EP0554369A1 - Melanges binaires de poly(alkylene cyclohexanedicarboxylate) - Google Patents

Melanges binaires de poly(alkylene cyclohexanedicarboxylate)

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Publication number
EP0554369A1
EP0554369A1 EP91920277A EP91920277A EP0554369A1 EP 0554369 A1 EP0554369 A1 EP 0554369A1 EP 91920277 A EP91920277 A EP 91920277A EP 91920277 A EP91920277 A EP 91920277A EP 0554369 A1 EP0554369 A1 EP 0554369A1
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EP
European Patent Office
Prior art keywords
composition
ether
poly
ester
acid
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.)
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EP91920277A
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German (de)
English (en)
Inventor
William Frederick Hendri Borman
Nan-I Liu
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General Electric Co
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • 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 comprising (A) polyester resins comprising the reaction product of at least one straight chain, branched, or cycloaliphatic C 2 -C 10 alkane diol or a chemical equivalent thereof, and at least one cycloaliphatic diacid or chemical equivalent thereof and (B) a poly (ether ester) elastomer, a poly(etherimide ester) elastomer, a copolymer elastomer comprising (ether ester) monomers and (etherimide ester) monomers, a copolymer comprising ethylene and one or more comonomers copolymerizable therewith to produce a solid copolymer, or a combination of any of the foregoing. Filled and flame retardant compositions as above are contemplated as well.
  • compositions have increased tensile strength when compared with the tensile strength of the polyester component or the modifier component alone. Surprisingly, the compositions exhibit enhanced melt flow in comparison with state of the art materials as well.
  • Novel compositions comprising a polyester resin which is the reaction product of at least one straight chain, branched, or cycloaliphatic C 2 ⁇ C 10 alkane diol or a chemical equivalent thereof and at least one cycloaliphatic diacid or a chemical equivalent thereof combined with a poly(ether ester) elastomer, a poly(etherimide ester) elastomer, a copolymer elastomer comprising (ether ester) monomers and (etherimide ester) monomers, a copolymer comprising (i) ethylene and (ii) one or more comonomers copolymerizable therewith to produce a solid copolymer have been discovered which have improved tensile strength.
  • Weatherable, UV radiation resistant, solvent resistant, resilient, high tensile strength, high impact polymers have great application in the manufacture of molded or thermoformed products such as automobile external parts, lawn and garden equipment, and sporting goods.
  • Crystallizable polyesters of cycloaliphatic diacids or derivatives thereof with aliphatic and/or cycloaliphatic diols have relatively high melting points and are quite UV resistant as they do not appreciably absorb near-UV light. Many of these polyesters were explored for use as hot melt adhesives. See, Jackson et al., J. Applied Polymer Science, Vol. 14, 685-98, (1970); U.S. Patent No. 3,515,628.
  • Friction activatable solvent-free adhesives comprising a thermoplastic polyester derived from one or more saturated aliphatic dicarboxylic acid and/or aromatic dicarboxylic acids and one or more saturated aliphatic diols, a tackifier, and a plasticizer are disclosed by Wayne et al, U.S. Patent No. 4,066,600.
  • thermoplastic elastomeric molding compositions comprising a poly(etherimide ester) elastomer modified with a combination of poly(butylene terephthalate) , a monoalkenyl arene-conjugated diene copolymer and a polycarbonate.
  • compositions of the present invention A major deficiency of the previous compositions has been their relatively low tensile strength. This disadvantage is overcome by the compositions of the present invention.
  • the tensile strength at yield of the polyester resins of the present invention are improved by the addition of polylether ester) elastomers, poly(ethermide ester) elastomers, (ether ester)/(etherimide ester) copolymer elastomers, EVA type copolymers or combinations of any of the foregoing modifier polymers each of wnich has a lower tensile strength than the polyester resin.
  • compositions comprising (A) a polyester resin comprising the reaction productof (a) at least one straight chain, branched, or cycloaliphatic C 2 -C- 0 alkane diol or chemical equivalent thereof; and (b) at least one cycioaliphatic diacid or chemical equivalent thereof; and (B)(a) a poly(ether ester) elastomer, (b) a poly (etherimide ester) elastomer, (c) a copolymer elastomer comprising (i) (ether ester) monomers and (ii) (etherimide ester) monomers, (d) a copolymer comprising (i) ethylene and (ii) one or more comonomers copolymerizable therewith to produce a solid copolymer, or (d) a combination of any of the foregoing.
