KR970009333B1 - Poly(alkyene cyclohexanedicarboxylate)-polycarbonate compositions and modifications - Google Patents

Abstract

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Description

Poly (alkylene cyclohexanedicarboxylate) -polycarbonate compositions and modified compositions

The present invention relates to a polyester resin comprising (A) at least one linear, branched or cycloaliphatic C ₂ to C ₁₀ alkane diol or a reaction product of which they are chemical equivalents with at least one cycloaliphatic diacid or chemical equivalents thereof, and (B) poly Not only relates to compositions consisting of carbonate resins, but also to core-shell multilayer polymers or vinyl cyanides having rubbery cores and vinyl-based polymers or copolymers outer shells derived from acrylates or (meth) acrylates, dienes or any mixtures thereof It relates to the above composition modified by adding an effective modulus mass of the conjugated diolefin-alkyl aromatic ABS-type terpolymer. Also included are modified and also flame retardant compositions as well as modified compositions that also include additional polyester resins that may be the same or different than the original polyester resin.

The unmodified composition remains homogeneous and transparent. All compositions of the present invention, whether modified or not, are significantly superior to the rigidity of the individual components, exhibit improved melt flow and possess excellent impact strength.

Background of the Invention

The novel composition comprising a polyester resin and a polycarbonate resin together which is a reaction product of at least one straight, branched or branched C ₂ to C ₁₀ alkane diol or a chemical equivalent thereof with at least one cycloaliphatic diacid or a chemical equivalent thereof. It was found that the homogeneity, transparency and rigidity measured as flexural modulus are significantly higher than the modulus of the individual components and have excellent impact strength over a wide range of temperatures.

Modified compositions comprising the composition and suitable core shell multilayered polymer modifiers or ABS-type polymer modifiers, as well as the modified compositions containing additional polyester resins, also possess better stiffness and impact properties.

Weather resistance, UV resistance, solvent resistance, elasticity, high impact polymers are widely used in the manufacture of molded or thermoformed products such as automotive exterior components, lawn and garden devices and fitness equipment.

Crystalline polyesters of aliphatic and / or cycloaliphatic diols and cycloaliphatic diacids or derivatives thereof have a relatively high melting point and are UV resistant, so they absorb almost no light in the vicinity of ultraviolet light. Many of these polyesters are being developed as hot melt complexes. Jackson et al., J. Applied Polymer Review, Vol. 14, 685-98 (1970); See US Pat. No. 3,515,628.

Wilfong, J. Polymer Sci. Vol. 54, 385-410 (1916), refer to polyesters of cis- / trans-mixtures of cyclohexanedicarboxylic acids obtained by hydrogenation of hexahydro terephthalic acid, terephthalic acid. US Patent No. 2,891,930 to Caldwell et al. (Including poly (neopentyl cyclohexane dicarboxylate)); Carpenter, J. Soc. Dyers and Colorists, Vol. 65, 469 (1941).

U.S. Patent No. 2,901,466 to Kibler et al. Discloses linear polyester and polyester amides prepared by condensation of cis- and / or trans-1,4-cyclohexanedimethanol with one or more bifunctional reactants. They have high melting temperatures and are advantageous for producing films for use as supporters for fibers and photographic emulsions for use in textiles.

Friction activated solvent-free adhesives comprising thermoplastic linear polyesters, tackifiers and plasticizers derived from one or more saturated aliphatic dicarboxylic acids and / or aromatic dicarboxylic acids and one or more saturated aliphatic diols are described in US Pat. No. 4,066,600 to Wayne et al. It is disclosed in the call.

Scott, US Pat. No. 4,125,572, includes copolyesners of polycarbonates, poly (1,4-butylene terephthalates), and mixtures of aliphatic or cycloaliphatic diols with terephthalic acid and isoterephthalic acid. Thermoplastic molding compositions and articles molded therefrom are described. Scott's literature discloses that blends of polycarbonates and polyalkylene terephthalates have transparency when the amount of poly (1,4-butylene terephthalate) is at least about 10% or when they are heat aged, as described in US Pat. No. 3,218,372. It is disclosed that there is a tendency to lose.

U.S. Patent No. 4,257,937 to Cohen et al. Describes a composition comprising a poly (1,4-butylene terephthalate) resin modified with a mixture of polyacrylate resins and aromatic polycarbonate resins.

US Pat. No. 4,327,206 to Jackson et al. Discloses a high content of trans-isomers comprising heating esters of trans-1,4-cyclohexanedicarboxylic acid and diacyl derivatives of aromatic diols in the presence of a suitable catalyst. A method for producing a (1,4-cyclohexanedicarboxylate) polyester is disclosed.

Avakian, U.S. Patent No. 4,555,540, discloses flame retardant blends of aromatic polycarbonates and polyesters incorporating certain phosphorus-containing materials for stability.

Nelson, U.S. Patent No. 4,760,107, includes one or more aromatic polycarbonate resins, one or more polyester resins, and a mixture of one or more polyols and one or more epoxides (epoxides are essential ingredients for preventing yellowing of the mixture). The resin composition is disclosed.

DeRudder, filed December 30, 1986, filed with U.S. Patent Application No. 06 / 947,671, which discloses polyester resins derived from aromatic polycarbonate resins, cyclohexane dimethanol and hexacarbocyclic dicarboxylic acids, and A low temperature impact resistant composition of an impact modifier comprising a core-shell acrylate (co-) polymer is disclosed.

The polyester of the deruder composition is different from the alkane diol cyclohexane dicarboxylate resin of the present invention.

US patent application Ser. No. 07 / 271,222 (currently granted), filed November 14, 1988, filed co-pending, discloses poly (1,4-butylene terephthalate), poly (bisphenol- A carbonate) and acryloid KM 653 (ACRYLOID) KM 653) (also paraloid EXEL 3691 (PARALOID) Comparative compositions comprising EXL 3691 (known as Rom and Haas Co.), which have no acceptable glossing properties.

United States Patent Nos. 07 / 271,246, filed November 14, 1988 and 07 / 356,356, filed May 29, 1989, disclose two or more other organosiloxane-based polyorganosiloxane / polyvinyl-based or A polyester / polycarbonate blend is disclosed that is modified by a mixture of diene rubber-based graft copolymers. However, the polyester resins of the present invention differ from the prior art resins because they contain alkane diol / cyclohexanedicarboxylate-based units.

A disadvantage of the preceding compositions is that they cannot withstand gamma rays without the necessity of adding property enhancers at the expense of tensile, flexibility and impact properties with loss of transparency.

Most of the above disadvantages are solved by various aspects of the compositions of the present invention. The unmodified compositions of the present invention are homogeneous and transparent and all of the compositions of the present invention exhibit the desired rigidity and impact properties.

Summary of the Invention

According to the present invention, there is provided a reaction product of (A) at least one straight chain, branched or cycloaliphatic C ₂ to C ₁₀ alkane diol or a chemical equivalent thereof and (b) at least one cycloaliphatic diacid or a chemical equivalent thereof There is provided a composition comprising a first polyester resin and (B) an aromatic polycarbonate resin, an aromatic polyester carbonate resin, a aromatic divalent phenol sulfone carbonate resin, or any mixture thereof.

In a preferred embodiment, the polyester (A) is the reaction product of at least one straight or branched C ₂ to C ₁₀ alkane diol (a) with the same component (b) as defined above.

