Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
  • C08L69/005—Polyester-carbonates

Definitions

• compositions comprised of (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 a chemical equivalent thereof; and (B) a polycarbonate resin, as well as to such compositions modified by the addition of an effective modulus modifying amount of a core-shell multi-stage polymer having a rubbery core derived from an acrylate or (meth)acrylate, a diene or a mixture of any of the foregoing and a vinyl-based polymer or copolymer outer shell or of a vinyl cyanide-conjugated diolefin-alkyl aromatic ABS-type terpolymer. Also included are modified compositions further comprising an additional polyester resin which may be the same as or different than the first polyester resin as well as filled and/or flame retardant compositions.
• compositions of the present invention are homogeneous and retain transparency. All of the compositions of the present invention, both modified and unmodified, exhibit significantly higher stiffness than that of the individual components, enhanced melt flow, and retain excellent impact strength.
• Novel compositions comprising a polyester resin which is the reaction product of at least one straight chain, branched, or cycloaliphatic C 2 -C ⁇ Q alkane diol or a chemical equivalent thereof and at least one cycloaliphatic diacid or a chemical equivalent thereof
• SU BSTITUTESHEET combined with a polycarbonate resin have been discovered which are homogeneous and transparent, have significantly higher stiffness measured as flexural modulus than the modulus of either component, and retain excellent impact strength at a wide range of temperatures.
• Modified compositions comprising the compositions above and an appropriate core-shell multi ⁇ stage polymer modifier or ABS-type polymer modifier as well as such modified compositions containing an additional polyester resin, retain superior stiffness and impact properties as well.
• Weatherable, UV radiation resistant, solvent resistant, resilient, 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 Review, Vol. 14, 685-98, (1970); U.S. Patent No. 3,515,628. ilfong, J. Polymer Sci., Vol. 54, 385-410
• polyesters of hexahydro terephthalic acid the cis-/trans-mixture of cyclohexanedicarboxylic acids obtained by the hydrogenation of terephthalic acid.
• Kibler et al, U.S. Patent No. 2,901,466, disclose linear polyesters and polyester-amides prepared by condensing cis- and/or trans-l,4-cyclohexanedimethanol
• Friction activatable solvent-free adhesives comprising a thermoplastic linear 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.
• Scott U.S. Patent No. 4,125,572, describes a thermoplastic molding composition and articles molded therefrom that retain optical clarity comprising a polycarbonate, a poly(1,4-butylene terephthalate), and a copolyester of an aliphatic or cycloaliphatic diol and a mixture of terephthalic and isoterephthalic acids. Scott discloses that blends of polycarbonate and polyalkylene terephthalate, as described in U.S. Patent No. 3,218,372, tend to lose their transparency when the amount of poly(1,4-butylene terephthalate) is greater than about 10 percent or when they are heat aged.
• compositions comprising a poly(1,4-butylene terephthalate) resin modified by a combination of a polyacrylate resin and an aromatic polycarbonate resin.
• the polyesters of the DeRudder compositions differ from alkane diol cyclohexane- dicarboxylate-based resins of the present invention.
• Example 19 Copending application, DeRudder et al, U.S. Serial No. 07/271,222 filed on November 14, 1988, now allowed, discloses in Example 19 a comparative composition comprising poly(1,4-butylene terephthalate), poly(bisphenol-A carbonate) and ACRYLOID® KM 653, also known as PARALOID® EXL 3691 (Rohm & Haas Company) which did not have acceptable gloss properties.
• polyester/p ⁇ lycarbonate blends modified by combinations of at least two different organosiloxane-based polyorganosiloxane/polyvinyl-based or diene rubber-based graft copolymers.
• the polyester resins of the present invention differ because they comprise alkane diol/cyclohexanedicarb ⁇ xylate-based units.
• compositions of the present invention are homogeneous and transparent, and all of the 10 compositions of the present-invention exhibit desirable stiffness and impact properties.
• compositions comprising (A) a first polyester resin comprising the reaction product of (a) at least one straight chain, branched, or cycloaliphatic C 2 -C 10 alkane diol or chemical equivalent thereof; and (b) at least one cycloaliphatic diacid or chemical equivalent thereof; and
• polyester (A) is the
• reaction product of (a) at least one straight chain or branched C 2 -C 10 alkane diol and (b) as above.
• compositions as described above further comprising (C) an effective modulus modifying amount of (a) a core-shell
• multi-stage polymer having a rubbery core derived from an acrylate or (meth)acrylate, diene or a mixture of any of the foregoing and a vinyl-based polymer or copolymer outer shell; (b) a vinyl cyanide-conjugated diolefin- alkyl aromatic terpolymer; or (c) a combination of (a)
• compositions comprising components (A), (B), and (C) above and (D) an additional polyester resin which may be same as or different than (A) are provided.