  • the diols useful in the preparation of polyester resins (A) of the present invention are straight chain, branched, or cycloaliphatic but preferably straight chain or branched alkane diols and may contain from 2 to 10 carbon atoms.
  • examples of such glycols include, but are not limited to, ethylene glycol; propylene glycol, i.e.
  • 1,2- and 1,3-propylene glycols 1,2- and 1,3-propylene glycols; butane diol, i.e., 1,3- and 1,4-butane diol; diethylene glycol; 2,2-dimethyl-l,3-propane diol; 2-ethyl, 2-methyl, 1,3-propane diol; 1,3- and 1,5-pentane diol; dipropylene glycol; 2-methyl, 1,5-pentane diol; 1,6-hexane diol; 1,4-cyclohexane dimethanol and particularly its cis- and trans-enantiomers; triethylene glycol; 1,10-decane diol; and mixtures of any of the foregoing. Particularly preferred is 1,4-butane diol.
  • a cycloaliphatic diol or chemical equivalent thereof and particularly 1,4-cyclohexane dimethanol or its chemical equivalents are to be used as the diol component, it is preferred that a mixture of cis- to trans-enantiomer thereof, ranging from 1 to 4 to 4 to 1 and preferably a ratio of 1 to 3 is used.
  • Chemical equivalents of these diols include esters and ethers such as dialkyl esters, diaryl esters, polytetramethylene oxide, and the like.
  • the diacids (A) (b) useful in the preparation of the polyester resins (A) of the present invention are cyclo- aliphatic diacids. This is meant to include carboxylic acids having two carboxyl groups each of which is attached to a saturated carbon in a saturated ring.
  • a preferred diacid is 1,4-cyclohexanedicarboxylic acid and most preferred is trans-l,4-cyclohexane dicarboxylic acid as further explained below.
  • Cyclohexanedicarboxylic acids and their chemical equivalents can be prepared, for example, by the hydrogenation of cycloaromatic diacids and corresponding derivatives such as isophthalic acid or terephthalic acid in a suitable solvent, water or acetic acid at room temperature and at atmospheric pressure using suitable
  • SUBSTITUTESHEET catalysts such as rhodium supported on a suitable carrier of carbon or alumina. See, Freifelder et al. Journal of Organic Chemistry, 31, 3438 (1966); U.S. Patent Nos. 2,675,390 and 4,754,064. They may also be prepared by the use of an inert liquid medium in which a phthalic acid is at least partially soluble under reaction conditions and a catalyst of palladium or ruthenium in carbon or silica. See, U.S. Patent Nos. 2,888,484 and 3,444,237. Typically, in the hydrogenation, two enantiomers are obtained in which the carboxylic acid groups are in cis- or trans-positions.
  • the cis- and trans-enantiomers can be separated by crystallization with or without a solvent, for example, n-heptane, or by distillation.
  • a solvent for example, n-heptane, or by distillation.
  • the cis-enantiomer tends to blend better; however, the trans-enantiomer has higher melting and crystallization temperatures and is especially preferred.
  • Mixtures of the cis- and trans-enantiomers are useful herein as well, and preferably when such a mixture is used, the trans-enantiomer will comprise at least 75 parts by weight and the cis-enantiomer will comprise the remainder based upon 100 parts by weight of cis- and trans-enantiomer combined.
  • component (A) When a mixture of enantiomers or more than one different diacid is used, a copolyester or a mixture of two polyesters for use as component (A) may be used.
  • Chemical equivalents of the cycloaliphatic diacids include esters, alkyl esters, e.g., dialkyl esters, diaryl esters, anhydrides, acid chlorides, acid bromides, and the like.
  • the preferred chemical equivalents comprise the dialkyl esters of the cycloaliphatic diacids, and the most preferred chemical equivalent comprises the dimethyl ester of the cycloaliphatic diacid, particularly dimethyl-trans-1,4- cyclohexanedicarboxylate.
  • Dimethyl-l,4-cyclohexanedicarboxylate can be obtained by ring hydrogenation of dimethylterephthalate, and two enantiomers having the carboxylic acid groups in the cis- or trans- positions are obtained.
  • the enantiomers can be separated as above, and the trans-enantiomer is especially preferred for the reasons above. Mixtures of the enantiomers are suitable as explained above and preferably in amounts as explained above.
