CA2063507A1 - Poly(akylene cyclohexane dicarboxylate)-(alkylene terephthalate) copolyesters - Google Patents

Abstract

336-2222 (8CV-5125) ABSTRACT OF THE DISCLOSURE

Copolyester compositions are provided which comprise the reaction product of at least one straight chain, branched, or cycloaliphatic C2-C10 alkane diol or a chemical equivalent thereof, a mixture of at least two cycloaliphatic diacide or chemical eguivalents thereof, the mixture comprising predominantly a trans-enantiomer, and at least one aromatic diacid or a chemical equivalent thereof. These copolyesters have superior ductility to the homopolymers of the diol component and either of the diacid components.

Description

2~63~07 -1- 336-2222 (8CV-5125) POLY(AL~YL~NE CYCLOC~AN~ DICARBOXYLATE)-(AL~YL~E T~REP~T~ALAT~) COPOLYESTLRS

CROSS-~LF~R~NC~ TO R~hATED ~PP~ICATIONS
This app}ication is related to the following commonly owned, concurrently filed U.S. patent applications.
SERIAL ATTY~S SU8JECT
NO._ DOCKET MATTER APPLICANT(S) 336-2220 Poly(alkylene cylohexane- W.F.H~ Borman (8CV-504~/ dicarboxylate)-polycarbonate N-I Liu 83) Compositions and Modifications 336-2221 Modifications of Poly(alky- W.F.H. Borman (8CV-5084/ lene cylcohexanedicarboxy- N-I Liu 5118) late) Blends 336-2223 Poly(alkylene cyclohexane- W.F.H. Borman lS (8CV-5117) dicarboxylate) Binary Blends N-I Liu This invention relates to copolyester compositions ~ comprised of the reaction product of at least one straight `~ chain, branched, or cycloaliphatic C2-C10 alkane diol or a chemical e~uivalent thereof, a mixtùre of at least two cycloaliphatic diacids or chemical equivalents thereof with the mixture predominantly comprising a trans-enantiomer, and at least one aromatic diacid or chemical equivalent thereof.
; Filled and flame-retardant compositions are contemplated as -` 25 well.
.~
These copolyester compositions are highly crystalline and crystallize rapidly. The ductility of these copolyesters, as measured by Notched Izod impact strength, is significantly improved over that of ~he homopolymers of the diol and either of the cycloaliphatic diacid or chemical equivalent thereof or aromatic diacid or chemical equivalent ` thereof. Surprisingly, the compositions exhibit enhanced mold flow in comparison with state of the art materials.

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-2- 336-22Z2 (8CV-5125) BAC~GRO~ND OF TB~ I~V~TION
Novel copolyester compositions comprising the reaction product of at least one straight chain, branched, or cycloaliphatic C2-C10 alkane diol or a chemical equivalent thereof, a mixture of at least two cycloaliphatic diacids or chemical equivalents thereof with the mixture predominantly comprising a trans-enantiomer, and at least one aromatic diacid or chemical equivalent thereof have been discovered which are highly crystalline, crystallize rapidly, and have improved ductility, impact strength, and enhanced melt flow c in comparison with state of the art materials.
Crystallizable polyesters of cycloaliphatic diacids or derivatives thereof with aliphatic and/or cycloaliphatic dio}s have relatively high melting points and are quite UV
resistant as they do not appreciably absorb near-UV li~ht.
Many of these polyesters including copolyesters incorporating (a)(i~ a 50:50 mixture of cis- and trans-1,4-cyclohexane dicarboxylic acid or (a)(ii) trans~cyclohexane dicarboxylic acid and (b) terephthalic acid were explored for use as hot melt adhesives. Howevec, the ratio of (a)(i):(b) was always less than or equal to 3:2 and the ratio of (a)(ii):(b) was always greater than or equal to 1:1. See, Jackson et al., J.
Applied Polymer Science! Vol. 14, 685-98, (197Q); U.S.
Patent No. 3,515,628.
Wilfong, J. Polymer Sci., Vol. 54, 385-410 (1961), referred to polyesters of hexahydro terephthalic acid, the cis-/trans-~ixture of cyclohexanedicarboxylic acids obtained by the hydrogenation of teEephthalic acid. See, ~aldwell et al, U.S. Patent No. 2,891,930 including poly(neopentyl cyclo-hexane dicarboxylatej; Carpenter, Journal of Soc. Dyers and Colorists, Vol. 65, 469 (1941).
Kibler et al, U.S. Patent No. 2,901,466, disclose linear polyesters and polyester-amides prepared by condensin~
cis- and/or trans-1,4-cyclohexanedimethanol with one or ~ore bifunctional reactants which, because of high melting ,:

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2~63~7 -3- 336-2222 (aCV-5125) temperatures, are advantageous for the preparation of fibers for use in fabrics and films for use as support for photographic emulsions.
Friction activatable solvent-free adhesives comprising a thermoplastic linear polyester derived from one or more saturated aliphatic dicarboxylic acids 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.
Low distortion fiberous, filler reinforced molding materials containing a copolyester, which has a crystallization temperature of 35C to 70C, based on poly(l,4-butylene terephthalate), and an amount which produces this crystallization temperature range of at least one co-component which is selected from orthophthalic acid; isophthalic acid;