• the compositions consist essentially of components (A) and (B) , components (A), (B) , and (C) , or components (A), (B), (C), and (D) .
• component (A) (a) can comprise at least one straight chain or branched C 2 ⁇ C 10 alkane diol or chemical equivalent thereof.
• the diols useful in the preparation of the first polyester resins (A) of the present invention are straight chain, branched, or cycloaliphatic but preferably straight chain or branched alkane diols and may contain 2 to 10 carbon atoms.
• glycois examples include but are not limited to ethylene glycol; propylene glycol, i.e., 1,2- and 1,3-propylene glycol; 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- or trans-enantiomers; triethylene glycol; 1,10-decane diol; and mixtures of any of the foregoing.
• propylene glycol i.e., 1,2- and 1,3-propylene glycol
• butane diol i.e., 1,3- and 1,4-butane di
• 1,4-butanediol Particularly preferred is 1,4-butanediol. If a cycloaliphatic diol or chemical equivalent thereof and particularly 1,4- cyclohexane dimethanol or chemical equivalent thereof 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.
• 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 cycloaliphatic 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 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, or by the hydrogenation of an alkali salt of trimelletic anhydride. See, U.S. Patent Nos. 2,888,484 and 3,444,237.
• cis- and trans-enantiomers 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.
• the cis-enantiomer tends to blend better; however, the trans- enantiomer has higher melting and crystallization
• SUBSTITUTE SHEET temperatures and is especially preferred.
• Mixtures of the cis- and transenantiomers are useful herein as well, and preferably when such a mixture is used, the trans- enantiomer will comprise at least about 75 parts by weight and the cis-enantiomer will comprise the remainder based upon 100 parts by weight of cis- and trans- enantiomer combined.
• a copolyester or a mixture of two polyesters for use as component (A) may be used.
• Chemical equivalents of the diacids include 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 acid, particularly dimethyl-trans-1,4- cyclohexanedicarboxylate.
• Dimethyl-1,4-cyclohexanedicarboxylate can be obtained by ring hydrogenation of dimethylterephthalate, and two enantiomers having the carboxylic acid groups in the cisor 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 the 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
• 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 chemical equivalents thereof;
• R 1 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 1 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 and 3,047,539.
• 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 polycarbonate resin component (B) can comprise non-aromatic as well as aromatic forms. With respect to aromatic polycarbonate resins, these can be made by those skilled in this art or can be obtained from a variety of commercial sources. They may be prepared by
• SUBSTITUTE SHEET reacting a dihydroxy compound such as a dihydric phenol and/or a polyhydroxy compound with a carbonate precursor, such as phosgene, a haloformate or a carbonate ester such as a diester of carbonic acid.
• a carbonate precursor such as phosgene, a haloformate or a carbonate ester such as a diester of carbonic acid.
• A is a divalent aromatic radical of the dihydric phenol employed in the polymer producing reaction.
• the aromatic polymers have an intrinsic viscosity ranging from 0.30 to 1.0 dl/g (measured in methylene chloride at 25°C) .
• Dihydric phenols are meant to include mononuclear or polynuclear aromatic compounds containing two hydroxy radicals, each of which is attached to a carbon atom of an aromatic nucleus.
• dihydric phenols include 2,2-bis-(4-hydroxy ⁇ phenyl)propane; 2,2-bis-(3,5-dimethyl-4-hydroxy- phenyl)propane; 4,4'-dihydroxy-diphenylether; bis(2- hydroxyphenyl)methane; mixtures thereof and the like.
• the preferred aromatic carbonate polymer as component (B) is a homopolymer derived from 2,2-bis(4-hydroxyphenyl)- propane( isphenol-A) , poly(bisphenol-A carbonate).
• Poly(ester-carbonate) resins for use in the invention are known and can be obtained commercially. Generally, they are copolyesters comprising recurring carbonate groups:
• These poly(ester carbonates), in general, are prepared by reacting a difunctional carboxylic acid, such as phthalic acid; isophthalic acid; terephthalic acid; homophthalic acid; o-, m-, and p-phenylenediacetic acid; the polynuclear aromatic acids, such as diphenic acid; 1,4-naphthalic acid; mixtures of any of the foregoing; and the like, with a dihydric phenol and a carbonate precursor, of the types described above.
• a difunctional carboxylic acid such as phthalic acid; isophthalic acid; terephthalic acid; homophthalic acid; o-, m-, and p-phenylenediacetic acid
• a particularly useful poly(ester carbonate) is derived from bisphenol-A, isophthalic acid, terephthalic acid, or a mixture of isophthalic acid and terephthalic acid, or the reactive derivatives of these acids such as terephthaloyl dichloride, isophthaloyl dichloride, or a mixture thereof, and phosgene.
• the molar proportions of dihydroxy diaryl units to benezenedicarboxylate units to carbonate units can range from 1:0.30-0.80:0.70-0.20 and the molar range of terephthalate units to isophthalate units can range from 9:1 to 2:8 in this preferred family of resins.