  • polyester resins (A) of the present invention are typically obtained through the condensation or ester interchange polymerization of the diol or diol equivalent component (A) (a) with the diacid or diacid equivalent component (A) (b) and have recurring units of the formula 0 0
  • R represents an alkyl or cycloalkyl radical containing 2 to 10 carbon atoms and which is the residue of a straight chain, branched, or cycloaliphatic alkane diol having 2 to 10 carbon atoms or of a chemical equivalent thereof;
  • R is a cycloaliphatic radical which is the decarboxylated residue derived from a cycloaliphatic diacid or chemical equivalent thereof. They particularly have recurring units of the formula
  • R from above is derived from 1,4-butane diol; and wherein R from above is a cyclohexane ring derived from cyclohexanedicarboxylate or a chemical equivalent thereof and is selected from the cis- or trans-enantiomers thereof.
  • polyesters can be made following the teachings of, for example, U.S. Patent Nos. 2,465,319
  • the reaction is generally run with an excess of the diol component and in the presence of a suitable catalyst such as a tetrakis(2-ethyl hexyl)titanate, in a suitable amount, typically about 20 to 200 ppm of titanium based upon the final product.
  • a suitable catalyst such as a tetrakis(2-ethyl hexyl)titanate
  • the poly(ether ester) elastomer modifier (B)(a) for use in the invention is a random or a block copolymer consisting of polyester segments and polyether segments having molecular weights of 400 to 20,000.
  • these are prepared by conventional esterification/polycondensation processes from (i) one or more diols, (ii) one or more dicarboxylic acids, (iii) one or more long chain ether glycols, and optionally, (iv) one or more lactones or polylactones.
  • Diols (B)(a)(i) which can be used in the preparation of these poly(ether ester) elastomers include both saturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds. These diols are preferably of low molecular weight, i.e. having molecular weight of about 250 or less.
  • diols and low molecular weight diols with respect to the poly(ether ester) elastomers 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 include 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 useful in the production of the poly(ether ester) elastomers are generally those having from about 2 to about 20 carbon atoms, including ethylene glycol; propanediol; butanediol; pentanediol; 2-methyl propanediol; 2,2-dimethyl propanediol; hexanediol; decanediol; 1,2-, 1,3- and ,4-dihydroxy cyclohexane; 1,2-, 1,3-, and 1,4-cyclohexane dimethanol; butenediol; hexenediol, and the like.
  • Aromatic diols suitable for use in the preparation of the poly(ether ester) elastomers are generally those having from 6 to about 19 carbon atoms. Included among the aromatic dihydroxy compounds are resorcinol; hydroquinone; 1,5-dihydroxy naphthalene; 4,41-dihydroxy diphenyl;bis(p-hydroxy phenyl)methane and 2,2-bis(p-hydroxy phenyl) propane.
  • Especially preferred 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.
  • the preferred poly(ether ester) elastomers are those in which 1,4-butane diol is present in a predominant amount.
  • Dicarboxylic acids (B)(a)(ii) which are suitable for use in the preparation of the poly(ether ester) elastomers include 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 350; however, higher molecular weight dicarboxylic acids, especially dimer acids, may also be used.
  • the term "dicarboxylic acids" with respect to the poly(ether ester) elastomers 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
  • SUBSTITUTESHEET acid halides and anhydrides may contain any substituent group(s) or combinations which do not substantially interfere with the polymer formation and use of the polymer in the practice of this invention.
  • Aliphatic dicarboxylic acids with respect to the poly(ether ester) elastomers, include 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 saturated ring, the acid is cycloaliphatic.
  • Aromatic dicarboxylic acids useful in the preparation of poly(ether ester) elastomers 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 -0- or ⁇ S0 2 ⁇ .
  • Representative aliphatic and cycloaliphatic acids which can be used in the preparation of the poiy(ether ester) elastomers are preferably C.-C.. dicarboxylic acids such as but not limited to 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, dimer acid, 2-ethylsuberic acid, tetramethylsuccinic acid, cyclopentane dicarboxylic acid, decahydro-l,5-naphthalene dicarboxylic acid,
  • SUBSTITUTESHEET 1,1-cyclobutanedicarboxylic acid Preferred aliphatic acids are cyclohexanedicarboxylic acid, sebacic acid, di er acid, glutaric acid, azelaic acid and adipic acid.