The present invention also provides a (C) modulus-modifying effective amount of (a) a core having a rubbery core derived from acrylate or (mat) acrylate, diene or any mixture thereof and a vinyl-based polymer or copolymer outer shell. A shell multilayer polymer, (b) vinyl cyanide-conjugated diolefin-alkylaromatic terpolymer, or (c) a composition as described above further comprising a mixture of (a) and (b). Furthermore, there is provided a composition comprising an additional (D) component polyester resin which may be the same as or different from the above components (A), (B), (C) and component (A).

In a preferred embodiment, the compositions consist essentially of components (A) and (B), components (A), (B) and (C), or components (A), (B), (C) and (D). .

In another aspect, component (A) (a) may comprise one or more straight or branched C ₂ to C ₁₀ alkane diols or their chemical equivalents.

Detailed description of the invention

Diols useful in the preparation of the (A) first polyester resin of the invention are linear, branched or cycloaliphatic but preferably linear or alkane diols and may contain 2 to 10 carbon atoms. Examples of such glycols are ethylene glycol, propylene glycol (ie 1,2 and 1,3-propylene glycol), butanediol (ie 1,3- and 1,4-butanediol), diethylene glycol, 2-dimethyl-1, 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- Hexanediol, 1,4-cyclohexane dimethanol and especially cis- or trans-enantiomers thereof, triethylene glycol, 1,10-decane diol and any mixtures thereof, but are not limited thereto. Especially 1,4-butane diol is preferable. When alicyclic diols or their chemical equivalents and especially 1,4-cyclohexane dimethanol or their chemical equivalents are used as the diol component, these are in a ratio of 1 to 4 to 4 to 1, preferably 1 to 3 Preference is given to using a mixture of cis and trans enantiomers.

Chemical equivalents of the diols include esters and ethers such as dialkyl esters, dialkyl esters, polytetramethylene oxides and the like.

Diacids (A) (b) useful in the production of the polyester resin (A) of the present invention are alicyclic diacids. This means that the carboxylic acid includes two carboxyl groups each bonded to a saturated carbon in the saturated ring. As described in detail below, preferred diacids are 1,4-cyclohexanedicarboxylic acid and trans-1,4-cyclohexane dicarboxylic acid is most preferred.

Cyclohexanecarboxylic acids and their chemical equivalents are, for example, high aromatics such as isophthalic acid or terephthalic acid using a suitable catalyst such as rhodium supported on carbon or alumina, which is a suitable carrier in suitable solvents, water or acetic acid at room temperature and under atmospheric pressure. It can be prepared by hydrogenating diacids and corresponding derivatives. Freifelder et al. , 31, 3438 (1966) and US Pat. Nos. 2,675,390 and 4.754,064. It can also be prepared using an inert liquid medium in which phthalic acid is at least partially dissolved under these reaction conditions and a palladium or ruthenium catalyst on carbon or silica or by hydrogenating the alkali salts of trimellitic anhydride. See US Pat. Nos. 2,888,484 and 3,444,237.

Upon hydrogenation, it is typical to obtain two enantiomers in which the carboxylic acid group is in the cis- or trans-position. The cis- and trans-enantiomers can be separated by crystallization or distillation with or without solvents such as n-heptane. Although the cis-enantiomers tend to blend better, the trans-enantiomers are particularly preferred because of their high melting point and crystallization temperature. Mixtures of cis- and trans enantiomers are also useful herein and when using such mixtures the trans-enantiomers comprise at least about 75% by weight based on the combined 100 parts by weight of the cis- and trans-enantiomers and the cis-enantiomers are It is desirable to occupy the rest.

When using a mixture of enantiomers or one or more diacids, it is possible to use copolyesters or mixtures of two polyesters as component (A).

Chemical equivalents of diacids include esters such as dialkyl esters, dialkyl esters, anhydrides, acids, acid chlorides, acid bromide and the like. Preferred chemical equivalents include dialkyl esters of cycloaliphatic diacids and most preferred chemical equivalents include dimethyl esters of acids, specifically dimethyl-trans-1,4-cyclohexanedicarboxylate.

Dimethyl-1,4-cyclohexanedicarboxylate can be obtained by ring hydrogenation of dimethylterephthalate to obtain two enantiomers having carboxylic acid groups in the cis- or trans-position. Enantiomers can be separated as above and trans-enantiomers are particularly preferred for this reason. Mixtures of enantiomers are suitable as described above and the amounts described above are preferred.

The polyester resin (A) of the present invention is typically obtained by condensation reaction or transesterification polymerization of a diol or diol equivalent component (A) (a) with a diacid or diacid equivalent component (A) (b), and the following general It has a repeat unit of formula:

Wherein R is a C ₂ to C ₁₀ alkyl or cycloalkyl radical, and is a residue of a straight chain, branched or cycloaliphatic C ₂ to C ₁₀ alkane diol or a chemical equivalent thereof, and R ₁ from an alicyclic diacid or equivalent thereof Cycloaliphatic radicals which are derived carboxylate residues. Specifically they have repeat units of the general formula:

Wherein R is derived from 1,4-butane diol and R ¹ is a cyclohexane ring derived from cyclo hexanedicarboxylate or a chemical equivalent thereof and is selected from cis- or trans-enantiomers thereof ).

All such polyesters can be prepared, for example, according to the teachings of US Pat. Nos. 2,465,319 and 3,047,539.

Generally, the reaction is carried out in the presence of a suitable catalyst such as tetrakis (2-ethylhexyl) titanium salt with an excess of diol component and at a suitable amount, typically about 20-200 ppm titanium, based on the weight of the final product. .

The polycarbonate resin component (B) may comprise not only aromatic forms but also non-aromatic forms. In the case of aromatic polycarbonate resins, those skilled in the art can prepare them or obtain them from various commercial sources. They can be prepared by reacting dihydroxy compounds such as dihydric phenols and / or polyhydroxy compounds with carbonate precursors such as phosgene, haloformates or carbonate esters such as diesters of carboxylic acids. Typically, they will have repeat units of the following general formula.

Wherein A is a divalent aromatic radical of the dihydric phenol used in the polymer production reaction.

Preferably, the aromatic polymer has an intrinsic viscosity in the range of 0.30 to 1.0 dl / g (measured in methylene chloride at 25 ° C.). Divalent phenols contain two hydroxy radicals, meaning that they each contain a mononuclear or multinuclear aromatic compound bonded to the carbon atom of the aromatic nucleus. Typically, dihydric phenols are 2,2-bis (4-hydroxy-phenol) propane, 2,2-bis- (3,5-dimethyl-4-hydroxy-phenyl) propane, 4,4-dihydroxy Diphenyl ether, bis (2-hydroxyphenyl) methane, mixtures thereof, and the like. Preferred aromatic carbonate polymers as component (B) are homopolymers derived from 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A), poly (bisphenol-A carbonate).