• the aromatic dihydric phenol sulfone resins useful as component (B) are a family of resins which can be made by those skilled in this art.
• homopolymers of dihydric phenol, and a dihydroxydiphenol sulfone and a carbonate precursor as well as copolymers of a dihydric phenol and a carbonate precursor can be made according to the description in Schnell et al, U.S. Patent No. 3,271,367.
• a preferred material is made by
• modifiers (C)(a) of the present invention comprise core-shell multi-stage polymers.
• the modifier core can comprise an acrylate or a (meth)acrylate, a diene, or a mixture of the foregoing.
• the core is polymerized from a C. to C 5 alkyl acrylate resulting in an acrylic rubber core having a Tg below about 10°C and preferably it contains cross-linking monomer and/or graft-linking monomer.
• the preferred acrylate is n-butyl acrylate.
• the cross-linkinig monomer is a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups all of which polymerize at substantially the same rate of reaction.
• Suitable cross-linking monomers include polyacrylic and poly(methacrylic esters) of polyois such as butylene diacrylate and dimethacrylate, trimethylol propane trimethacrylate and the like, di- and tri-vinyl benzene, vinyl acrylate and methacrylate and the like.
• the preferred cross-linking monomer is butylene diacrylate.
• the graft-linking monomer is a polyethylenically unsaturated monomer having a plurality of addition 5 polymerizable reactive groups, at least one of which polymerizes at a substantially different rate of polymerization from at least one other of said reactive
• the function of the graft-linking monomer is to provide a residual level of unsaturation in the elastomeric phase, particularly in the latter stages of polymerization, and consequently, at or near the surface of the elastomer particles.
• the rigid thermoplastic shell stage is subsequently polymerized at the surface of the elastomer, the residual unsaturated, addition polymerizable reactive group contributed by the graft- linking monomer participates in the subsequent reaction so that at least a portion of the rigid shell stage is chemically attached to the surface of the elastomer.
• allyl group-containing monomers of allyl esters of ethylenically unsaturated diacids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, allyl acid maleate, allyl acid fumarate, and allyl acid itaconate.
• diallyl esters of polycarboxylic acids which do not contain polymerizable unsaturation.
• the preferred graft-linking monomers are allyl methacrylate and diallyl maleate.
• the final or outer shell stage monomer can be comprised of C.-C 16 methacrylate, styrene, acrylonitrile, alkyl acrylates, alkyl methacrylate, dialkyl methacrylate, and the like.
• the final outer shell stage monomer includes a major portion of a C 1 -C 4 alkyl methacrylate.
• One type of preferred core-shell multi-stage polymer (C)(a) has only two stages, the first stage or core being polymerized from a monomer system comprising butylene diacrylate as a cross-linking agent, allyl methacrylate or diallyl maleate as a graft-linking agent and with a final stage or outer shell of polymerized methyl methacrylate.
• a preferred two stage core-shell multi-stage ' polymer of this type is commercially
• ACRYLOID® KM 330 also known as PARALOID® EXL 3330, from Rohm & Haas Company.
• core-shell multi-stage polymers are prepared sequentially by emulsion polymerization techniques wherein each successive outer stage or shell coats the previous stage polymer.
• the monomeric C 1 -C 6 acrylate, the cross ⁇ linking monomer and the graft-linking monomer are copolymerized in water in the presence of a free-radical generating catalyst and a polymerization regulator which serves as a chain transfer agent at a temperature on the order of from 15°C to 80°C.
• the first elastomeric phase is formed in situ to provide a latex of the core copolymer.
• the second rigid thermoplastic phase monomers are added and are emulsion polymerized with the core copolymer latex to form the core-shell multi-stage polymers. More detailed description of the preparation of the acrylate-based core-shell multi-stage polymers for use herein as component (C) are found in U.S. Patent Nos. 4,034,013 and 4,096,202.
• the amorphous copolymer resin for use herein as component (C)(a) comprises a diene-based and preferably a butadiene-based core-shell multi-stage polymer resin.
• These diene-based core shell multi-stage polymers generally comprise a conjugated diene-based core, an intermediate graft shell of polymerized vinyl monomer units and a final or outer shell comprised of a polymerized monomeric component selected from the group consisting of an alkyl acrylate, preferably a C.-C 6 alkyl acrylate; an alkyl methacrylate, preferably a C.-C, alkyl methacrylate; acrylic acid; methacrylic acid; or a mixture of any of the foregoing with a cross-linking monomer.
• the core stage of diene or butadiene-based core-shell multi-stage polymer component (C) (a) comprises polymerized conjugated diene units of a copolymer of polymerized diene units with polymerized units of a vinyl aromatic compound or mixtures of such compounds.