  • aromatic dicarboxylic acids which can be used in this preparation include terephthalic, phthalic and isophthalic acids, bi-benzoic acid, substituted dicarboxy compounds with two benzene nuclei such as bis(p-carboxyphenyl) methane, oxybis (benzoic acid), ethylene, l , 2 - b i s - ( p - o x y b e n z o i c a c i d ) , 1 , 5 -naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene- dicarboxylic acid, phenanthrenedicarboxylic acid, anthracenedicarboxylic acid, 4,4'-sulfonyldibenzoic acid, and halo and C.
  • terephthalic, phthalic and isophthalic acids bi-benzoic acid, substitute
  • dicarboxylic acids for the preparation of the poly(ether ester) elastomers are the aromatic dicarboxylic acids, mixtures thereof and mixtures of one or more dicarboxylic acids with an aliphatic and/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. Especially preferred is dimethyl terephthalate.
  • dicarboxylic acids where mixtures of dicarboxylic acids are employed, it is preferred that at least about 60 mole percent, and preferably at least about 80 mole percent, based on 100 mole percent of dicarboxylic acid (B)(a)(ii) are of the same dicarboxylic acid or ester derivative thereof.
  • the preferred dicarboxylic acid (B)(a)(ii) are of the same dicarboxylic acid or ester derivative thereof.
  • SUBSTITUTESHEET poly(ether esters) are those in which dimethyl terephthalate is the predominant dicarboxylic acid.
  • Suitable long chain ether glycols (B)(a)(iii) which can be used in the preparation of the thermoplastic poly(ether ester) elastomers 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 have a carbon-to-oxygen ratio of from about 1.8 to about 4.3, exclusive of any side chains.
  • poly(oxyalkylene) glycols are 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 end-capped poly(propylene ether)glycol or propylene oxide end-capped poly(ethylene ether)glycol and predominately poly(ethylene ether), poly(propylene ether), or poly(ethylene ether) and poly(propylene 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 used in proportions such
  • Polyformal glycols prepared by reacting formaldehyde with diols such as 1,4-butanediol and 1,5-pentanediol are also useful.
  • Especially preferred poly(oxyalkylene) glycols are poly(propylene ether) glycol, poly(tetramethylene ether) glycol and predominantly poly(ethylene ether), poly(propylene ether), or poly(ethylene ether) and poly(propylene ether) backbone copoly(propylene ether-ethylene ether)glycol.
  • these poly(ether ester) elastomers may have incorporated therein one or more lactones or polylactones (iv) .
  • lactone modified poly(ether esters) are disclosed in pending U.S. Patent Application Serial No. 643,985 filed August 24, 1984.
  • Lactones (B)(a)(iv) suitable herein are widely available commercially, e.g.. Union Carbide Corporation and Aldrich Chemicals. While epsilon caprolactone is especially preferred, it is also possible to use substituted lactones wherein the lactone is substituted by a lower alkyl group such as a methyl or ethyl group at the alpha, beta, gamma, delta, or epsilon positions. Additionally, it is possible to use polylactone, including homopolymers and copolymers thereof with one or more components, as well as hydroxy terminated polylactone, as block units in these poly(ether esters). Suitable polylactones and processes for their production are described in for example, U.S. Patent Nos. 3,761,511; 3,767,627; and 3,806,495.
  • suitable poly(ether ester) elastomers (B)(a) are those in which the weight percent of ( ⁇ i) long chain ether glycol component or the combined weight percent of (iii) long chain ether glycol component and (iv) lactone component in the poly(ether ester) is from about 5 to about 80 weight percent.
  • the weight percent of (iii) or (iii) and (iv) is from about 10 to 50 weight percent.
  • the poly(ether ester) elastomers (B)(a) 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.
  • polyester segment are poly(l,4-butylene terephthalate) and poly(ethylene terephthalate) .
  • Preferred polyether segments include a polyalkylene ether glycol, e.g., polyethyleneoxide glycol, polytetramethylene oxide glycol, polypropylene oxide glycol, or a mixture thereof; an aliphatic polyester; or polyalphacaprolactone.
  • the poly(etherimide esters) elastomers (B) (b) of the present invention comprise the reaction product of (i) one or more diols; (ii) one or more dicarboxylic acids; and (iii)(l)(I) one or more polyoxyalkylene diimide diacids; and optionally (II) one or more tricarboxylic acids or derivatives thereof; (2) a combination of (I) one or more polyoxyalkylene diimide diacids; (II) one or more dimer acids wherein the amount of dimer is from about 5 to about 40 parts by weight based upon 100 parts by weight of (I) and (II); and optionally, (III) one or more tricarboxylic acids or derivatives thereof; or (3) a combination of (I) one or more high molecular weight poly(oxyalkylene) diamines; and (II) one or more tricarboxylic acids or derivatives thereof.