Poly (ester-carbonate) resins for use in the present invention are known and can be obtained commercially. In general, these are carbonate groups that repeat in a linear polymer chain. , Carboxylate groups And copolyesters comprising aromatic carbocyclic groups, wherein at least some carboxylate groups and at least some carbonate groups are bonded directly to the ring carbon atoms of the aromatic carbocyclic group. Generally, the poly (ester carbonate) is a bifunctional carboxylic acid (e.g. phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, o-, m-, and p-phenylenediacetic acid), polynuclear aromatic acid (e.g., diphenic acid, 1,4-naphthalic acid), any mixtures thereof, and the like, by reacting with divalent phenol and carbonate precursors of the type described above. Particularly useful poly (ester carbonates) are bisphenol-A, isophthalic acid, terephthalic acid or a mixture of isophthalic acid and terephthalic acid or reactive derivatives of such acids (e.g. Derived from. The molar ratio of dihydroxy diaryl units to benzenedicarboxylate units to carbonate units in the above preferred resins may be 1: 0.30 to 0.80: 0.70 to 0.20, and the molar ratio of terephthalate units to isophthalate units is from 9: 1 to 1. It may range from 2: 8.

Aromatic divalent phenol sulfone resins useful as component (B) are resins that can be prepared by those skilled in the art. For example, homopolymers of dihydric phenol, dihydroxydiphenol sulfone and carbonate precursors as well as copolymers of dihydric phenol and carbonate precursors can be prepared according to the description of US Pat. No. 3,271,367 to Schnell et al. Preferred materials can be prepared by polymerizing bis- (3,5-dimethyl-4-hydroxy phenyl) sulfones alone or in combination with bisphenol-A with phosgene or phosgene precursors as described in Fox US Pat. No. 3,737,409. have. Particular preference is given to copolymers prepared by reacting 40 to 99% by weight of sulfo and 1 to 60% by weight of bisphenol with phosgene.

Any mixture of the above polycarbonate resins is also suitable for use as component (B).

Modifiers (C) (a) of the present invention comprise a core-cell multilayer polymer. The modifier core may comprise acrylates or mats (acrylates), dienes or mixtures thereof.

In a preferred embodiment, the core polymerizes C ₁ to C ₆ alkyl acrylates to obtain an acrylic rubber core having a Tg of about 10 ° C. or less and preferably comprises cross-linking monomers and / or graft-linking monomers. Preferred acrylates are n-butyl acrylates.

Cross-linking monomers are polyethylene type unsaturated monomers having a plurality of addition polymerizable reactive groups which polymerize at about the same reaction rate. Suitable cross-linking monomers include polyacrylic and poly (methacrylic esters) of polyols (eg butylene diacrylate and dimethacrylate, trimethylol propane trimethacrylate, etc.), di- and tri-vinyl benzene, Vinyl acrylate, methacrylate and the like. Preferred cross-linking monomer is butylene diacrylate.

Graft bond-monomers are polyethylene-type unsaturated monomers having a plurality of addition polymerizable reactive groups in which at least one is polymerized at a different polymerization rate from at least one other reactive group. The role of the graft-bonding monomer is to provide the residual amount of elastomeric phase, in particular at the end of the polymerization, as a result, at or near the surface of the elastomeric particles. When the hard thermoplastic shell layer polymerizes at the surface of the elastomer, the remaining unsaturated, addition polymerizable reactive groups provided by the graft-bonding monomer participate in subsequent reactions such that at least a portion of the hard shell layer is chemically applied to the surface of the elastomer. Combined.

Effective graft-linking monomers are allyl-group containing monomers of allyl esters of ethylenically unsaturated diacids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl itaconate, allyl acid maleate, allyl acid Fumarate and allyl acid itaconate. Some less preferred are diallyl esters of polycarboxylic acids that do not contain a polymerizable unsaturated group. Preferred graft-binding monomers are allyl methacrylate and diallyl maleate.

Final or outer shell layer monomers may include C ₁ to C ₁₆ methacrylates, styrene, acrylonitrile, alkyl acrylates, alkyl methacrylates, dialkyl methacrylates, and the like. Preferably, the final outer shell monomers comprise large amounts of C ₁ to C ₄ alkyl methacrylates.

One type of preferred core-shell multilayer polymer (C) (a) has only two layers, wherein the first layer or core is butylene diacrylate as cross-linking agent, allyl methacrylate as graft-binding agent or diallyl maly In a monomer system comprising an ate, the final layer or outer shell is polymerized with methyl methacrylate. Preferred two-layer core shell multilayer polymers of this type are acryloids from Rom and Haas Co. KM 330, also pararaloid It is commercially available under the trade name known as EXEL 3330.

The core-shell multilayer polymers are produced continuously by emulsion polymerization techniques in which each successive outer layer or cell covers its full layer polymer. In the description, the monomeric C ₁ to C ₆ acrylates, cross-linking monomers and graft-linking monomers are present in the presence of a polymerization regulator which acts as a catalyst and chain transfer agent to generate free-radicals at temperatures ranging from 15 ° C. to 80 ° C. Copolymerize in water. The first elastic polymeric phase is prepared in situ to provide the latex of the core copolymer.

Second hard thermoplastic phase monomers are then added to emulsion polymerize with the core copolymer latex to form a core-shell polymer. Further details of the preparation of acrylate-based core-shell multilayer polymers for use in the present invention as component (C) are in US Pat. Nos. 4,034,013 and 4,096,202.

In another preferred embodiment, the amorphous copolymer resin for use in the present invention as component (C) (a) is a diene-based, preferably butadiene-based core-shell multilayer polymer resin. Generally, the diene-based coreshell multilayer polymers are conjugated diene-based cores, intermediate graft shells of polymerized vinyl monomer units and alkyl acrylates, preferably C ₁ to C ₆ alkyl acrylates, alkyl methacrylates, preferably And a final or outer shell consisting of a polymerized monomer component selected from C ₁ to C ₆ alkyl methacrylates, acrylic acid, methacrylic acid, or any mixture thereof, together with the crosslinking monomer.

More specifically, the core layer of the diene or butadiene-based core-shell multilayer polymer component (C) (a) is a polymerized conjugated diene of a copolymer of polymerized diene units and polymerized units of vinyl aromatic compounds or mixtures of these compounds. Contains units.

Conjugated dienes suitable for use in the core layer include butadiene, isoprene, 1,3-pentadiene and the like. Examples of vinyl aromatic compounds include styrene, alphamethylstyrene, vinyl toluene, paramethylstyrene and the like and esters of acrylic or methacrylic acid. The core of the copolymer should contain most of the diene units. Preferred core-shell multilayer polymers of this type include cores of styrene-butadiene copolymers having a molecular weight within the range of about 150,000 to 500,000. The core layer can also include cross-linking monomers.

Optionally but preferably, the butadiene-based core-shell polymer may comprise a second intermediate layer of polymerized vinyl monomers grafted to the core layer. Suitable vinyl monomers for use in the second intermediate shell layer include, but are not limited to, styrene, vinyl toluene, alphamethylstyrene, halogenated styrene, naphthalene or divinylbenzene. Particular preference is given to vinyl cyanide compounds such as styrene and acrylonitrile, methacrylonitrile, and alphahalogenated acrylonitrile. The vinyl monomers may be used alone or in combination.

The final or outer shell layer of the diene-based core-shell multilayer polymer is alkyl acrylates, in particular C ₁ to C ₆ alkyl acrylates, alkyl methacrylates, in particular C ₁ to C ₆ alkyl methacrylates, acrylic acid, methacrylic acid or Polymeric units of monomeric compounds selected from the group consisting of any mixtures thereof are included together with the crosslinking monomers.

More specifically, the monomeric compound may be selected from C ₁ to C ₆ alkyl acrylates such as methyl acrylate, methyl acrylate, hexyl methacrylate, etc., C ₁ to C ₆ alkyl methacrylates such as methyl methacrylate. Acrylate, ethyl methacrylate, hexyl methacrylate, and the like, or acrylic acid or methacrylic acid. Methyl methacrylate is preferred.