• Suitable conjugated dienes for use in said core stage include butadiene, isoprene, 1,3-pentadiene and the like.
• Illustrative vinyl aromatic compounds include styrene, alphamethylstyrene, vinyl toluene, paramethylstyrene, and the like and esters of acrylic or methacrylic acid.
• the core of these copolymers should comprise a major portion of diene units.
• the preferred core-shell multi-stage polymer of this type includes a core of a styrene-butadiene copolymer having a molecular weight within the range of about 150,000 to 500,000.
• the core stage may also include a cross-linking monomer.
• the butadiene-based core-shell polymer may include a second intermediate stage of a polymerized vinyl monomer grafted to the core stage.
• Suitable vinyl monomers for use in the second intermediate shell stage include, but are not limited to, styrene, vinyl toluene, alphamethylstyrene, halogenated styrene, naphthalene, or divinylbenzene.
• Styrene and vinyl cyanide compounds such as acrylonitriles, methacrylonitriles, and alphahalogenated acrylonitriles, are especially preferred.
• These vinyl monomers can be used either alone or in admixture.
• the final or outer shell stage of the diene- based core-shell multi-stage polymer comprises polymerized units of a monomeric compound selected from the group consisting of alkyl acrylates, especially C ⁇ C g alkyl acrylate; alkyl methacrylate, especially C 1 ⁇ C 6 alkyl methacrylates; acrylic acid; methacrylic acid; or a mixture of any of the foregoing together with a cross-
• the monomeric compound may be a C -C 6 alkyl acrylate, e.g., methyl acrylate, ethyl acrylate, hexyl acrylate, and the like; a C ⁇ -C. alkyl methacrylate, e.g., methyl methacrylate, ethyl methacrylate, hexyl methacrylate, and the like; acrylic acid or methacrylic acid. Methyl methacrylate is preferred.
• the final or outer shell stage of the diene-based core shell multi-stage polymer also includes a cross-linking monomer.
• the cross-linking monomer as described above, is a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups, all of which polymerize at substantially the same reaction rate.
• Suitable cross-linking monomers include poly acrylic and poly methacrylic acid esters of polyois such as butylene diacrylate and dimethacrylate, trimethylol propane trimethacrylate and the like, divinyl- and trivinylbenzene, vinyl acrylate and methacrylate and the like.
• the preferred cross-linking monomer is butylene diacrylate.
• a particularly preferred core-shell multi-stage polymer for use as component (C)(a) herein is a core- shell polymer having a core polymerized from butadiene and styrene, methylmethacrylate and divinylbenzene, a second, intermediate stage or shell polymerized from styrene, and a third stage or outer shell polymerized from methyl methacrylate and 1,3-butylene glycol dimethacrylate.
• Such a commercially available core-shell multi-stage polymer is ACRYLOID® KM 653, also known as PARALOID® EXL 3691, from Rohm and Haas Co.
• diene-based core-shell multi-stage polymers are also prepared sequentially by emulsion polymerization techniques wherein each successive stage or shell coats
• the modifiers (C) (b) of the present invention comprise acrylonitrile-butadiene-styrene (ABS) graft copolymers well known to those of ordinary skill in the art.
• ABS impact modifier can be produced according to the procedures as set forth in u.S. Patent No. 4,764,563.
• ABS impact modifiers are prepared by grafting particular ratios of styrene and acrylonitrile on butadienebased rubber substrates.
• these impact modifiers are ABS graft copolymer resins prepared by graft polymerizing particular ratios of styrene and acrylonitrile in the presence of particular styrene-butadiene rubber substrates.
• the butadiene-based rubber substrates useful in preparing such impact modifiers are conventional copolymers of styrene and butadiene which optionally include up to 15 weight percent of acrylonitrile and/or an alkyl acrylate in which the alkyl group contains 4 or more carbon atoms, and comprise from 78 to 95 weight percent butadiene and from 22 to 5 weight percent styrene.
• the rubber substrate may further include up to 2 weight percent of additional copolymerizable cross ⁇ linking monomers such as divinylbenzene, triallyl- cyanurate or the like, up to 2 weight percent of chain transfer agents, such as tertiary dodecyl mercaptan, and up to 2 weight percent of graft enhancers such as alkyl methacrylate, diallylmaleate and the like. Diene polymer and copolymer rubbers are well known and widely employed commercially for a number of purposes. The preparation
• SUBSTITUTESHEET of such rubbers may be accomplished by any of a variety of processes well known and conventionally used. Particularly used are emulsion polymerization processes which provide the rubber in latex form suitable for use in subsequent graft polymerization processes.
• ABS-type impact modifiers are prepared by graft polymerizing from about 40 to about 70, preferably from 47 to 61 parts by weight of a grafting monomer mixture comprising a monovinyl aromatic compound (MVA) , such as styrene, a methyl styrene, p-methyl styrene or a combination thereof and an ethylenically unsaturated nitrile (EUN) such as acrylonitrile and/or methacrylonitrile in the presence of 100 parts by weight of butadiene-based rubber substrate.