4,4'-diphenylsulphonedicarboxylic acid; 2,2-bis-(4-~hydroxy-ethoxyphenyl))-propane; 1,3-bis-hydroxyethyl-5,5-dialkyl-hydantoin; 1,3,3,-trimethyl-5-carboxy-3-(p-carboxyphenyl)-indane; and l,4-cyclohexanedimethanol are disclosed by Breitenfellner et al, U.S. Patent No. 4,066,607.
Esters comprising the reaction product of a diol, a triol, a cyclic carboxylic acid, an unsaturated aliphatic dicarboxylic acid, and a saturated, aliphatic dicarboxylic acid cross-linked with an aminoplast resin were combined to form a one step chemical coating by Lasken, U.S. Patent No.
4,071,578.
Scott et al, U.S. Patent No. 4,125,571, disclose a combination of a poly(l,4-butylene terephthalate) resin or a copolyester thereof and a polyester resin derived from a cyclohexanedimethanol and a hexacarbocyclic dicarboxylic acid, while Scott, U.S. Patent No. 4,125,572, describes thermoplastic molding compositions and articles molded therefrom that retain optical clarity comprising a polycarbonate, a poly(l,4-butylene terephthalate), and a copolyester of an 20~3~r~) -4- 336-2222 (8CV-5125) aliphatic or cycloaliphatic diol and a mixture of terephthalic and isophthalic acids.
Copolyesters of poly(ethylene cyclohexane dimethylent terephthalatel and a flexible copolymer containing alternating covalently bonded blocks of poly(butylene terephthalate) and poly(l,4-butylene ether) are disclosed by Dennehey et al, U~S. Patent No. 4,225,688, as exhibiting good bonding characteristics to polyvinyl chloride as well as good impact resistance and improved resistance to crazing or cracking in `_ 10 the presence of solvents such as alcohol.
Jackson et ai, U.S. Patent No. 4,327,206~ disclose a process for the preparation of poly(l,4-cyclohexane dicarboxylate) polyesters with high trans-isomer content comprising heating, in the presence of a suitable catalyst, an ester of trans-1,4-cyclohexanedicarboxylic acid and a diacyl derivative of an aromatic diol.
~ vakian, U.S. Patent No. 4,555,540, discloses ~lame retardant blends of aromatic polycarbonates and polyesters incorporating certain phosphorous containing materials for stability.
An improved method for the sterilization of transparent plastic articles by ionizing radiation comprising the use of an article made from a polymer composition comprising poly(bisphenol-A) carbonate and a copolyester of ethylene glycol, cyclohexane dimethanol and an aromatic acid are disclosed by Allen et al in U.S. Patent No. 4,77~,656.
None of these prior compositions have been determined to posse~s impr~ved ductility over the homopolymers which form from the same reactants.
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S~MARY OF_T~ rNVeNTION
According to the present invention, there are provided copolyester compositions comprising the reaction product of (A) at least one straight chain, branched, or cycloaliphatic C2-C10 alkane diol or chemical equivalent thereof; (B) a mixture of at least two cycloaliphatic diacids ; '~ ' ' : .

~3~

-5- 336-2222 ~8CV-5125) or chemical equivalents thereof, the mixture comprising predominantly a trans-enantiomer; and (C) at least one aromatic diacid or chemical equivalent thereof.
When the expression mixture comprising predominantly a trans-enantiomer is used herein and in the appended claims, it is meant to contemplate from about 51 to about 99.5 parts by weight of trans-enantiomer and from about 0.5 to about 49 parts by weight of cis-enantiomer based upon }00 parts by weight of cis- and trans-enantiomers combined.
In preferred embodiments, the copolyester compositions comprise the reaction product of (A) 1,4-butane diol, (B) a mixture of from about 51 to about 99.5 parts by weight of dimethyl-trans-1,4-cyclohexanedicarboxylate and from about 0.S to about 49 parts by weight of dimethyl-cis-lS 1,4-cyclohexanedicarboxylate based upon 100 parts by weight of the cis- and trans-enantiomers combined and ~C) dimethyl terephtha}ate.

D~TAIL~D DESCRIPTIO~ OF T~E INV~NTION
The diols (A) useful in the preparation of the copolyester compositions of the present invention are straight chain, branched or cycloaliphatic but preferably straight chain or branched alkane diols and may contain from 2 to 10 carbon atoms. Examples of such glycols include but are not limited to ethylene glycol; propylene glycol, i.e., 1,2- and 1,3-propylene glycol; butane diol, i.eO, 1,3- and 1,4-butane diol; diethylene glycol; 2,2-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-hexane diol; 1,4-cyclohexane dimethanol and particularly its cis- and trans-enantiomers triethylene glycol 1,10-decane diol; and mixtures of any of the foregoing. Particularly preferred is 1,4-butane diol. If a cycloaliphatic diol or chemical equivalent thereof and particularly 1,4-cyclohexane-dimethanol or its chemical equivalents are to be used as the diol component, it is pre~erred that a ratio of cis- to ;

.