The final or outer shell layer of the diene-based core shell multilayer polymer, in addition to the monomeric compound, also includes crosslinking monomers. As described above, crosslinking monomers are polyethylene-type unsaturated monomers having a plurality of addition polymerizable reactive groups, all of which are polymerized at about the same reaction rate. Suitable cross-linking monomers are polyacrylic acid and polymethacrylic acid esters of polyols, such as butylene diacrylate and dimethacrylate, trimethylolpropane trimethacrylate, such as divinyl- and trivinylbenzene, vinyl Acrylates and methacrylates and the like. Preferred cross-linking monomers are butylene diacrylates.

Particularly preferred core-shell multilayer polymers for use as component (C) (a) of the present invention are cores polymerized from butadiene and styrene, methyl methacrylate and divinylbenzene, second intermediate layers or shells polymerized from styrene and Core-shell polymer having a third layer or outer shell polymerized from methyl methacrylate and 1,3-butylene glycol dimethacrylate. Such commercially available core-shell multilayer polymers. Such commercially available core-shell multilayer polymers are acryloids from Rohm and Haas Co. KM 653, also pararaloid It is known as EX3691.

Diene-based core-shell multilayer polymers are also continuously produced by emulsion polymerization techniques in which each successive layer or shell covers its full layer polymer. Diene-based core-shell multilayer polymers and methods for their preparation are described in more detail in US Pat. No. 4,180,494. Modifiers (C) (b) of the present invention include acrylonitrile-butadiene-styrene (ABS) graft copolymers that are well known to those of ordinary skill in the art.

Particularly suitable ABS impact modifiers can be prepared according to the method as described in US Pat. No. 4,764,563.

The ABS impact modifiers are prepared by grafting a certain proportion of styrene and acrylonitrile on a butadiene-based rubber substrate.

Specifically, the impact modifiers are ABS graft copolymer resins prepared by graft polymerizing a certain proportion of styrene and acrylonitrile in the presence of a specific styrene-butadiene rubber substrate.

Butadiene-based rubber substrates useful for preparing such impact modifiers optionally comprise up to 15% by weight of acrylonitrile and / or alkylacrylates, wherein alkyl groups contain at least 4 carbon atoms, and 78 to 95% by weight. Is a copolymer of conventional styrene and butadiene comprising butadiene and 22 to 5% by weight of styrene. The rubber base may further contain up to 2% by weight of additional copolymerizable crosslinking monomers such as divinylbenzene, triallyl cyanurate, etc. up to 2% by weight of chain transfer agents such as tertiary dodecyl mercaptan and 2 Up to% graft weight may include, for example, alkyl methacrylate, diallyl maleate, and the like. Diene polymers and copolymer rubbers are well known and widely used commercially for many purposes. Methods for producing such rubbers may be carried out by any of a variety of methods that are well known and commonly used. In particular, an emulsion polymerization process is used which provides a latex form of rubber suitable for use in subsequent graft polymerization processes.

Preferred ABS-type impact modifiers are monovinyl aromatic compounds (MVA) and acrylonitrile and / or methacrylo such as styrene, methyl styrene, p-methyl styrene or mixtures thereof in the presence of 100 parts by weight of a butadiene-based rubber base. A graft monomer mixture comprising ethylenically unsaturated nitrile (EUN) such as nitrile is prepared by graft polymerization of about 40 to about 70, preferably 47 to 61 parts by weight. Thus, the impact modifier has a rubber content of about 50 to about 80 weight percent, preferably 62 to 78 weight percent and correspondingly about 50 to about 20, preferably 48 to 22 weight percent of the graft monomer component or gas. It is a high content of rubber graft copolymers.

The weight ratio of MVA to EUN in the graft monomer mixture is in the range of 3: 1 to 5: 1 and preferably 3.8: 1 to 4.2: 1.

Graft polymerization of MVA / EUN monomer mixtures in the presence of a rubbery substrate can be prepared by any of the graft polymerization methods well known and widely used in polymerization techniques for preparing ABS resins, including emulsification, suspension and bulk processes. Typical such methods are emulsion graft polymerization methods wherein the graft monomer is added to the rubbery based emulsion latex with surfactants and chain transfer agents as desired and polymerized using an initiator. The initiator may be any of the free-radical generators commonly used, including peroxidants such as alcumyl peroxide or azo initiators such as azobisisobutyronitrile. Alternatively, various redox polymerization catalysts can be used, such as mixtures of cumene hydroperoxide and ferrous sulfate and sodium formaldehyde sulfoxylate, which are known and widely used in the process. Thus, the graft polymerization methods used to prepare the ABS impact modifiers, as well as the methods used to coagulate and isolate the impact modifiers for further use, are well known and conventional and, therefore, the preparation of the impact modifiers for further use. The application of the method is also well known, conventional and is apparent to those skilled in the art.

In addition, ABS impact polymers suitable for use in the present invention may include styrene polymers including hard parts and rubber parts. The hard portion is formed from two or more ethylenically unsaturated monomers, one of which is styrene and / or substituted styrene.

Preferred substituted styrenes include, but are not limited to, halogen-substituted styrenes (specifically halogen is substituted on the aromatic ring). Alpha-methyl styrene and para-methyl styrene. Other ethylenically unsaturated monomers used to form the hard moiety include acrylonitrile, substituted acrylonitrile, acrylates, alkyl substituted acrylates, methacrylates, alkyl substituted methacrylates and ethylenically unsaturated carboxylic acids, moving, Dianhydrides, acid esters, diacid esters, amides, imides and alkyl and aryl substituted amides. Preferably, the second monomer used to form the hard moiety comprises a crowd consisting of acrylonitrile, alkyl methacrylonitrile, alkyl methacrylate, maleic anhydride, maleimide, alkyl maleimide and aryl maleimide and mixtures thereof. Is selected. The hard portion also comprises from about 60 to about 95 weight percent and more preferably from 60 to 80 weight percent of styrene and / or substituted styrene monomers, and from about 5 to about 40 weight percent and more preferably from 20 to 40 weight percent It is preferably formed of a second monomer.

The rubber portion may be formed from a polymer or copolymer 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 polymer (EPDM) rubbers. Can be. Preferred rubber parts include polybutadiene.

The styrenic polymer component can be prepared by grafting the hard portion to the rubber portion. Alternatively, the hard portion can be blended with the rubber portion. When blending the hard part with the rubber part, it is preferred to pre-graft the rubber part with at least one graft monomer. Thus, the styrenic polymer component can be prepared by any method known in the art, for example, by emulsification, bulk, bulk or suspension polymerization methods. The styrene-based polymer component contains about 10 to 90% by weight of the rubber part and about 10 to 90% by weight of the hard part based on the content of the rubber part and the hard part. More preferably, the styrene-based polymer component includes about 40 to about 80 weight percent rubber portion and about 20 to about 60 weight percent hard portion based on the content of the rubber portion and the hard portion.

Mixtures of such core-shell multilayer modifiers and ABS modifiers are also suitable for use in the present invention.

In another embodiment, the composition of the present invention may comprise a second polyester resin (D) which may be the same as or different from component (A) in addition to components (A), (B) and (C).