• MVA monovinyl aromatic compound
• EUN ethylenically unsaturated nitrile
• the impact modifier is thus a high rubber graft copolymer having a rubber content of from about 50 to about 80 weight percent, preferably from 62 to 78 weight percent and, correspondingly, a graft iuonomer component or superstrate of from about 50 to 20, preferably from 48 to 22 weight percent.
• the weight ratio of the MVA to the EUN in the grafting monomer mixture will be in the range of from 3:1 to 5:1 and preferably, from 3.8:1 to 4.2:1.
• This graft polymerization of the MVA/EUN monomer mixture in the presence of the rubbery substrate may be carried out by any of the graft polymerization processes well known and widely Used in the polymerization art for preparing ABS resins, including emulsion, suspension and bulk processes. Typical of such processes are emulsion graft polymerization processes wherein the grafting monomers are added together with surfactants and chain transfer agents as desired, to an emulsion latex of the rubbery substrate and polymerized using an initiator.
• the initiator may be any of the
• SUBSTITUTE SHEET commonly used free-radical generators including peroxides such as alcumyl peroxide or azo initiators such as azobisisobutyronitrile.
• peroxides such as alcumyl peroxide or azo initiators such as azobisisobutyronitrile.
• azobisisobutyronitrile any of the variety of redox polymerization catalysts such as the combination of cumene hydroperoxide with ferrous sulfate and sodium formaldehyde sulfoxylate which are well known and widely used in such proceesses may be employed.
• the ABS impact polymer suitable for use in the present invention may also comprise a styrenic polymer which comprises a rigid portion and a rubber portion.
• the rigid portion is formed from at least two ethylenically unsaturated monomers, one of which comprises styrene and/or substituted styrene.
• Preferred substituted styrenes include, but are not limited to, halogen-substituted styrene, particularly wherein the halogen is substituted on the aromatic ring, alpha-methyl sytrene and para-methyl styrene.
• the other ethylenically unsaturated monomer which is used in forming the rigid portion may be selected from acrylonitrile, substituted acrylonitriles, acrylates, alkyl, substituted acrylates, methacrylates, alkyl substituted methacrylates, and ethylenically unsaturated carboxylic acids, diacids, dianhydrides, acid esters, diacid esters, amides, imides and alkyl and aryl substituted imides.
• the second monomer which is used to form the rigid portion is selected from the group consisting of acrylonitrile.
• the rigid portion is formed from about 60 to about 95 weight percent, and more preferably 60 to 80 weight percent of the styrene and/or substituted styrene monomers, and from about 5 to about 40 weight percent, and more perferably 20 to 40 weight percent of the second monomer.
• the rubber portion may be formed from polymers or copolymers of one or more conjugated dienes, copolymers of conjugated dienes and non-diene vinyl monomers, alkyl acrylate polymers, and copolymers of ethylenically unsaturated olefins and non-conjugated diene polymers (EPDM) rubbers.
• a preferred rubber portion includes polybutadiene.
• the styrenic polymer component may be formed such that the rigid portion is grafted to the rubber portion.
• the rigid portion may be blended with the rubber portion.
• the rubber portion it is preferred that the rubber portion has been previously grafted with one or more grafting monomers. Accordingly, the styrenic polymer component may be so produced by any method known in the art, for example, emulsion, bulk, mass or suspension polymerization processes.
• the styrenic polymer component contains from about 10 to 90 weight percent of the rubber sortion and from about 10 to 90 weight percent of the rigid portion, based on the rubber portion and the rigid portion, more preferably, the styrenic polymer component comprises from about 40 to about 80 weight percent of the rubber portion and from about 20 to about 60 weight percent of the rigid
• SUBSTITUTE SHEET portion based on the rubber portion and the rigid sortion.
• compositions of the present invention may include a second polyester resin (D) which may be the same as or different than (A) in addition to components (A), (B) and (C) .
• Polyesters (D) suitable for use herein may include those of (A) above and may be saturated or unsaturated. They are preferably, however, derived from an aliphatic or cycloaliphatic diol, or mixtures thereof, containing from 2 to about 10 carbon atoms, and at least one aromatic dicarboxylic acid.
• Preferred saturated polyester resins comprise the reaction product of a dicarboxylic acid or a chemical equivalent thereof and a diol.
• Preferred polyesters are derived from an aliphatic diol and an aromatic dicarboxylic acid and have repeated units of the following general formula:
• n is an integer of from 2 to 4.
• polyesters are poly(ethylene terephthalate) and poly(l,4-butylene terephthalate).
• polyesters with minor amounts, e.g., from 0.5 to about 2 percent by weight, of units derived from aliphatic acid and/or aliphatic polyois to form copolyesters.
