a amount ranging from about 80 to about 20 parts by weight, mos preferably from about 60 to about 40 parts by weight.
• the compositions of the presen invention comprise about 50 parts by weight polyetherimid ester and about 50 parts by weight polyacrylate elastomer.
• the mixing compositions may also contain, in addition to resin and rubber, various additives known to those skilled in the art for use in compounding of thermoplastics, rubbers, and their blends, to modify the properties thereof, such as, but not limited to fillers, stabilizers, antidegradents, processing aids, plasticizers, pigments and the like.
• Typical fillers would include carbon blacks, silicas, clays, minerals or mixtures threof. Both low and high molecular weight plasticizers are contemplated.
• the thermoplastic copolyetherimide ester resin, rubber and additives are mixed in the appropriate device at a temperature high enough to soften and/or melt the materials such that an intimate mixture is obtained.
• the rubber material is cured by the addition of crosslinking agents, and optionally accelerators and heating, e.g., at from about 200° C to about 250° C, for from about 30 min. to about 30 sec, preferably from 5 min. to about 30 sec.
• Crosslinking agents are any agents which promote vulcanization of the acrylic elastomer.
• the cure system employed varies with type of cure-site monomer present in the acrylic elastomer.
• Preferred crosslinking agents are soaps including metallic carboxylates such as sodium or potassium stearate.
• the cure system may also comprise an accelerator as well as a crosslinking agent.
• Preferred accelerators include sulfur; sulfur donors such as tetramethylthiouram; or bases such as magnesium oxide or tertiary amines.
• Ammonium benzoate, ammonium adipate, and soap/quaternary amine systems are also known to be effective cure systems, as are red lead/ethylene thiourea and diamines and polyamines. Most preferred is a soap/quaternary ammonium system.
• the mixture is mixed to form an intimate blend.
• a crosslinker sodium stearate
• an accelerator quaternary ammonium complex, "NPC-50", Zeon Chemical Co., Japan
• the mixture is then dynamically cured by mixing for 3 to 4 minutes at a temperature of 200 ° to 220° C.
• the composition is injection molded into test specimens and tested for tensile strength properties.
• a back-to-back sample is prepared, except that a copolyether ester resin similar to those described in EPO 0 327 010 A2 ("HYTREL" G-4078) is employed as the thermoplastic elastomerinstead of the polyetherimide ester resin.
• the formulations used and the physical properties obtained are set forth in Table 1. TABLE 1 Example 1A* .
• composition prepared by dynamically vulcanizing a crosslinkable polyacrylate rubber with a thermoplastic copolyetherimide ester resin unexpectedly provides better retention of tensile properties than a composition prepared by dynamically vulcanizing a polyacrylate rubber with a thermoplastic copolyether ester resin, as taught in the prior art EPO 0 327 010.
• the mixture is dynamically cured by mixing for 2 to 3 minutes at 220°C an the composition is compression molded into test specimens an tested for tensile strength properties according to AST D-412. For comparative purposes, tests are run without curing.
• the results along with compositional data are set forth belo in Table 2.
• Polyacrylate elastomer having alkylhalide vinyl ether cure sites (Zeon Chemicals Co.) Polyetherimide ester ("LO-MOD” J1013, General Electric Co., prepared in accordance with Exampl c 1 of McCready, U.S. Pat. No. 4,556,705) d Polyetherimide ester ("LO-MOD” JB1090, General Electric Co.) e Polyetherimide ester (General Electric Co., see footnote c) f Quaternary Ammonium Accelerator (Zeon Chemicals Co.) Sodium Stearate
• Example Type 1 bars Tensile Break, psi Elongation Break, % Young's Modulus, psi 100% Modulus, psi 200% Modulus, psi Percent Strain at Yld. Hardness, Shore-A
• compositions of the present invention are placed under Dynamic Mechanical Thermal Analysis (DMTA) to produce DMTA curves ' .
• DMTA Dynamic Mechanical Thermal Analysis
• Typical thermoplastic materials such as the thermoplastic elastomers used herein, exhibit storage modulus versus temperature DMTA curves which can be described as possessing a glassy plateau which is generally constant in magnitude, followed by a glass transition region which is characterized by a two to three order of magnitude drop in the storage modulus to the so-called rubbery plateau.
• the rubbery plateau-storage modulus value is then usually observed to decrease with increasing temperature in thermoplastics (i.e. viscous flow) .
• semi-crystalline thermoplastics the rubbery plateau is then followed by a large drop off at the crystalline melting point of the polymer.
• the drop off of modulus associated with the melting of the polyetherimide ester is observed to be followed by what may be termed a second rubbery plateau which was found to be of essentially constant magnitude to the extent of the temperature tested (250° C) .
• the presence of this second rubbery plateau was found to be dependent on the ratio of rubber to thermoplastic with compositions having below 50 weight percent rubber not exhibiting the second rubbery plateau.
• the storage modulus would be essentially constant in the rubbery plateau region and would not drop off with increasing temperature (until degradation occurs), due to crosslinking of the system.
• thermoplastici y of the compositions a typical material which exhibits the second rubbery plateau was prepared, molded and then heated for 75 minutes at 200° C in an air circulating oven. The material is then charged into a Brabender mixer and mixed to a molten state in which the consistency was observed to be constant as a function of time over a ten minute test period.
• the materials are thermoplastics. If the materials were becoming thermoset above the melting point of the crystalline thermoplastic polyetherimide ester, they would have shear degraded when reprocessed as does a true thermoset material.

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