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-6- 336~2222 (8CV~5125) trans-enantiomer thereof ranging from 1 to 4 to 4 to 1, and preferably a ratio of 1 to 3 is used.
Chemical equivalents to the diols include esters or ethers such as dialkyl esters, diaryl esters, polytetra-methylene oxide, and the like~
The cycloaliphatic diacids (B) useful herein include carboxylic acids having two carboxyl groups each of which is attached to a saturated carbon in a satura~ed ring.
A preferred mi~ture of cycloaliphatic diacids is a mixture of predominantly the trans-enantiomer of 1,4-cyclohexane dicarboxylic acid and the remainder, the cis-enantiomer of 1,4-cyclohexane dicarboxylic acid.
Cyclohexanedicarboxylic acids and their chemical equivalents can be prepared, for example, by the hydrogenation o~ cycloaromatic diacids and oorresponding 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. Pate~t Nos. 2,675,390 and 4,754,064. They may also be prepared by the use of an inert liquid medium in which a phthalic acid is at least partially soluble under reaction conditions and a catalyst of palladium or ruthenium in carbon or silica. See, U.S. Patent Nos. 2,888,484 and 3,444,237.
Typically in the hydrogenation, two enantiomers are obtained in which the carboxylic acid groups are in cis- or - trans-positions. The cis- and trans-enantiomers can be separated by crystallization with or without a solvent, for example, n-heptane, or by distillation. The cis-enantiomer tends to blend better; however, the trans-enantiomer has higher melting and crystallization temperatures and is preferred in a major proportion in a mixture of the enantiomers. Mixtures oE the cis- and trans-enantiomers ~ ` .
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~3~7 -7- 336-2222 (8CV-5125) useful herein comprise predominantly the trans-enantiomer with the remainder comprising the cis-enantiomer, i.e. from about 51 to ahout 99.5 parts by weight of the trans-enantiomer and from about 0.5 to about 49 parts by weight of the cis-i enantiomer based upon 100 parts by weight of the cis- and the trans-enantiomers combined. Most preferably, 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.
Chemical equivalents of the cycloaliphatic diacids include esters, alkyl esters, e.g. dialkyl esters, diaryl esters, anhydrides, acid chlorides, acid bromides, and the like. The preferred chemical equivalents comprise the dialkyl esters of the cycloaliphatic diacids, and the most preferred chemical equivalent comprises the dimethyl ester of the cycloaliphatic diacid, particularly dimethyl-1,4-cyclo-hexanedicarboxylate.
Dimethyl-1,4-cyclohexanedicarboxylate can be obtained by ring hydrogenation of dimethylterephthalate, and two enantiomers having the carboxylic acid groups in the cis-or trans- positions are obtained. The enantiomers can be separated as above, and the trans-enantiomer is especially preferred in a major proportion for the reasons above.
Mixtures of the enantiomers are suitable as explained above and preferably in amounts as explained above.
Examples of aromatic diacids (C) include isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl) ethane, ; 4,4'-dicarboxydiphenyl ether, etc. and mixtures of these.
The preferred aromatic dicarboxylic acid is terephthalic acid.
Chemical equivalents of the aromatic diacids also include esters, alkyl esters, e.g. dialkyl esters, diaryl esters~ anhydrides, acid chlorides, acid bromides and the like. The preferred chemical equivalents comprise the dialkyl esters of the aromatic di~cids, and the ~ost , :

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-8- 336-2222 (3CV-5125) preferred chemical equivalents comprise the dimethyl esters of the aromatic acids, particularly dimethyl terephthalate.
The copolyester compositions of the present invention are typically obtained throu9h the condensation or transesterification of the diol or diol equivalent component (A~ with the mixture of at least two cycloaliphatic diacids or chemical equivalents component ~B) and the aromatic diacid or chemical equivalent component (C) and have recurring units of the formula ~ o o _ O-R-O-C-R -C
x O O
~ O-R-O-C-R~ -~t Y , wherein R represents an alkyl or cycloalkyl radical containing 2 to 10 carbon atoms and which is the residue of a straight chain, branched, or cycloaliphatic alkane diol having 2 to 10 carbon atoms or of a chemical equivalent thereof;
R is a mixture of at least two cycloaliphatic radicals which are the decarboxylated residue derived from a cycloaliphatic diacid or chemical equivalent thereof, the mixture comprising predominantly a trans-enantiomer;
R" is an aromatic radical which is the decarboxylated residue derived from an aromatic diacid or chemical equivalent thereof; and the x units comprise rom about 10 to about 90 parts by 2S weight and the y units comprise from about 90 to about 10 parts by weight of 100 parts by weight of the copolyester.
They particularly have recurring units of the formula -9- 336-22~ (8CV-5125) ~--o-CH2-C~2~CH2~Cll2~o-c{}

_~--O-C12-Cl12-c~2-cil2-o-c~}

wherein R from above is derived from 1,4-butane diol;
: R from above i5 a trans- or cis-cyclohexane ring derived from trans- or cis-cyclohexanedicarboxylate or a chemical eguivalent thereof and is a mixture of predominantly the trans-enantiomer thereof;
R" is an aromatic unsaturated ring derived from terephthalic acid or a chemical equivalent thereof; and ~ 10 the x units and the y units are as defined above.
~ All such polyesters can be made following the teachings of, or example, U.S. Patent Nos. 2,465,319, ~`. 2,901,466, 3,047,539, and 3,515,628.
The reaction is generally run with an excess of the . 15 diol component and in the presence of a suitable catalyst .. ~ such as a tetrakis(2-ethyl hexyl)titanate, in a suitable : amount, typlcally about 20 to 200 ppm of titanium based upon .~ the final product.
The molar ratio of cycloaliphatic diacid or ~ 20 chemical equivalent to aromatic diacid or chemical equivalent `-~ should be such that impact strength of the copolyester is increased over that of the separate homopolymers. The ratio . genera}ly ranges from about 1 to 9 to about 9 to 1 and ; preferably from about 1 to 5 to about 5 to 1. In a preferred embodiment, the molar ratio ranges from less than about 1 to 1 to about 1 to 9, particularly when the cycloaliphatic : diacid or chemical equivalent components comprises a mixture of cis- and trans-1,4-cyclohexane dicarboxylic acid or cis-and trans-dimethyl-1,4-cyclohexanedicarboxylic acid with only a small but measurable amount of cis-enantiomer, a mixture of ~, - .. . . :
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2~3~7 -lO- 336-2222 (8CV-5125) the cis- and trans-enantiomers thereof wherein the ratio of cis:trans is 1:3 or less, or when only the trans-enantiomer thereof is used. In another oreferred embodiment, when ~he cycloaliphatic diacid or chemical equivalent component comprises only a small but measurable amount of l,4-cis-cyclohexane dicarboxylate acid or dimethyl cis-1,4-cyclo-hexanedicarboxylic acid and the remainder the correspondin~
trans-enantiomer, the molar ratio of cycloaliphatic to aromatic diacid or chemical equivalent is less than l to l and when the cycloaliphatic diacid or chemical equivalent component comprises a mixture of at least ~bout 75 parts by weight of the trans- and the remainder the cis-enantiomer of 1,4-trans-cyclohexane dicarboxylic acid or dimethyl-trans-l,4-cyclohexane dicarboxylate based upon lO0 parts by weight of the cis- and trans-enantiomers combined, the molar ratio of cycloaliphatic to aromatic diacid or chemical equivalent thereof ranges from greater than 3 to 2 to 9 to l.
The copolyester compositions of the present invention are highly crystalline and crystallize rapidly.
They have single melting points int~rmediate between those of homopolymer~ of the diol and either of the cycloaliphatic or aromatic diacid components, indicating true co-crystallization of the two different ester segments. In contrast, melt blends of the homopolymers demonstrate distinct melting peaks and two distinct crystallization peaks.
Special mention is made of blends comprising the compositions of the present invention. Additionally, the compositions of the present invention may be molded, extruded, or thermoformed into articles by conventional methods known to one of ordinary skill in the art.
Conventional processes for mixing thermoplastic polymers can be used for the manufacture of compositions within the present invention. For example, the compositions can be manufactured using any suitable mixing equipment, 2~1~3~7 -11- 336-2222 (8CV-5125) cokneaders, or extruders under conditions known to one of ordinary skill in the art.
Additionally, conventional additives such as other thermoplastic resins, reinforcing fibers or fillers, impact modifiers, flame retardants, pigments, or combinations of any of the foregoing may be added to compositions of the present invention.
Illustrative of the thermoplastic resins are a vinyl resin, a polyester resin, a polyamide resin, a polycarbonate resin, a polyacetal resin, a polyether resin, a poly(etherester) resin, a poly(etherimide) resin, a poly(etherimide ester) resin, a poly(sulfone) resin, a poly~e~hersulfone) resin, interpolymers comprising units of any of the foregoing resins, compositions comprising blends of any of them or a combination of any of the foregoing.
Examples of suitable vinyl resins include styrene polymers and copolymers as w211 as substituted styrene polymers and copolymers, e.g., those from vinyl toluene and alpha-methylstyrene and any copolymerizable vinyl monomer, such as acrylonitrile, methyl methacrylate, maleimide, or maleic anhydride, as well as grafts of styrene and related compounds and backbone polymers such as butadiene, i.e., the styrene polymers known as high i~pact polystyrene, also known as, HIPSo Examples of suitable polyesters are linear saturated polyesters which can be obtained either by polycondensation of a hydroxycarboxylic acid, or preferably, by synthesis from a dicarboxylic acid and a saturated diol.
These include but are not limited to poly(butylene trans-1,4-cyclohexane dicarboxylate), poly(l,4-butylene terephthalate) and the like.
Examples of suitable nylons are linear polycondensates of lactams of 6 to 12 carbon atoms and conventional polycondensates of diamines and dicarboxylic acids, e.g. nylon 6,6; nylon 6,8; nylon 6,9; nylon 6,10;
~. , 2~3~