• the aliphatic polyois include glycois, such as poly(ethylene glycol) . All ' such polyesters can be made following the
• polyesters which are derived from a cycloaliphatic diol and an aromatic dicarboxylic acid are prepared, for example, by condensing either the cis- or trans-isomer (or mixtures thereof) of, for example, 1,4- cyclohexanedimethanol with an aromatic dicarboxylic acid to produce a polyester having recurring units of the following formula:
• cyclohexane ring is selected froin the cis- and trans-isomers thereof and R represents an aryl radical containing 6 to 20 carbon atoms and which is the decarboxylated residue derived from an aromatic dicarboxylic acid.
• aromatic dicarboxylic acids represented by the decarboxylated residue R are isophthalic or terephthalic acid, l,2-di(p-carbox ⁇ phenyl) ethane, 4,4'-dicarboxydiphenyl ether, etc., and mixtures of these. All of these acids contain at least one aromatic nucleus. Acids containing fused rings can also be present, such as in 1,4- or 1,5-naphthalene- dicarboxylic acids.
• the preferred dicarboxylic acids are terephthalic acid or a mixture of terephthalic and isophthalic acids.
• Another preferred polyester may be derived from the reaction of either the cis- or trans-isomer (or a mixture thereof) of 1,4-cyclohexanedimethanol with a mixture of isophthalic and terephthalic acids. Such a polyester would have repeating units of the formula:
• Still another preferred polyester is a copolyester derived from a cyclohexanedimethanol, an alkylene glycol and an aromatic dicarboxylic acid.
• copolyesters are prepared by condensing either the cis- or trans-isomer (or mixtures thereof) of, for example, 1,4-cyclohexanedimethanol and an alkylene glycol with an aromatic dicarboxylic acid so as to produce a copolyester having units of the following formula:
• cyclohexane ring is selected from the cis- and trans-isomers thereof, R is as previously defined, n is an integer of 2 to 4, the x units comprise from about 10 to about 90 percent by weight and the y units comprise from about 90 to about 10 percent by weight.
• Such a preferred copolyester may be derived from the reaction of either the cis- or trans-isomer (or mixtures thereof) of 1,4-cyclohexanedimethanol and ethylene glycol with terephthalic acid in a molar ratio of 1:2:3.
• These copolyesters have repeating units of the following formula:
• polyesters described herein are either commercially available or can be produced by methods well known in the art, such as those set forth in, for example, U.S. Patent No. 2,901,466.
• polyesters used herein as component (D) have an intrinsic viscosity of from about 0.4 to about 2.0 dl/g as measured in a 60:40 phenol:tetrachloroethane mixture or similar solvent at 23°C-30°C.
• 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.
• component (A) the first polyester resin, comprises a minor portion and component (B), the polycarbonate resin, comprises a major portion of the polyester/polycarbonate composition.
• the first polyester component (A) comprises from about 1 to about 49 parts by weight and the polycarbonate resin comprises from about 99 to about 51 parts by weight based upon 100 parts by weight of (A) and (B) combined, and most preferably, the first polyester component (A) comprises from about 1 to about 25 by weight and especially 25 parts by weight and the polycarbonate
• SUBSTITUTESHEET component (B) comprises from about 99 to about 75 parts by weight and especially 75 parts by weight based upon 100 parts by weight of (A) and (B) combined.
• component (A) comprises a minor amount and component (B) comprises a major amount of (A) and (B) combined as above and components (A) and (B) combined comprise from about 80 to about 99 parts by weight and component (C) comprises from aoout 20 to about 1 part by weight based upon 100 parts by weight of (A), (B) and (C) combined.
• component (A) comprises a minor amount and component (B) comprises a major amount of (A) and (3) combined as above and components (A) and (B) combined comprise from about 50 to about 75 parts by weight, component (C) comprises from about 1 to about 20 parts by weight, and component (D) comprises from about 5 to about 35 parts by weight based upon 100 parts by weight of (A), (B), (C), and (D) combined.
• thermoplastic polymers can be used for the manufacture of 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 flow promoters, antioxidants, nucleating agents, other stabilizers, reinforcing agents, fillers, pigments, flame retardants, or combinations of any of the foregoing may be added to compositions of the present invention.
• PBCD poly(1,4-butylene-trans-1,4-cyclohexanedicarboxylate)
• PC polycarbonate resin
• the extruded blend was observed to be homogeneous and transparent. Tensile, notched Izod, and
• Dynatup bars were molded on a 3.5 oz. Van Dorn injection molding machine at 250°C barrel temperatures and 75°C mold temperature in a 30 second cycle.
• Example 1 The procedure of Example 1 was followed substituting 100.0 parts by weight of PBCD (melt viscosity 2400 poise at 250°C) for the dry blend. Properties are summarized in Table 1.