Polyesters (D) suitable for use herein may include the polyesters of (A) above and may be saturated or unsaturated. However, they are preferably derived from aliphatic or cycloaliphatic diols containing C ₂ to C ₁₀ or mixtures thereof and at least one aromatic dicarboxylic acid. Preferred saturated polyester resins include the reaction products of dicarboxylic acids or their chemical equivalents with diols. Preferred polyesters are derived from aliphatic diols and aromatic dicarboxylic acids and have repeating units of the general formula:

Wherein n is an integer from 2 to 4.

Most preferred polyesters are poly (ethylene terephthalate) and poly (1,4-butylene terephthalate).

Also contemplated herein for the preparation of copolyesters are those polyesters containing small amounts of units derived from aliphatic acids and / or aliphatic polyols, for example in amounts of from 0.5 to about 2% by weight. Aliphatic polyols include glycols such as poly (ethylene glycol).

All such polyesters can be prepared, for example, according to the teachings of US Pat. Nos. 2,465,319 and 3,047,539.

Polyesters derived from cycloaliphatic diols and aromatic dicarboxylic acids are, for example, condensed cis- or trans-isomers (or mixtures thereof) with aromatic dicarboxylic acids of 1,4-cyclohexanedimethanol to repeat units of the general formula Made of polyester with

Wherein the cyclohexane ring is selected from their cis- and trans-isomers, R is an aryl radical containing C ₆ to C ₂₀ and a dicarboxylated moiety derived from an aromatic dicarboxylic acid. Examples of aromatic dicarboxylic acids represented by dicarboxylated moiety R are isophthalic acid or terephthalic acid, 1,2- (p-carboxyphenyl) ethane, 4,4-dicarboxydiphenylether and the like and mixtures thereof. All of these acids contain one or more aromatic nuclei. Acids containing fused rings may also be present, such as 1,4- or 1,5-naphthalenedicarboxylic acid.

Preferred dicarboxylic acids are terephthalic acid or a mixture of terephthalic acid and isophthalic acid.

Another preferred polyester can be derived from the reaction of cis- or trans-isomers (or mixtures thereof) of 1,4-cyclohexanedimethanol with mixtures of isophthalic acid and terephthalic acid. Such polyesters have repeat units of the general formula:

Another preferred polyester is copolyesters derived from cyclohexanedimethanol, alkylene glycols and aromatic dicarboxylic acids. The copolyester is condensed with, for example, any one of cis- or trans-isomers (or mixtures thereof) of 1,4-cyclohexanedimethanol and alkylene glycol and aromatic dicarboxyl to form repeating units of the general formula It can be prepared with a copolyester having:

Wherein the cyclohexane ring is selected from their cis- and trans-isomers, R is as defined above, n is an integer from 2 to 4, x unit comprises from about 10 to about 90 weight percent, y The unit comprises about 90 to about 10 weight percent.

Such preferred copolyesters can be prepared by reacting cis- or trans-isomers of 1,4-cyclohexanedimethanol (or mixtures thereof) and ethylene glycol and terephthalic acid in a molar ratio of 1: 2: 3. The copolyester has repeating units of the general formula:

Wherein x and y are as previously defined.

The polyesters described herein are either commercially available or can be prepared by methods known in the art, such as those described in US Pat. No. 2,901,466.

The polyesters used herein as component (D) have an intrinsic viscosity of about 0.4 to about 2.0 dl /, measured in a phenol to tetrachloromethane mixture or similar solvent of 60:40 at 23 to 30 ° C.

Particular mention is made of blends comprising the compositions of the invention. In addition, the compositions of the present invention may be molded, extruded or thermoformed into articles by conventional methods known to those of ordinary skill in the art.

In the two component composition of the present invention, component (A), i.e., the first polyester resin, constitutes a minimum portion of the polyester / polycarbonate composition and component (B), i.e., the polycarbonate resin, Occupies most of it. Preferably, the first polyester component (A) comprises about 1 to about 49 parts by weight, and the polycarbonate resin comprises about 99 to about 51 parts by weight, based on 100 parts by weight of the components (A) and (B), Preferably the first polyester component (A) comprises from about 1 to about 25 parts by weight and in particular 25 parts by weight and the polycarbonate component (B) is about 99, based on 100 parts by weight of the components (A) and (B) To about 75 parts by weight, and in particular 75 parts by weight.

In the improved composition of the present invention, as described above, component (A) is a small amount in the contents of components (A) and (B), and component (B) accounts for the majority, and components (A) and (B) The content of c) is about 80 to about 99 parts by weight based on 100 parts by weight of the total amount of components (A), (B) and (C) and component (C) is about 20 to about 1 part by weight.

In the improved composition containing the additional polyester resin (D), in the content of components (A) and (B) as above, component (A) is a small amount and component (B) accounts for a large part, The content of components (A) and (B) is about 50 to about 75 parts by weight based on 100 parts by weight of the components (A), (B), (C) and (D), and component (C) is about 1 To about 20 parts by weight, and component (D) comprises about 5 to about 35 parts by weight.

Conventional methods for mixing thermoplastic polymers can be used to prepare the compositions of the present invention. For example, the composition can be prepared using any suitable mixing device, auxiliary kneader or extruder under conditions known to those of ordinary skill in the art.

In addition, flow promoters, antioxidants, nucleators, other stabilizers, reinforcing agents, fillers, pigments, flame retardants or any of the above mixtures may be added to the compositions of the present invention.

Description of the preferred sun

The following examples illustrate the invention without limiting it. All parts are by weight unless otherwise indicated. Impact strength is expressed as notched and unnotched izods following Dynatup impact at ASTM-D-256 or at room temperature (RT) (23 ° C.) unless otherwise specified. Tensile properties are measured by ASTM-D-638, flexibility is measured by ASTM-D-638 and flexibility is measured by ASTM-D-790. Appearance is opague, transparent or clear and colorless.

25.0 parts poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate) (PBCD)

(Melt viscosity at 250 ° C: 1100 poise), 74.65 parts of polycarbonate resin (PC) (poly (bisphenol-A carbonate), lexan 141 (Lexan 141) -general electric company of Pittsfield, Maryland) and anhydrous blends of 0.35 parts of stabilizer package were thoroughly mixed and extruded on a 2.5HPM extruder with a barrel band at 250 ° C. and operated at 100 rpm.

The extruded blend was homogeneous and transparent. Tensile, notched Izod and dynatub bars were molded on a 3.5 ounce Van Dorn injection molding machine at 250 ° C. barrel temperature and 75 ° C. molding temperature at 30 second intervals.

The properties are shown in Table 1 below.

Comparative Example 1A ^*

The method of Example 1 was carried out by replacing the dry blend of Example 1 with 100.0 parts by weight of PBCD (melt viscosity at 2400 ° C .: 2400 poise).

The properties are shown in Table 1 below.

Comparative Example 1B ^*

99.65 parts by weight of poly (1,4-butylene terephthalate) (PBT) (balox) was added to the anhydrous blend of Example 1. 315 (Valox 315) -General Electric Company) and 0.35 parts by weight of a stabilizer package were replaced with anhydrous blends to carry out the method of Example 1.

The properties are shown in Table 1 below.

Comparative Example 1C ^*

The method of Example 1 was performed by replacing the anhydrous blend of Example 1 with an anhydrous blend of 98.97 parts by weight of PBCD (melt viscosity at 2500 ° C .: 2500 poise) and 1.03 parts by weight of stabilizer package.