-12- 336-2222 (8CV 5125) nylon 6,}~; nylon 8,8; and nylon 12,12. Purther examples to be mentioned are nylon 6, nylon 11 and nylon 12, which are manufactured from the corresponding lactams. In addition, it is possible to use polycondensates of aromatic dicarboxylic acids, e.g., isophthalic aicd or terephthalic acid, with diamines, e.g., hexamethylenediamine or octamethylenediamine, polycondensates of aliphatic starting materials, e.g., m- and p-xylylenediamines, with adipic acid, suberic acid and sebacic acid, and polycondensates basecl on alicyclic starting materials, e.g., cyclohexanedicarboxylic acid, cyclohexane-c diacetic acid, 4,4'-diaminodicyclohexylmethane and 4,41_ diaminodicyclohexylpropane. The nylons preferably have a relative viscosity of from 2.30 to 3.60 measured at 1 percent s~rength in concentrated sulfuric acid at 24C.
A polycarbonate is poly-2,2~propane-bis(4-phenyl~-carbonate, which is manufactured in accordance with con~entional processes by reacting phosgene or diphenyl-carbonate with 2,2-bis(4'-hydroxyphenyl)-propane. Other preferred polycarbonates contain tetrabromobisphenol-A as an additional comonomer, which improves the fire resistance of the molding compositions.
Examples of polyacetals which may be employed are, in particular, the oxymethylene polymers, polyoxymethylene being of particular importance. However, oxymethylene copolymers which, in addition to oxymethylene groups, con~ain up to 30 percent by weight, preferably from 0.1 to 25 percent by weight, of other oxyalkylene groups, for example the oxyethylene group, the trimethylene oxide group, or preferably, the tetramethylene oxide group~ are also suitable, as are terpolymers. The use of oxyme~hylene homopolymers in which the end groups of the molecules have been stabilized against ~egradation by esterifying, etherifying or some other conventional chain termination is preferred. The oxymethylene polymers usually have a ~elting point of about 130C.

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-13- 336-2222 (8CV-5125) Polyethers which can be used include polyarylene ethers amongst which polyphenylene ethers deserve particular mention. ~he use of poly(2,6-dimethyl-1,4~phenylene oxide) is preferred~ and in ordee to lower its melt viscosity and improve its processability, it may be advantageous to admix it with from about 10 to 90 percent by weight of polystyrene (based on the mixture of polyphenylene ether and polystyrene).
If polyphenylene ethers are to be blended, e.g., with polyamides, polycarbonatas, polyesters, mixtures thereof, and the like, a small amoun~ of functionalizing agent, e~g., maleic anhydride, fumaric acid, etc., can be reacted with the polyphenylene ether in known ways to improve compatibility.
Impact modifiers useful herein include but are not llmited to multi-stage core-shell po}ymers havlng a rubbery core derived from an acrylate or a (meth)acrylate, a diene, or a mixture of the foregoing, and a vinyl-based polymer or copolymer outer shell, some of which are available commercially under the tradenames ACRYLOID~ KM 330, also known as PARALOID~ EXL 3330, or ACRYLOID~ R~ 653, also known as PARALOIDa EXL 3691, from Rohm ~ Haas Company.
` Suitable impact modifiers also include but are not limi~ed to A~S modifiers which are typically represen~ed by graft copolymers of vinyl cyanide-conjugated dio}efin-alkenyl aromatic. They particularly comprise acrylonitrile-butadiene-styrene graft copolymers, but also encompass mixtures of a~alogous materials.
Preferably, the ratio of styrene to acrylonitrile in the terpolymer ranges f-rom about 3.5 to 1 to about 2.5 to 1 and the ratio of butadiene to styrene/acrylonitrile is 7 to 3. Most preferably, the ratio of sytrene to acrylonitrile is either 3.5 to 1, 3 to 1 or 2.5 to 1.