• Example 1 The procedure of Example 1 was followed substituting a dry blend of 99.65 parts of poly(1,4- butylene terephthalate) (PBT) (Valox® 315 - General Electric Company) and 0.35 part of a stabilizer package.
• PBT poly(1,4- butylene terephthalate)
• Valox® 315 - General Electric Company 0.35 part of a stabilizer package.
• Example 1 The procedure of Example 1 was followed substituting a dry blend of 98.97 parts of PBCD (melt viscosity 2500 poise at 250°C) and 1.03 parts of stabilizer package.
• Example 1 The procedure of Example 1 was followed substituting a dry blend of 98.97 parts by weight of PBT (Valox® 315 - General Electric Company) and 1.03 parts of a stabilizer package. Properties are summarized in Table 1.
• Example 1 The procedure of Example 1 was followed substituting a dry blend of 100.0 parts of PC (poly(bisphenol-A carbonate) Lexan® 141 - General Electric Company) and a trace of a stabilizer package. Properties are summarized in Table 1.
• a copolyester comprising a 23:77 ratio of cis- to trans-1,4-butylene-l,4-cyclohexanedicarboxylate monomers was prepared by reacting 515.0 parts of trans- dimethyl-trans-l,4cyclohexane dicarboxylate and 265.0 parts of a 60:40 mixture of cis- and trans-dimethyl-1,4-
• Example 1 Example 1
• test pieces were transparent as molded. Some of the test pieces were annealed in an oven for 4 hours at 100°C without turning opaque. Other test pieces were annealed in an oven for 4 hours at 120°C without turning opaque, but some bubbles developed in these pieces due to the presence of moisture.
• Example 3 The procedure of Example 2 was followed substituting a dry blend of 25.0 parts of PBCD (poly(l,4- butylene-trans-l,4-cyclohexanedicarboxylate) ) and 75.0 parts of a polycarbonate resin (poly(bisphenol-A carbonate) - Lexan® 141 - General Electric Company).
• PBCD poly(l,4- butylene-trans-l,4-cyclohexanedicarboxylate)
• a polycarbonate resin poly(bisphenol-A carbonate) - Lexan® 141 - General Electric Company
• SUBSTITUTESHEET Example 1 shows that PBCD/PC compositions retain the transparency of polycarbonates.
• Examples 1-3 when compared with Comparative Examples 1A*-1E*, illustrate the improvement in flexural modulus PBCD/PC compositions provide over that of the individual components and over other polyester resins such as PBT, as well as the excellent retention of practical impact strength as measured by unnotched Izod impact strength and Dynatup impact strength and the retention of transparency of the compositions of the present invention.
• Example 4A The procedure of Example 1 was followed substituting a dry blend of 39.0 parts of PBT (poly(l,4- butylene terephthalate) - Valox® 315 - General Electric Company), 49.25 parts of PC (poly(bisphenol-A carbonate) - Lexan® 141 - General Electric Company), 10.5 parts of C/S modifier (ACRYLOID® KM 653, also known as PARALOID® EXL 3691 - Rohm & Haas Company), and 1.25 parts of a stabilizer package.
• PBT poly(l,4- butylene terephthalate) - Valox® 315 - General Electric Company
• PC poly(bisphenol-A carbonate) - Lexan® 141 - General Electric Company
• C/S modifier ACRYLOID® KM 653
• Example 1 The procedure of Example 1 was followed substituting a dry blend of 38.34 parts of PBCD (poly(1,4-butylene-trans-1,4-cyclohexanedicarboxylate) melt viscosity 2500 poise at 250°C), 46.0 parts of PC
• PBCD poly(1,4-butylene-trans-1,4-cyclohexanedicarboxylate) melt viscosity 2500 poise at 250°C
• SUBSTITUTESHEET poly(bisphenol-A carbonate) Lexan® 141 - General Electric Company
• 14.0 parts of CIS modifier ACRYLOID® KM 653, also known as PARALOID® EXL 3691 - Rohm & Haas Company
• 1.66 parts of a stabilizer package Properties are summarized in Table 2.
• Example 1 The procedure of Example 1 was followed substituting a dry blend of 38.34 parts of PBT (poly(l,4- butylene terephthalate) - Valox® 315 - General Electric
• PC poly(bisphenol-A carbonate)
• CIS modifier ACRYLOID® KM 653, also known as PARALOID®
• Example 2 The procedure of Example is followed substituting a dry blend of 39.0 parts of PBCD (poly(l,4- butylene-trans-1,4cyclohexanedicarboxylate) melt viscosity 1100 poise at 250°C), 49.25 parts of PC
• PBCD poly(l,4- butylene-trans-1,4cyclohexanedicarboxylate) melt viscosity 1100 poise at 250°C
• PC poly(l,4- butylene-trans-1,4cyclohexanedicarboxylate) melt viscosity 1100 poise at 250°C
• ABS-BLENDEX® an acrylonitrile- butadiene-styrene graft copolymer modifier
• Typical properties will be substantially the same as those of Example 4 and are summarized in Table 2.