The properties are shown in Table 1 below.

Comparative Example 1D ^*

98.97 parts by weight of PBT (balox) was added to the dry blend of Example 1. The method of Example 1 was carried out by substituting anhydrous blend of 315-General Electric Co. Ltd.) and 1.03 parts by weight of stabilizer package.

The properties are shown in Table 1 below.

Comparative Example 1E ^*

100.0 parts by weight of PC (poly (bisphenol-A carbonate), lexan The method of Example 1 was carried out by replacing anhydrous blends of 141-General Electric Co.) and traces of stabilizer packages.

The properties are shown in Table 1 below.

Example 2

A copolyester comprising a 23:77 ratio of cis to trans-1,4-butylene-1,4-cyclohexane dicarboxylate monomer was 515.0 in the presence of 1.0 part titanium in the form of tetra (2-ethylhexyl) titanate. 60:40 mixture of negative trans-dimethyl-trans-1,4-cyclohexane dicarboxylate and 265.0 parts cis- and trans-dimethyl-1,4-cyclohexanedicarboxylate (DMCD-HP-NY, Rochester Eastman Chemical Co., Ltd.) was reacted with 550.0 parts of 1,4-butanediol under exchange conditions, and then an excess butanediol was recovered under vacuum at 260 ° C. C ₁₃ NMR analysis showed that the resulting copolyester contained 23% cis-cyclohexane dicarboxylate residues. Differential scanning calorimetry showed a peak crystallization temperature of 132 ° C. and a heat of fusion of 18.3 J / g.

25.0 parts copolyester and 75.0 parts polycarbonate resin (poly (bisphenol-A-carbonate), lexan from above Anhydrous blend of 141-General Electric Co., Ltd. was thoroughly mixed and extruded and molded as in Example 1.

The molded test sample was transparent. Some test samples did not change opaque upon annealing at 100 ° C. for 4 hours. Other test seals did not change opaque upon annealing at 120 ° C. for 4 hours, but bubbles were generated in the sample due to the presence of moisture.

The properties are shown in Table 1 below.

Example 3

The blend of Example 2 was prepared with 25.0 parts of PBCD (poly (1,4-butylene-trans-1,4-cyclohexane carboxylate)) and 75.0 parts of polycarbonate resin (poly (bisphenol-A carbonate), lexan The method of Example 2 was carried out by replacement with anhydrous blend of 141-General Electric.

The molded test sample was transparent but turned opaque due to crystallization of the polyester component upon annealing.

The properties are shown in Table 1 below.

Example 1 shows that the PBCD / PC composition maintains the transparency of the polycarbonate. Compared with Comparative Examples 1A-1E, Examples 1-3 show that the PBCD / PC compositions not only provide an improvement in flexural modulus as compared to the properties of the individual components and other polyester resins such as PBT. Good retention of actual impact strength and good transparency retention are measured as measured by the unnoched anizod impact strength and dynatub impact strength of the compositions of the invention.

A-poly (1,4-butylene-trans-1,4-cyclohexane-dicarboxylate)

B-23: Copolyester of cis to trans poly (1,4-butylene-1,4-cyclohexane dicarboxylate) monomers of 77

C-poly (1,4-butylene terephthalate) -balox 315-General Electric Company

D-poly (bisphenol-A carbonate) -rexane 141 General Electric Company

E-O = opaque; T = transparent; TB = transparent and bubbling

Example 4

The blend of Example 1 was prepared with 39.0 parts of PBCD (poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate), melt viscosity at 250 ° C .: 1100 poise), 49.25 parts of PC (poly (bisphenol- Acarbonate) Lexan 141-General Electric Company, 10.5 parts core-shell multilayer polymer (C / S modifier) (core = polymerized butadiene and styrene, polymerized methylmethacrylate and divinylbenzene second layer / shell = polymerized styrene , Outer shell = polymerized methylmethacrylate and 1,3-butylene glycol dimethacrylate-acryloid, manufactured by Rohm and Haas Co., Philadelphia, PA KM 653 also paraloid The method of Example 1 was carried out by replacing with anhydrous blends of EXEL 3691) and 1.25 parts of stabilizer package.

The extrusion composition was opaque in appearance. The properties are shown in Table 2.

Comparative Example 4 *

The blend of Example 1 was prepared with 39.0 parts of PBT (poly (1,4-butylene terephthalate), balox 315-General Electric Co., Ltd., 49.25 parts of PC (poly (bisphenol -A carbonate)-lexan 141-General Electric Company, 10.5 parts C / S modifier (Acryloid, manufactured by Rohm and Haas Company) KM 653 also pyraloid The method of Example 1 was carried out by replacing with anhydrous blends of EXEL 3691) and 1.25 parts of stabilizer package.

The properties are shown in Table 2 below.

Example 5

Anhydrous blend of Example 1 was prepared with 38.34 parts of PBCD (poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate), melt viscosity at 250 ° C .: 2500 poise), 46.0 parts of PC (poly (bisphenol -A carbonate) Lexan 141-General Electric Company, 14.0 parts C / S modifier (Acryloid, manufactured by Rohm and Haas Company) KM 653 also paraloid The method of Example 1 was carried out by replacement with anhydrous blend of EXEL 3691) and 1.66 parts of stabilizer package.

The properties are shown in Table 2 below.

Comparative Example 5A *

Anhydrous blend of Example 1 was prepared using 38.34 parts of PBT (poly (1,4-butylene terephthalate) -balox 315-General Electric Co., Ltd.), 46.0 parts of PC (poly (bisphenol -A carbonate)-lexan 141-General Electric Company, 14.0 parts C / S modifier (Acryloid, manufactured by Rohm and Haas Company) KM 653 also paraloid The method of Example 1 was carried out by replacement with anhydrous blend of EXEL 3691) and 1.66 parts of stabilizer package.

The properties are shown in Table 2 below.

Example 6

Anhydrous blend of Example 1 was prepared with 39.0 parts of PBCD (poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate), melt viscosity at 250 ° C .: 1100 poise), 49.25 parts of PC (poly (bisphenol -A carbonate)-lexan 141-General Electric Co., Ltd.), 10.5 parts of acrylonitrile-butadiene-styrene-graft copolymer modifier (AB-blendex) 388 (ABS-BLENDEX 338), manufactured by General Electric Co., Ltd.) and 1.25 parts of the stabilizer package were replaced with anhydrous blend of the Example 1 method.

Representative characteristics are almost the same as those of Example 4 and are shown in Table 2 below.

Examples 4,5 and 6 demonstrate that the modified PBCD / PC compositions have superior low temperature properties as well as higher than average stiffness and excellent impact strength. Compared with Comparative Examples 1A ^* and 1C ^* , the modified composition illustrates that it is superior to the individual components.

A-poly (1,4-butylene-trans-1,4-cyclohexane-dicarboxylate)-melt viscosity at 250 ° C .: 1100 poise

B-poly (1,4-butylene-trans-1,4-cyclohexane-dicarboxylate)-melt viscosity at 250 ° C .: 2500 poise

C-poly (1,4-butylene terephthalate) -balox 315-General Electric Company

D-poly (bisphenol-A carbonate) -rexane 141-General Electric Company

E-core-shell multi-layer polymer (core = polymerized butadiene and styrene, polymerized methylmethacrylate and divinylbenzene, second layer / shell = polymerized styrene, outer shell = polymerized methylmethacrylate and 1,3 Butylene Glycol Dimethacrylate-Acryloid, manufactured by Rohm and Haas Co., Ltd., Philadelphia, PA. KM 653 also pyraloid This is known as XL 3691)

F-acrylonitrile-butadiene-styrene graft copolymer (ABS) blendex 338-General Electric Company

G-O = opaque; T = transparent

F-representative characteristics are almost the same as those of Example 4.