DESCRI2TION OF T~ PREF~RR~D EMBODIMRNTS
The following examples illustrate the invention without limitation. ~11 parts are given by weight unless otherwise indicated. Impact strengths are represented as ~; , , ,, .~ ;

20fi35~

-14- 336-2222 (8CV-5125) notched and unnotched Izods according to ASTM~D-256 or Dynatup impact at room temperature (RT) (23C) unless otherwise specified. Strength properties are measured by ASTM-D-638 as flexural modulus, flexural strength, tensile break s~rength and tensile elongation. Melt viscositieS are determined at 250C unless otherwise indicated. All poly(l,4-butylene-1,4-trans-cyclohexane dicarboxylate), all 1,4-trans-cyclohexanedicarboxylate and chemical equivalents thereof, and compositions containing the same used in the axamples below had a measurable, but very small cis-enantiomer c content.

CO~PARATIV~ ~XA~L~ lA~
Poly(1,4-butylene-1,4-trans-cyclohexane dicarboxylate) (P~CD) was produced by the transesterification of 133,0 parts of trans-1,4-dimethylcyclohexane dicarboxylate ~t-DMCD~, 101.0 parts of 1,4-butane diol (aD) and about 160 ppm of titanium in the form of tetrakis(2-ethyl hexyl) titanate.
Tensile and Izod bars were molded on a 3.5 oz. Van Dorn injection molding machine with barrel zone temperatures at 250C, nozzle temperature at 260C and mold temperature at 75C.
Properties are summarized in Table 1.

EXAMPL~ 1 A copolyester was produced by transesterification of 14.0 parts of trans-1,4-dimethylcyclohexane dicarboxylate (t-DMCD) and 7.0 parts of dimethyl terephthalate (DMT) in a molar ratio of 2:1, an excess of 1,4-butane diol (~D), and about 160 ppm of titanium in the form of tetrakis(2-ethyl hexyl) titanate.
Tensile and Izod bars were molded on a 3.5 oz. Van Dorn injection molding machine with barrel zone temperatures at 250C, nozzle temperatuce at 260C and mold temper~tuce at 75C.

- ' ~

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-15- 336-2222 (8CV-5125) Spiral flow was measured on a 3.5 oz. Van Dorn injection molding machine at a pressure of 600 psi, a cycle time of 30 seconds, barrel zone temperatures of 250C, nozzle temperature of 260C, and mold temperature of 75C in two molds, one having three channels having cross-sections of .048" x .313~, .032" x .313~, and .016" x .313" radiating from the center and one having a single mold channel .096" x .313".
DSC measurements were made with a heating rate of 20C/min. to determine peak melt temperature, Tm, and enthalpy of fusion, Hm; and with a cooling rate of 60C/min.
to determine peak crystallization temperature, Tc, and enthalpy of crystallization, Hc.
Properties are summarized in Table 1.

XA~PL~ 2 The procedure of Example 1 was followed substituting a molar ratio of t-DMCD:DMT of 1:1.
Properties are summari2ed in Table 1.

EXAi~PL~ 3 -The procedure of Example 1 was followed substituting a molar ratio of t-DMCD:DMT of 1:2.
Properties are summarized in Table 1.

EXA~PLE 4 The procedure of Example 1 was followed substituting a molar ratio of t-DMCD:DM~ of 1:2 to produce a copolyester (melt viscosity 5000 poise) which was molded and tested as in Example 1.
Properties are summarized in Table 1.

EXAMPL~ 5 The procedure of Example 1 was followed substituting a molar ratio of t-DMCD:DMT of 1:2 to produce a copolyester 2~33~7 -16- 336-2222 (~CV-~125) (melt viscosity 3000 poise) which was molded and tested as in Example 1.
Pcoperties are summarized in Table 1.

2XAoPL~ 6 The procedure of Example 1 was followed substituting a molar ratio of t-DMCD:DMT of 1:2 to produce a copolyester (melt viscosity 1900 poise) which was molded and tested as in Example 1.
Properties are summarized in Table 1.

lo e~P~ 7 The copolyester of Example 6 was blended with 0.1 part of a mold release package. The resultant composition : was extruded on a 2.5~ single screw extruder operating at 100 rpm with barrel zone temperatures at 250C. The extruded composition was molded and tested following the procedure of Example 1.
Properties are summarized in Table 1.

EXA~PL~ 8 The procedure of Example 1 was followed substituting a molar ratio of t-DMCD:DMT of 1:3 to produce a copolyester (melt viscosity 4800 poise) which was molded and tested as in Example 1.
Properties are summarized in Table 1.

EXA~PL~ 9 The procedure of Example 1 was followed substituting a molar ratio of t-DMCD:~MT of 1:3 to produce a copolyester (melt viscosity 2000 poise) which was molded and tested as in Example 1.
Properties are summarized in Table 1.

.. : ., .
.~ . . . .
. . ~ . .

20~3~7 -17- 33~-~222 (~CV-5125) E~A~PLE 10 .
The copolyester of Example 9 was blended with 0.1 part of a mold release package. The resultant blend was . extruded, molded and tested following the procedure of .~ 5 Example 1.
Properties are summarized in Table 1.
.
.
The procedure of Example 1 was followed substituting `~ a molar ratio of t-DMCD:DMT of 1:3 to produce a copolyester (melt viscosity 5600 poise) which was molded and tested as in Example 1.