• Examples 4, 5 and 6 demonstrate that modified PBCD/PC compositions retain higher than average stiffness and excellent impact strength as well as excellent low temperature properties.
• Example 1 The procedure of Example 1 was followed substituting a dry blend of 10.0 parts of PBCD (poly(l,4- butylene-trans-1,4-cyclohexanedicarboxylate) (melt viscosity -2500 poise at 250°C), 28.34 parts of PBT
• Example 8 The procedure of Example 1 was followed substituting 20 parts of PBCD (poly(1,4-butylene-trans- 1,4-cyclohexanedicarboxylate) (melt viscosity -2500 poise at 250°C), 18.34 parts of PBT (poly(1,4-butylene terephthalate) - Valox® 315 General Electric Company), 46.0 parts of PC (poly(bisphenol-A carbonate) - Lexan® 141 - General Electric Company), 14.0 parts of C/S modifier (ACRYLOID® KM 653, also known as PARALOID® EXL 3691 - Rohm & Haas Company), and 1.66 parts of stabilizer package. Properties are summarized in Table 3.
• Example 9 The procedure of Example 1 was followed substituting 28.34 parts of PBCD (poly(1,4-butylene- trans-l,4-cyclohexanedicarboxylate) (melt viscosity 2500 poise at 250°C), 10.0 parts of PBT (poly(1,4-butylene terephthalate) - Valox® 315 General Electric Company), 46.0 parts of PC (poly(bisphenol-A
• Example 1 The procedure of Example 1 is followed substituting a dry blend of 10.0 parts of PBCD (poly(l,4- butylene-transl,4-cyclohexanedicarboxylate) melt viscosity 2500 poise at 250°C), 28.34 parts of PBT
• ABS BLENDEX® 338 - General Electric Company 46.0 parts of acrylonitrile-butadiene- styrene graft copolymer modifier (ABS BLENDEX® 338 - General Electric Company), and 1.66 parts of a stabilizer package.
• Typical properties will be substantially the same as those of Example 7 and are summarized in Table 3.
• Examples 7, 3, 9 and 10 demonstrate that modified PBCD/PC/PE compositions retain higher than average stiffness, excellent impact strength, and excellent tensile properties at all temperatures.
• ABS acrylonitrile-butadiene-styrene graft copolymer
• SUBSTITUTE SHEET EXAMPLE 11 A well mixed dry blend of 50.0 parts of a copolyester of a 25:75 ratio of cis- to trans-1,4-cyclo- hexanedimethanol and dimethyl trans-1,4-cyclohexane- dicarboxylate (PCCD) having a melt viscosity of 3000 poise at 250°C and 50.0 parts of a polycarbonate resin (poly(bisphenol-A carbonate) - Lexan® 141 - General Electric Company) was extruded and molded as in Example 1. The molded pieces were transparent.
• PCCD polycarbonate resin
• EXAMPLE 13 A well mixed dry blend of 49.975 parts of a copolyester of PCCD, a 25:75 ratio of cis- to trans-1,4- cyclohexanedimethanol anddimethyl trans-1,4-cyclohexane ⁇ dicarboxylate having a melt viscosity of 3000 poise at 250°C, 49.975 parts of a polycarbanate resin (poly(bisphenol-A carbonate) - Lexan® 141 - General Electric Company) modified with a small amount of blue
• the molded pieces were water clear and colorless. Properties are summarized in Table 4.
• Examples 11-13 demonstrate the combination of transparency and excellent ductility of the unmodified compositions of the present invention.
• Example 17 The procedure of Example 1 is followed substituting a dry blend of 10.0 parts of PCCD, a copolyester of a 25:75 ratio of cis- to trans-1,4- cyclohexanedimethanol and dimethyl trans-l,4-cyclo- hexanedicarboxylate having a melt viscosity of 3000 poise at 250°C, 28.34 parts of PBT (poly(1,4-butylene terephthalate - Valox® 315 - General Electric Company), 46.0 parts of acrylonitrile-butadienestyrene graft copolymer modifier (ABS - BLENDEX® 338 - General Electric Company), and 1.66 parts of a stabilizer package as indicated in Table 5. Substantially the same results as Examples Il ⁇ ls will be obtained, except stiffness is reduced, and the sample is opaque.
• ABS Acrylonitrile-butadiene-styrene graft copolymer
• BLENDEX® 338 General Electric Co.

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• 1991
  • 1991-08-27 JP JP92504254A patent/JPH05506478A/ja active Pending
  • 1991-08-27 KR KR1019930701238A patent/KR970009333B1/ko not_active IP Right Cessation
  • 1991-08-27 EP EP92904005A patent/EP0554410A1/de not_active Withdrawn
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