  • Preferred poly(etherimide ester) elastomers may be prepared from (i) one or more diols, preferably low molecular weight diols, and preferably, one or more C 2 - C 15 aliphatic and/or cycloaliphatic diols, (ii) one or more dicarboxylic acids, preferably, one or more C.
  • the amount of polyoxyalkylene diimide diacid employed is generally dependent upon the desired properties of the resultant poly(etherimide ester) .
  • the weight ratio of polyoxyalkylene diimide diacid component (iii)(l), (2), and/or (3) to dicarboxylic acid (b) is from about 0.25 to about 2.0, and preferably from about 0.4 to about 1.4.
  • These elastomers may contain additional stabilizers for even greater stabilization and low temperature impact strength.
  • Suitable diols (B)(b)(i) for use in preparing the poly(etherimide esters) elastomers include those described above in the preparation of the poly(ether ester) elastomers (B)(a).
  • Dicarboxylic acids (B)(b)(ii) which are suitable for use in the preparation of the poly(etherimide esters) herein are as described above in the preparation of poly(ether esters) above.
  • the molecular weight preference pertains to the acid and not to its equivalent ester or ester-forming
  • poly(etherimide ester) elastomers are high molecular weight diimide diacids wherein the number average molecular weight is greater than about 700 and 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.
  • 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.
  • they may be derived from trimellitic anhydride and a polyalkylene diamine having the formula H 2 N-G-NH 2 wherein G is the divalent radical remaining after removal of the amino groups of a large chain alkylene ether diamine having a molecular weight of from about 600 to 1200.
  • polyoxyalkylene diimide diacids 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 1 is independently selected from the group consisting of hydrogen, C, to C 6 aliphatic and cycloaliphatic monovalent organic radicals and C g to C 12 aromatic monovalent organic radicals, e.g.
  • G is the divalent radical remaining after the removal of the terminal (or as nearly terminal as possible) hydroxy groups of a long chain ether glycol or the divalent radical remaining after the reinoval of the terminal (or as nearly terminal as possible) amino groups of a long chain alkylene ether diamine, either of which have 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 from about 1.8 to about 4.3.
  • Representative long chain ether glycols from which the polyoxyalkylene diamines are 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 or ethylene oxide terminated with poly(propylene ether)glycol or a combination thereof; 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).
  • a second monomer such as methyl tetrahydrofuran
  • poly(alkylene ether)glycols are poly(propylene ether)glycol and poly(ethylene ether)glycols end-capped with poly(propylene ether)glycol and/or propylene oxide, poly(ethylene ether)glycol and/or ethylene oxide or a combination thereof.
  • the useful polyoxyalkylene diamines will have an average molecular weight of from about 600 to 12000, preferably from about 900 to about 4000.
  • the tricarboxylic acids useful herein 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 nonimidizable.
  • 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-naphthalenetricarboxylic anhydride; 3,3' ,4-diphenyl tricarboxylic anhydride; 3,3', 4- benzophenonetricarboxylic anhydride;
  • 1,3,4 - cy c 1 open tane tricarboxylic anhydride 2,2' ,3 -diphenyl tricarboxylic anhydride; diphenyl sulfone-3,3 '4-tricarboxylic anhydride, ethyl enetricarboxyl ic anhydride ;
  • R is a trivalent organic radical, preferably a C 2 to C 20 aliphatic, aromatic, or cycloaliphatic trivalent organic radical and R 1 is preferably hydrogen or a monovalent organic radical preferably selected from the
  • SUBSTITUTE BHE ⁇ group consisting of C. to C 12 aromatic radicals, e.g. benzyl; and most preferably hydrogen.
  • 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 ° 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.
  • Dimer acids (B) (b) (iii) (2) (II) useful herein are themselves prepared by the dimerization of unsaturated fatty acids of 18 carbons.
  • exemplary of fatty acids from which they may be prepared include but are not Omited to oleic acid, linoleic acid and linolenic acid.
  • the preparation and structure of dimer acid is described in Journal of the American Oil Chemists Society, 39, 534-545 (1962), Journal of the American Chemical Society, 66, 84 (1944) and U.S. Patent No. 2,347,562.
  • Suitable dimer acids may be employed in their unhydrogenated or hydrogenated form and include the acid derivatives thereof.