CO~PARATI~ ~XA~PL~ llA*
.: Poly(1,4-butylene terephthalate) (P~T) was produced by the transesterification of dimethyl terephthalate (DMT), :- 15 an excess of 1,4-butane diol (BDI, and 160 ppm of titanium in the form of tetrakis(2-ethyl hexyl) titanate.
The polyester was molded and tested following the procedure of Example 1.
Properties are summarized in Table 1.

COMPARATIV2 EXA~PLZ llB~
100.0 parts by weight of poly(l,4 butylene : terephthalate) produced by the transesterification of dimethyl terephthalate and 1,4-butane diol (PBT-Valox' 307 -General Electric Company) were molded and tested following the procedure of Example 1-.
Properties are summarized in Table 1.

CO~PARATIV~ eXAMPL~ llC~
99.75 parts of poly(l,4-butylene terephthalate) produced by the transesterification of dimethyl terephthalate and 1,4-butane diol (P8T-Valox~ 325M - General Electric Company) and 0.25 part of a mold release/stabilizer ~, .

: .
:

2~i3~3~P.~

.
-18- 336-2222 (8CV-51~5) : package were extruded, molded and tested following the procedure of Example 1.
Properties are summarized in Table 1.

CO~PARATIV~ ~AoPL~ llD*
: S 99.65 parts of poly(l,4-butylene terephthalate~
: produced by the transesterification of dimethyl terephthalate and 1,4-butane diol ~PBT-Valox~ 325 ~ General Electric Company) and 0.35 part of a mold release/stabilizer package were extruded, molded and tested following the procedure of Example 1 Properties are summarized in Table 1.

Examples 1 and 3-10 when compared with Comparative Example lA* and llA-D~ illustrate that the ductility of : copolyesters of the present invention, as measur~d by Notched Izod impact strength, is significantly superior to that of the homopolymers~
Examples 1 and 4-10 when compared with Comparative Exampl~s llA-D~ illustrate the improved melt flow of the copolyesters of the present invention.

-19- 336-2222 ( aCV~5125 ~ 2 0 ~ 3 5 ~ ~

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2~35~7 -21- 336-2222 (8CV-5125) CO~PARATIVE_EXAMPL~ 1~*
A melt blend of 2.0 parts of poly(l,4-butylene terephthalate) (melt viscosity 7500 poise), 1.0 part of poly(l,4-butylene-trans-cyclohexanedicarboxylate) (PBCD) (melt viscosity 6000 poise) and 0.2 part of antioxidant was prepared, extruded, molded and tested as in Example 1.
The parts had a pearlescent appearance. The DSC
curves indicated double melting and crystallization temperatures corresponding to separate melting and crystallization of the individual components.
Properties are summarized in Table 2.

COMPARATIV~ EXAMPLE 13*
~- A melt blend of equal parts of poly(l,4-butylene terephthalate) (PBT) (melt viscosity approximately 8000 poise) (Valox 315 - General Electric Company - Pittsfield, MA) and poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate) ~P~CD) (melt viscosity 2500 poise~ was prepared and was extruded, molded and tested as in Example 1.
Two distinct DSC melting peaks at 161C and 22~C
respectively were found. Additionally, two distinct crystallization peaks at 170C and 132C were found.
Properties are summarized in Table 2.

COMP~RATIV~ ~XAMP~E 14*
A melt blend of 1.0 part of poly(l,4-butylene terephthalate) (melt viscosity 7500 poise~, 2.0 parts of poly(l,4-butylene-trans-1~4-cyclohexanedicarboxylate) ~PBCD) (melt viscosity 6000 poise) and 0.2 parts of antioxidant was prepared, extruded, molded and tested as in Example 1.
~he parts had a pearlescent appearance. The DSC
curves indicated double melting and crystalliz~tion temperatures corresponding to separate melting and crystallization of the individual components.
Properties are summarized in Table 2.

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-22- 336-2222 (8CV-5125) CO~PARATIV~ 8XAMPL~ 15~
A me}t blend of 3.0 parts of poly(l~4-butylene terephthalate) (PBT) (Valox~ 315 - General Electric Company) and 1.0 part of poly(l,4-butylene-trans 1,4-cyclohexane-dicarboxylate) (PBCD) (melt viscosity 1100 poise) wasprepared. The melt blend was extruded, molded and tested as in Example 1.
Properties are summarized in Table 2.

Examples 1-4 when compared with Comparative Examples 12*-15* illustrate the improved ductility, as measured by Notched Izod, that copolyesters of the present invention exhibit over melt blends of homopolymer polyesters prepared from the same reactants.
The single melting and crystallization peaks observed in Examples 1-4 when compared with the two distinct melting peak~ observed in Comparative Examples 12* and 15*
and the two distinct crystallization peaks observed in Comparative Example 12* indicate the surprising co-crystallization of the butylene cyclohexanedicarboxylate and the butylene terephthalate segments of the copolyesters of the present invention.

-~, ' . , 2~3~7 -~3- 3~6-2222 (8CV-5125) T~BL~ 2 PBCD-PBT M~LT BLBNDS

A 8 - 13 14~ 15*
PBCD :PBT
(weight ratio) 1:2 1:1 2~ 3 Antioxidant (~) 0.2 - 0.2 M~lt Viscosity @ 250C (poise) - - - 5100 DSC Data Tm (C) 162/227 161/226 163/229 163/225 Hm (J/g)5.7/27.1 - 15.1/16.7 Tc (C) 187/135 170/132 185/135 . Hc (J/g)21.1/8.0 - 10.4/17.1 Tensile Strength (psi) - - - 6300 Tensile Elongation (~ 150 Flexural Modulus (Kpsi) 257 - 133 298 Flexural Strength (psi) 10~00 - 13300 11200 Notched I~od @ RT
(ft-lbs/in) 0.9 - 1.0 0.86 Unnotched Izod @ RT
(ft-lbs/in) - - - ~B
Falling Dart Impact @ max. load (ft.-lbs.) - - - 1 total load (ft.-lbs.) - - - 27 A - poly(l,4-butylene-trans-1,4-cyclohexanedicarboxylate).
B - poly(l,4-butylene terephthalate) - Valox~ 315 - General Electric Company - Pittsfield, MA.