Example 7

The anhydrous blend of Example 1 was prepared with 10.0 parts of PBCD (poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate), melt viscosity at 250 ° C .: 2500 poise), 28.34 parts of PBT (poly (1 , 4-butylene terephthalate), balox 315-General Electric Co., Ltd.), 46.0 parts of PC (poly (bisphenol -A carbonate)-lexan 141 General Electric Co., Ltd., 14.0 parts C / S modifier (Acryloid, manufactured by Rohm and Haas Co., Ltd.) KM 653 also paraloid The method of Example 1 was carried out by replacement with anhydrous blend of EXEL 3691) and 1.66 parts of stabilizer package.

The properties are shown in Table 3 below.

Example 8

Anhydrous blend of Example 1 was prepared with 20 parts of PBCD (poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate), melt viscosity at 250 ° C .: 2500 poise), 18.34 parts of PBT (poly (1 , 4-butylene terephthalate) -balox 315-General Electric Co., Ltd.), 46.0 parts of PC (poly (bisphenol -A carbonate)-lexan 141-General Electric Company, 14.0 parts C / S modifier (Acryloid, manufactured by Rohm and Haas Company) KM 653 also paraloid The method of Example 1 was carried out by substituting anhydrous blend of XL 3691) and 1.66 parts of stabilizer package.

The properties are shown in Table 3 below.

Example 9

Anhydrous blend of Example 1 was prepared with 28.34 parts of PBCD (poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate), melt viscosity at 250 ° C .: 2500 poise), 10.0 parts of PBT (poly (1 , 4-butylene terephthalate), balox 315-General Electric Co., Ltd., 46.0 parts PC (poly (bisphenol -A carbonate) lexan 141-General Electric Company, 14.0 parts C / S modifier (Acryloid, manufactured by Rohm and Haas Company) KM 653 also paraloid The method of Example 1 was carried out by replacement with anhydrous blend of EXEL 3691) and 1.66 parts of stabilizer package.

The properties are shown in Table 3 below.

Example 10

Anhydrous blend of Example 1 was prepared with 10.0 parts of PBCD (poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate), melt viscosity at 250 ° C: 2500 poise), 28.34 parts of PBT (poly (1 , 4-butylene terephthalate), balox 315-General Electric Co., Ltd.), 46.0 parts acrylonitrile-butadiene-styrene graft copolymer modifier (ABS Brendex) The method of Example 1 was carried out by substituting anhydrous blends of 338-General Electric Company) and 1,66 parts of stabilizer package.

Representative characteristics are almost the same as those of Example 7, and are shown in Table 3 below.

Examples 7,8, 9 and 10 demonstrate that the modified PBCD / PC / PE compositions are higher than average stiffness at all temperatures and have excellent impact strength and excellent tensile properties.

A-poly (1,4-butylene-trans-1,4-cyclohexane-dicarboxylate) Melt viscosity at 250 ° C .: 2500 poise

B-poly (1,4-butylene terephthalate) -balox 315-General Eletic Company

C-Poly (bisphenol-A Carbonate) -Lexane 141-General Eletic Company

D-core-shell multilayer polymer (core = polymerized butadiene and styrene, polymerized methylmethacrylate and divinylbenzene, second layer / shell = polymerized styrene, outer shell = polymerized methylmethacrylate and 1,3 -Butylene Glycol Dimethacrylate-Acryloid, manufactured by Rohm and Haas Co., Ltd., Piradelpia, PA KM 653 also pyraloid Known as EXL 3691)

E-acrylonitrile-butadiene-styrene graft copolymer (Abis) blendex 338-General Electric Company

F-representative characteristics are almost the same as those of Example 7.

Example 11

50.0 parts of copolyester of 25:75 cis-to-trans-1,4-cyclohexanedimethanol and dimethyltrans-1,4-cyclohexanedicarboxylate having a melt viscosity of 3000 poise at 250 ° C. and polycarbonate Resin (poly (bisphenol -A carbonate)-lexan 141-General Electric Company 50.0 parts of anhydrous blend was sufficiently mixed and extruded and molded as in Example 1.

The molded sample was transparent. Differential scanning calorimeters showed that the blend was inherently crystalline and not prone to crystallization at the annealing temperature.

The properties are shown in Table 4 below.

Example 12

49.8 parts of a copolyester (PCCD) of cis-to-trans-1,4-cyclohexanedimethanol and dimethyl trans-1,4-cyclohexanedicarboxylate having a melt viscosity of 3000 poise at 250 ° C. , Polycarbonate resin (poly (bisphenol-A carbonate)-lexan 141-General Electric Company 49.8 parts and 0.4 parts of stabilizer package were thoroughly mixed and tested by extrusion and molding as in Example 1.

The properties are shown in Table 4 below.

Example 13

49.975 parts of a copolyester (PCCD) of cis-to-trans-1,4-cyclohexanedimethanol and dimethyltrans-1,4-cyclohexanedicarboxylate in a ratio of 25:75 with a 250 ° C melt viscosity of 3000 poise, 49.975 parts polycarbonate resin (poly (bisphenol-A carbonate) -rexane modified with a small amount of blue dye to block slightly yellowish hue 141-General Electric Company) and anhydrous blends of 0.05 parts of stabilizer package were thoroughly mixed and tested by extrusion and molding as in Example 1.

The molded sample was clear watery colorless. The properties are shown in Table 4 below.

Examples 11-13 demonstrate the transparency and excellent ductility of the unmodified compositions of the present invention.

A-25: copolyester of cis-to-trans-1,4-cyclohexanedimethanol and 75 dimethyl trans-1,4-cyclohexanedicarboxylate having a melt viscosity of 3000 poise at 250 ° C

B-poly (bisphenol-A carbonate) -rexane 141-General Electric Company

Blue dye to block C-yellow tint

D-O = opaque; T = transparent; C-clear water and colorless

Example 14

39.0 parts of copolyester (PCCD) of cis-to-trans-1,4-cyclohexanedimethanol and dimethyltrans-1,4-cyclohexanedicarboxylate in a ratio of 25:75 with a melt viscosity of 3000 poise at 250 ° C. , 49.25 parts of PC (poly (bisphenol-A carbonate)-lexan 141-general electric) and 10.5 parts of core-shell multilayer polymer (C / S modifier) (core = polymerized butadiene and styrene, polymerized methylmethacrylate and divinylbenzene, second layer / shell = polymerized styrene, Outer Shell = Acryloid, polymerized methyl methacrylate and 1,3-butylene glycol dimethacrylate, manufactured by Rohm and Haas Co., Ltd., Philadelphia, Pennsylvania. KM 653 also paraloid Known as EXXL 3691) and 1.25 parts of the stabilizer package were replaced with anhydrous blends and the general methods of Examples 11-13 were repeated and the properties are shown in Table 5 below.

Almost the same results as in Examples 11-13 were obtained except that the stiffness was reduced and the sample was opaque.