  • EMPOL 1010 (a hydrogenated dimer acid) and EMPOL 1014.
  • EMPOL 1010 is reported as typically containing 97 percent dimer acid, 3 percent trimer acid and essentially no monobasic acid and extremely low unsaturation, whereas EMPOL 1014 is typified as containing 95 percent, 4 percent and 1 percent of dimer, trimer and monobasic acids respectively. Also available are the dimer acids sold under the tradename HYSTRENE from the Humko Products Division of Witco
  • SU BST ITUTESHEET typically contain 95 percent dimer acid and a weight ratio of dimer to trimer of 36:1. Preferred grades are substantially free of such monomer and trimer fractions, most preferably less than 5 percent by weight, and are fully saturated, or substantially so.
  • the dimer acid member may be substantially freed of monomer and trimer fractions by molecular distillation or other suitable means.
  • the dimer acid exists in the poly(etherimide ester) elastomers as a soft or rubber segment, and accordingly, dimer acids of relatively high molecular weight (preferably greater than about 500) are preferred so that the poly(etherimide ester) elastomers are resilient, but do not deform until relatively high temperatures are reached.
  • the weight ratio of the above ingredients is not critical.
  • the poly(etherimide ester) elastomers comprise the reaction product of dimethylterephthalate, optionally with up to 40 mole percent of another dicarboxylic acid; 1,4-butane diol, optionally with up to 40 mole percent 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 600 to about 12000, preferably from about 900 to about 4000, and trimellitic anhydride.
  • the diol will be 100 mole percent 1,4-butane diol and the dicarboxylic acid, 100 mole percent dimethylterephthalate.
  • the poly(etherimide ester)elastomer will comprise the reaction product of dimethylterephthalate, optionally with up to 40 mole percent of another dicarboxylic
  • SUBS TITUTE &HEg ⁇ acid 1,4-butane diol, optionally with up to 40 mole percent of another saturated or unsaturated aliphatic and/or cycloaliphatic diol; and a combination of (I) a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene diamine of molecular weight of from about 600 to about 12000, preferably from about 900 to 4000 and (II) dimer acid in an amount of from about 10 to about 40 percent by weight, most preferably from about 15 to about 30 percent by weight based on the combined weight of (I) and (II), and optionally trimellitic anhydride.
  • a polyoxyalkylene diimide diacid prepared from a polyoxyalkylene diamine of molecular weight of from about 600 to about 12000, preferably from about 900 to 4000 and (II) dimer acid in an amount of from about 10 to about 40 percent by weight, most preferably from about 15 to about 30 percent by weight based
  • the diol will be 100 mole percent 1,4-butane diol
  • the dicarboxylic acid will be 100 mole percent dimethylterephthalate.
  • These poly(etherimide ester) elastomers 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. Patent Nos. 3,023,192; 3,763,109; 3,651,014; 3,663,653; and 3,801,547. 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 of the coly(etherimide ester) elastomers 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 appropriate, 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 or salts thereof, in order to increase 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 or salts thereof, in order to increase the thermal stability of the resultant polymer.
  • Suitable catalysts include but are not limited to the acetates, carboxylates, hydroxides, oxides, alcoholates or organic complex compounds of zinc, manganese, antimony, cobalt, lead, calcium and the alkali metals insofar as these compounds are soluble in the reaction mixture. Specific examples include, zinc acetate, calcium acetate and combinations thereof with antimony trioxide and the like. These catalysts as well as additional useful catalysts are described in U.S. Patent Nos. 2,465,319; 2,534,029; 2,850,483; 2,892,815; 2,937,160; 2,998,412; 3,047,539; 3,110,693 and 3,385,830.
  • the titanium catalysts including the inorganic and organic titanium containing catalysts, such as those described in, for example U.S. Patent Nos. 2,720,502; 2,727,881; 2,729,619; 2,822,348; 2,906,737; 3,047,515; 3,056,817; 3,056,818; and 3,075,952.
  • the 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.
  • etherimide esters as described above are suitable for use in the present invention.
  • a copolymer will comprise a block copolymer having polylether ester) blocks and poly(etherimide ester) blocks. Preparation of such copolymers can be affected as above and would be within the skill of one of ordinary skill in the art.