: , 2 0 ~

-24- 336-2222 (8CV-5125) A melt blend of 50.0 parts of a copolyester prepared by the procedure of Example 3 and 50.0 parts of poly~l,4-butylene terephthalate) (PBT) (Valox a 315 - melt viscosity approximately 8000 poise General Electric Company) having an overall t-DMCD:DMT ratio of 1:5 was extruded, molded and ~ested as in Example 1.
Transmission electron microscopy indicated the blend was homogeneous.
Properties are summari2ed in Ta~le 3.

~XAMPLE 17 .
A melt blend of 50.0 parts of a copolyes~er prepared by the procedure of Example 3 and 50.0 parts of poly(l,4-butylene trans-1,4-cyclohexane dicarboxylate) (PBCD) (melt viscosity 3000 poise) having an overall t-DMCD:DMT
ratio of 2:1 was extruded, molded and tested as in Example 1.
Transmission electron microscopy indicated that the blend was not homogeneous but formed continuous interpenetrating network domains.
Pcoperties are summarized in Table 3 ~_ . .
A melt blend of 50.0 parts of a copolyester prepared by the procedure of Example 1 and 50.0 parts of poly(l,~-butylene terephthalate) (PBT) (Valox 315 - melt viscosity approximately 8000 poise - General Electric Company) having an overall-t-DMCD:DMT ratio of 1:2 was extruded, molded and tested as in Example 1.
The blend had a pearlescent appearance, and the DSC
curves showed separate melting points of the individual copolyester and polyester components.
Transmission electron microscopy indicated that the blend was not homogeneous but formed continuous interpenetrating network domains.
Properties are summarized in Tab}e 3.

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.

2~fi35~7 -25- 336-2222 (aCV-5125) EXA~PLE 19 A melt blend of 50.0 parts of a copolyester prepared by the procedure of Example 1 and 50.0 parts of polybutylene cyclohexane dicarboxylate (PBCD) (melt viscosity 3000 poise) having an overall t-DMCD:DMT ratio of 5:1 was extruded, molded and tested as in Example 1.
Transmission electron microscopy indicated that the blend was homogeneous.
Properties are summarized in Table 3.

eXA~P~E 20 A melt blend of 60.0 parts of a copolyester having a melt viscosity of 2200 poise at 250C prepared by the transes~erification of trans-1,4-dimethylcyclohexane dicarboxylate (t-DMCD) and dimethyl terephthalate (DMT) in a molar ratio of 1:2, an excess of 1,4-butane diol (BD), and about 160 ppm of titanium in the form of tetrakis(2-ethyl hexyl) titanate and 40.0 parts of poly(l,4-butylene terephthalate~ (PBT - Valox9 325 - General Electric Company) having an overall t-DMCD:DMT ratio of 1:4 was extruded, molded and tested as in Example 1.
The blend is homogeneous.
Properties are illustrated in Table 3.

EXAMPL~ 21 ; A melt blend of 75.0 parts of the copolyester of Example 20 and 25.0 parts of poly(lr4-butylene terephthalate) (PBT - Valox' 325 - melt v-iscosity approximately 5800 poise -- General Electric Company~ having a~ overall t-DMCD:DMT ratio -;~ of 1:3 was extruded, molded and tested as in Example 1.
The blend is homogeneous.
Properties are summarized in Table 3.

~AMPL~ 22 A melt blend of ~0.0 parts of 2 copolyester having a melt viscosity of 2400 poise was prepared by the trans-~'; .
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2~3~7 -26- 336-2222 (8CV-5125) esterification of trans-1,4-dimethylcyclohexane dicarboxylate (t-DMCD) and dimethylterephthalate (DMT) in a molar ratio of 1:3, an excess of 1,4-butane diol (BD), and about 160 ppm of titanium in the form of tetrakis(2-ethyl hexyl tttanate), and 20.0 parts of poly(l,4-butylene terephthalate (PBT - Valox~
325 - General Electric Company) having an overall t-DMCD:DMT
ratio of 1:4 was extruded, molded and tested as in Example 1.
Properties are summarized in Table 3.

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2~6~7 -~9~ 336-2222 (8CV-5125) ~YA~PLY 23 A blend of 50.0 parts of the copolyester of Example 3 and 50.0 parts of polycarbonate cesin (poly(bisphenol-A) carbonate - Lexan~ 120 - General Electric Co.) was extruded, blended and tested as in Example 1.
The blend was observed to be homogeneous and transparent. On heating at 20C per minute in the DSC, the blend crystallized at 133C with an enthalpy of crystallization of 14.2 ~/g.
Properties are summarized in Table 4.

,~ , 2 ~ 7 -30- 336-2222 ~8CV-5125) TA~L~ 4 COPOL~EST~R~PC BL~DS

CopolyesterA
(t-DMCD:DMT-1:2) 50 PolycarbonateB 50 DSC:
Tm (C) 185 Hm (J/g)C 14.1 Tch (C) 133 Hch (J/g)D 14.2 Tensile Strength ~psi) 8900 Tensile Elongation (%) 200 Flexural Modulus (Kpsi) 348 Flexural Strength ( psi ) 13100 Notched Izod @ RT
(ft.-lbs./in.) 0.8 Unnotched Izod @ RT
(ft.-lbs./in.) 18 A - melt viscosity - 4700 poise at 250C - Example 3.
- poly(bisphenol-A) carbonate - Lexan~ 120 - Genecal Elect~ic Co. - Pittsfield, MA.
C - pe~k temperature of crystallization on heating at 20C/min.
D - enthalpy of crystalli2ation on heating at 20"C/min.