Example 15

39.0 parts of PCCD (25:75 ratio cis-to-trans-1,4-cyclohexanedimethanol and dimethyl trans-1,4-cyclohexanedicarboxylate with a melt viscosity of 3000 poise at 250 ° C.) , 49.25 parts of PC (poly (bisphenol-A carbonate)-lexan 141 General Electric Co.) and 10.5 parts of acrylonitrile-butadiene-styrene graft copolymer modifier (ABS blendex 338-General Electric Co.) and 1.25 parts of the stabilizer package were replaced with anhydrous blends and the general procedure of Examples 11-13 was repeated and the properties are shown in Table 5 below.

Almost the same results as in Examples 11-13 were obtained except that the stiffness was reduced and the sample was opaque.

Example 16

10.0 parts of copolyester (PCCD) of cis-to-trans-1,4-cyclohexanedimethanol and dimethyltrans-1,4-cyclohexanedicarboxylate in a 25:75 ratio with a melt viscosity of 3000 poise at 250 ° C. 28.34 parts PBT (poly (1,4-butylene terephthalate) -balox 315-General Electric Co., Ltd., 40.0 parts of PC (poly (bisphenol -A carbonate)-lexan 141-General Electric Co.) and 14.0 parts C / S modifier (Acryloid, manufactured by Rohm and Haas Co., Ltd.) KM 653 also paraloid The general procedure of Examples 11-13 was repeated and replaced with anhydrous blends of EXEL 3691) and 1.66 parts of stabilizer package, and the properties are shown in Table 5 below.

Almost the same results as in Examples 11-13 were obtained except that the stiffness was reduced and the sample was opaque.

Example 17

10.0 parts of copolyester (PCCD) of cis-to-trans-1,4-cyclohexanedimethanol and dimethyltrans-1,4-cyclohexanedicarboxylate in a ratio of 25:75 with a melt viscosity of 3000 poise at 250 ° C. 28.34 parts PBT (poly (1,4-butylene terephthalate) -balox 315-General Electric Company, 46.0 parts acrylonitrile-butadiene styrene graft copolymer modifier (ABS-Blendex 338-General Electric Co.) and 1.66 parts of a stabilizer package were replaced with anhydrous blends to perform the method of Example 1 and the properties are shown in Table 5 below.

Almost the same results as in Examples 11-13 were obtained except that the stiffness was reduced and the sample was opaque.

A-25: 75 phosphorus cis: copolyester of trans 1,4-cyclohexane-dimethanol and dimethyl trans-1,4-cyclohexane-dicarboxylate at 250 ° C melt viscosity: 3000 poise

B-poly (1,4-butylene terephthalate) -balox 315-General Electric Company

C-Poly (bisphenol-A Carbonate) -Lexane 141-General Electric Company

D-core-shell multi-layer polymers (core = polymerized butadiene and styrene, polymerized methylmethacrylate and divinylbenzene, second layer / shell = polymerized styrene, outer shell = polymerized methylmethacrylate and 1,3 -Butylene Glycol Dimethacrylate-Acryloid, manufactured by Rohm and Haas Co., Ltd., Philadelphia, PA KM 653 also paraloid Known as EXL 3691)

E-acrylonitrile-butadiene-styrene graft copolymer (ABX) -blendex 338-General Electric Company

All patents, publications, applications and test methods mentioned above are incorporated herein by reference.

Many variations of the invention will become apparent to those skilled in the art upon reference to the above detailed description.

All such obvious modifications are within the scope of the appended claims.

Claims (25)

(A) a first poly comprising a reaction product of (a) one or more straight chain, branched or cycloaliphatic C ₂ to C ₁₀ alkanediols or their chemical equivalents, and (b) one or more cycloaliphatic diacids or their chemical equivalents A composition comprising an ester resin and (B) an aromatic polycarbonate resin, an aromatic polyester carbonate resin, an aromatic dihydric phenol sulfone carbonate resin, or a mixture thereof. The composition of claim 1 wherein said alkanediol (A) (a) is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol and cyclohexane dimethanol. The composition of claim 2, wherein said alkanediol (A) (a) comprises 1,40 butylene glycol. The composition of claim 1, wherein said diacid (A) (b) comprises 1,4-cyclohexanediacid. 5. The composition of claim 4, wherein the diacid (A) (b) comprises trans-1,4-cyclohexanedicarboxylic acid. The composition of claim 4, wherein said diacid (A) (b) comprises a mixture of cis- and trans-1,4-cyclohexanedicarboxylic acid. The composition of claim 1, wherein the chemical equivalent of diacid (A) (b) comprises a dialkyl ester of diacid. 8. The composition of claim 7, wherein said dialkyl ester (A) (b) comprises dimethyl-1,4-cyclohexane dicarboxylate. The composition of claim 8, wherein the dialkyl ester (A) (b) comprises dimethyl-trans-1,4-cyclohexanedicarboxylate. 10. The process of claim 8, wherein the dialkyl ester (A) (b) comprises a mixture of dimethyl-cis-1,4-cyclohexanedicarboxylate and dimethyl-trans-1,4-sineclohexanedicarboxylate. Composition. The composition of claim 1, wherein the first polyester resin (A) comprises poly (1,4-butylene-1,4-cyclohexanedicarboxylate). 12. The composition of claim 11, wherein said first polyester resin (A) comprises poly (1,4-butylene-trans-1,4-cyclohexanedicarboxylate). The method of claim 11, wherein the first polyester resin (A) is a 1,4-butylene-cis-1,4-cyclohexanedicarboxylate monomer and 1,4-butylene-trans-1,4-cyclo A composition comprising a copolymer of hexanedicarboxylate monomers. The composition of claim 1 wherein component (B) comprises an aromatic polycarbonate resin. The composition of claim 14 wherein component (B) comprises a poly (bisphenol-A carbonate) resin. The composition according to claim 1, comprising 1 to 49 parts by weight of component (A) and 51 to 99 parts by weight of component (B), based on 100 parts by weight of the components (A) and (B). The composition of claim 16 comprising 25 parts by weight of component (A) and 75 parts by weight of component (B), based on 100 parts by weight of the components (A) and (B). An article molded of the composition as defined in claim 1. An article extruded from a composition as defined in claim 1. A product which thermoforms the composition as defined in claim 1. A first poly comprising (A) a reaction product of (a) one or more straight-chain, branched or cycloaliphatic C ₂ to C ₁₀ alkanediols or their chemical equivalents, and (b) one or more cycloaliphatic diacids or their chemical equivalents A composition consisting of an ester resin, and (B) an aromatic polycarbonate resin, an aromatic polyester carbonate resin, an aromatic dihydric phenol sulfone carbonate resin, or a mixture thereof. The composition of claim 1, wherein said alkanediols or their chemical equivalents comprise 1,4-cyclohexanedimethanol or their chemical equivalents. 23. The method according to claim 22, wherein the alkanediols or their chemical equivalents are from 20 to 80 parts by weight of the cis-enantiomer and from 80 to 20 parts by weight of the trans-mirror phase, based on 100 parts by weight of their cis- and trans-enantiomers. A composition comprising an isomer. 24. The composition of claim 23, wherein the cis- and trans-enantiomers comprise 25 parts by weight of the cis-enantiomer and 25 parts by weight of the trans-enantiomer. The composition of claim 1 further comprising a reinforcing filler, pigment, flame retardant stabilizer, nucleating agent or mixtures thereof.