  • copolymers (B)(d) comprising (i) ethylene and (ii) one or more comonomers copolymerizable therewith to produce a solid copolymer preferably comprise 40 to 80 parts by weight of (i) and 20 to 60 parts by weight of (ii) based upon 100 parts by weight of (i) and (ii) combined, and most preferably comprise 50 to 70 parts by weight of (i) and 30 to 50 parts by weight of (ii) based upon 100 parts by weight of (i) and (ii) .
  • the comonomer (B)(d)(ii) comprises an unsaturated mono- or dicarboxylic acid of 2-20 carbon atoms, esters of unsaturated mono- or dicarboxylic acids, vinyl esters of saturated carboxylic acids where the acid has 1-13 carbon atoms, vinyl alkyl ethers wherein the alkyl group has 1-18 carbon atoms, acrylonitrile, norbornene, alpha-olefins of 3-12 carbon atoms, and vinyl aromatic compounds.
  • vinyl acetate is especially preferred.
  • component (A) comprises a major portion and component
  • component (B) comprises a minor portion of (A) and (B), preferably component (A) comprises from about 75 to about 99 parts by weight and component (B) comprises from about 1 to about 25 parts by weight based upon 100 parts by weight of (A) and (B) combined, and most preferably, component (A) comprises about 80 parts by weight and component (B) comprises about 20 parts by weight based upon 100 parts by weight of (A) and (B) combined.
  • compositions of the present invention may be molded, extruded or thermoformed into articles by conventional methods known to one of ordinary skill in the art.
  • Conventional processes for mixing thermoplastic polymers can be used for the manufacture of the compositions within the present invention.
  • the compositions can be manufactured using any suitable mixing equipment, cokneaders, or extruders under conditions known to one of ordinary skill in the art.
  • additives such as stabilizers, for example 3,5-di-tert-butyl-4 hydroxy hydrocinnamic triester with l,3,5-tris-(2-hydroxy ethyl)-3-triazine-2,4,6-(lH,3H,5H) trione, reinforcing fillers, flame retardants, impact modifiers, pigments or combinations of any of the foregoing, may be added to the compositions of the present invention.
  • stabilizers for example 3,5-di-tert-butyl-4 hydroxy hydrocinnamic triester with l,3,5-tris-(2-hydroxy ethyl)-3-triazine-2,4,6-(lH,3H,5H) trione
  • reinforcing fillers such as flame retardants, impact modifiers, pigments or combinations of any of the foregoing
  • Impact modifiers useful herein include but are not limited to multi-stage core-shell polymers having a rubbery core derived from an acrylate or a (meth)acrylate, a diene, or a mixture of the foregoing, and a vinyl-based polymer or copolymer outer shell, some of which are available commercially under the tradenames ACRYLOID®KM 330, also known as PARALOID® EXL 3330, or ACRYLOID ® KM 653, also known as PARALOID ® EXL 3691, from Rohm & Haas Company.
  • ACRYLOID®KM 330 also known as PARALOID® EXL 3330
  • ACRYLOID ® KM 653 also known as PARALOID ® EXL 3691
  • Suitable impact modifiers also include ABS modifiers which are typically represented by graft copolymersof vinyl cyanide-conjugated diolefin-alkenyl aromatic .
  • the ratio of styrene to acrylonitrile in the terpolymer ranges from about 3.5 to 1 to about 2.5 to 1 and the ratio of butadiene to styrene/acrylonitrile is 7 to 3. Most preferably, the ratio of styrene to acrylonitrile is either 3.5 to 1, 3 to 1 or 2.5 to 1.
  • EXAMPLE 1 A well mixed dry blend of 80.0 parts of poly(l,4-butylene cyclohexanedicarboxylate) (PBCD)
  • Example 1 The procedure of Example 1 was followed substituting 100.0 parts of PBCD (melt viscosity 5500 poise) for the dry blend. Properties are summarized in Table 1.
  • Example 2 The procedure of Example 1 was followed substituting a dry blend of 80.0 parts of PBCD (melt viscosity 5500 poise) and 20.0 parts of poly(etherimide ester) (LOMOD J25-General Electric Company) .
  • Example 2A The procedure of Example 1 was followed substituting 100.0 parts of poly(etherimide ester) elastomer (LOMOD ® J25 General Electric Company) for the dry blend.
  • LOM ® J25 General Electric Company poly(etherimide ester) elastomer
  • Example 1 The procedure of Example 1 is followed substituting a dry blend of 80.0 parts by weight of
  • PBCD melt viscosity 5500 poise
  • Example 1 The procedure of Example 1 was followed substituting 100.0 parts ethylene-vinyl acetate copolymer (ELVAX ® 350-EVA-E.I. DuPont de Nemours & Co.
  • Examples 1-4 when compared with Comparative Examples 1A*, IB*, 2A* and 3A* illustrate the improvement in tensile strength at yield by the addition of the particular modifiers with relatively low tensile strength impart to polyesters of the present invention.
  • the blends of the examples can comprise poly(25-cis:75-trans-l,4-cyclohexanedimethylene- trans-l,4-cyclohexanedicarboxylate) . All such obvious variations are within the full intended scope of the appended claims.

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

Cette invention concerne des compositions comprenant une résine polyester qui contient le produit de réaction d'au moins un diol alcane C2-C10 à chaîne linéaire, ramifiée, ou cycloaliphatique ou d'un équivalent chimique de ce dernier et d'un diacide cycloaliphatique ou d'un équivalent chimique de ce dernier; un élastomère de poly(éther ester), un élastomère de poly(étherimide ester), un élastomère de copolymère comprenant des monomères d'(ether ester) et des monomères d'(étherimide ester), un copolymère comprenant de l'éthylène et un ou plusieurs comonomères pouvant être copolymérisés avec ce dernier pour produire un copolymère solide, ou une combinaison de n'importe lequel de ces derniers. Ces compositions présentent d'excellentes propriétés mécaniques à la traction.
EP91920277A 1991-08-27 1991-08-27 Melanges binaires de poly(alkylene cyclohexanedicarboxylate) Ceased EP0554369A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PCT/US1991/006094 WO1993004124A1 (fr) 1991-08-27 1991-08-27 Melanges binaires de poly(alkylene cyclohexanedicarboxylate)
EP92300155A EP0551685B1 (fr) 1991-08-27 1992-01-08 Poly(cyclohexanedicarboxylate d'alcoylène)-(téréphthalate d'alcoylène) copolyesters et compositions
EP92300163A EP0551686A1 (fr) 1991-08-27 1992-01-08 Modification de mélanges de poly(cyclohexanedicarboxylate d'alcoylène)
JP4075621A JPH05287182A (ja) 1991-08-27 1992-02-27 改質ポリエステル樹脂組成物

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EP0554369A1 true EP0554369A1 (fr) 1993-08-11

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EP91920277A Ceased EP0554369A1 (fr) 1991-08-27 1991-08-27 Melanges binaires de poly(alkylene cyclohexanedicarboxylate)
EP92300163A Withdrawn EP0551686A1 (fr) 1991-08-27 1992-01-08 Modification de mélanges de poly(cyclohexanedicarboxylate d'alcoylène)
EP92300155A Expired - Lifetime EP0551685B1 (fr) 1991-08-27 1992-01-08 Poly(cyclohexanedicarboxylate d'alcoylène)-(téréphthalate d'alcoylène) copolyesters et compositions

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EP92300163A Withdrawn EP0551686A1 (fr) 1991-08-27 1992-01-08 Modification de mélanges de poly(cyclohexanedicarboxylate d'alcoylène)
EP92300155A Expired - Lifetime EP0551685B1 (fr) 1991-08-27 1992-01-08 Poly(cyclohexanedicarboxylate d'alcoylène)-(téréphthalate d'alcoylène) copolyesters et compositions

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EP (3) EP0554369A1 (fr)
JP (1) JPH05287182A (fr)
DE (1) DE69233006T2 (fr)
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CN103788595A (zh) * 2014-01-17 2014-05-14 安徽万泰电缆有限公司 一种高强阻燃电缆护套材料
CN103788596A (zh) * 2014-01-17 2014-05-14 安徽万泰电缆有限公司 一种无卤耐磨电缆护套材料

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CN103788595A (zh) * 2014-01-17 2014-05-14 安徽万泰电缆有限公司 一种高强阻燃电缆护套材料
CN103788596A (zh) * 2014-01-17 2014-05-14 安徽万泰电缆有限公司 一种无卤耐磨电缆护套材料

Also Published As

Publication number Publication date
DE69233006D1 (de) 2003-05-22
EP0551686A1 (fr) 1993-07-21
EP0551685B1 (fr) 2003-04-16
EP0551685A1 (fr) 1993-07-21
DE69233006T2 (de) 2004-03-11
WO1993004124A1 (fr) 1993-03-04
JPH05287182A (ja) 1993-11-02

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