~ , .
~ ' ' ~0~3~7 -31- 336-2222 (8CV-5125) ~XA~PL~ 24 A b}end of 65.0 parts of the copolyester of Example 20, 15.0 parts of poly(butylene cyclohexane dicarboxylate) having a melt viscosity of approximately S000 poise at 250C, 15.0 parts of a core-shell multi-stage polymer having a core of polymerized butadiene and styrene, methylmethacrylate and divinylbenzene, a second stage/shell of polymerized styrene and an outer shell of polymerized methylmethacrylate and 1,3-butylene glycol ~ethacrylate (ACRYLOID KM 330, also known as PARALOID- EXL 3330 - Rohm & Hass Co. - Philadelphia, c PA) and 1.0 part of a stabllizer package was extruded, molded and tested as in Example 1.
The blended product was observed to be flexible and elastomeric.
Properties are summarized in Table 5.
.

'''' '''- ' ~' ~3~

-32- 336-22~2 (8CV-5125) T~BLE S
I~PACT ~ODIFI~D COPOLYEST~ BLRND

Example 24 CopolyesterA 69.0 PBCDB 15 . O
C

Modifier 15.0 Stabilizers 1.0 Overall t-DMCD:DMT 9:11 Tensile Strength (psi) 3800 Tensile Elongation (~) 325 Flexural Modulus (Kpsi) 109 Plexural Strength (psi) 6500 Notched Izod (fpi) @ 25~ 9.2 -40C 2.6 Unnotched Izod tfpi) @ 25C 13.4 Falling ~art Impact @ max. load (ft.-lbs.) 12.7 total (ft.-lbs.) 23.2 A - DMCD/3M~ ratio is 1:2 - melt viscosity 2200 poise at 250C.
B - melt viscosity 5000 poise at 250C.
C - core-shell multi-stage polymer - core = polymerized butadiene and styrene, methylmethacryl3te and divinyl benzene - second stage/shell = polymerized styrene -outer shell = polymerized methylmethacrylate and 1,3-butylene ~lycol dimethacrylate - (AC~YLOID3 KM 653, also known as PARALOID~ EXL 3691 - Rohm & Haas Co. -Philadelphia, PA).

.

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-33- 336-2222 (8CV-5125) ~XA~PL~ 25 A random copolymer was prepared by reacting 7.4 parts of 1,4-cyclohexanedimethanol (25:75 cis to trans catio) with 5.0 parts each of dimethyl terephthalate and 5.0 parts of dimethyl-trans-1~4-cyclohexanedicarbo~ylate in the presence of a small amount of titanium ester catalyst.
The product was amorphous, but crystallized on heating in the Differential Scanning Calorimeter with a peak crystallization temperature of 151C and an enthalpy of crystallization of 16.9 J/g. On further heating, the product showed a single me~ling point at 222C with an enthalpy of fusion of 20.5 J/g. The material did not crystallize significantly when cooled in the DSC apparatus at a rate of 60C/min, in contrast to the random PBCD/T copolymers of the present invention.

ex~u~Le ~6 A copolyester was prepared from 5.0 parts of DMT
and 5.0 parts of dimethyl-trans-1,4-cyclohexane dicarboxylate with 7.4 parts of cyclohexanedimethanol with 25:75 cis- to trans-enantiomer ratio and a small amount of tetrakis(2-ethyl hexyl)titanate catalyst using the procedure described above.
The product had a single melting point at 222C
with an enthalpy of fusion of 20.5 J/g. On heating, the material crystallized at 150.8C with an enthalpy of crystallization of 16.9 J/g.
. .
A11 patents' applications, publications and test ; methods mentioned above are hereby incorporated by reference.
Many variations of the present invention will suggest themselves to those skilled in this art in light of the above, detailed description. All such obvious variations are within the Eull intended scope o~ the appended clsims.

, ,

Claims (33)

1. A copolyester composition comprising the reaction product of (A) at least one straight chain, branched, or cycloaliphatic C2-C10 alkane diol or a chemical equivalent thereof; (B) a mixture of at least two cyclo-aliphatic diacids or chemical equivalents thereof, said mixture comprising predominantly a trans enantiomer; and (C) at least one aromatic diacid or chemical equivalent thereof.

2. A composition as defined in Claim 1 wherein said alkane diol (A) is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol and cyclohexane dimethanol.

3. A composition as defined in Claim 2 wherein said alkane diol (A) comprises 1,4-butane diol.

4. A composition as defined in Claim 4 wherein said mixture of cycloaliphatic diacids (B) comprises a mixture of cis- and trans-1,4-cyclohexane dicarboxylic acid.

5. A composition as defined in Claim 4 wherein said cis-enantiomer comprises from about 0.5 to about 49 parts by weight and said trans-enantiomer comprises from about 51 to about 99.5 parts by weight based upon 100 parts by weight of cis- and trans-enantiomers combined.

6. A composition as defined in Claim 5 wherein said mixture of cis- and trans-1,4-cyclohexane dicarboxylic acid comprises at least about 75 parts by weight of the trans-enantiomer and the remainder comprises the cis-enantiomer based upon 100 parts by weight of cis- and trans-enantiomers combined.

7. A composition as defined in Claim 1 wherein at least one of said mixture of at least two cycloaliphatic diacids or chemical equivalents (8) comprises dialkyl esters of cycloaliphatic diacids.

-35- 336-2222 (8CV-5125)

8. A composition as defined in Claim 7 wherein said mixture of cycloaliphatic diacid chemical equivalents (B) comprises a mixture of cis- and trans-dimethyl-1,4-cyclohexane dicarboxylate.

9. A composition as defined in Claim 8 wherein said cis-enantiomer comprises from about 0.5 to about 49 parts by weight and said trans-enantiomer comprises from about 51 to about 99.5 parts by weight of cis- and trans-enantiomers combined.

10. A composition as defined in Claim 9 wherein said mixture of dimethyl-cis- and dimethyl-trans-1,4-cyclo-hexane dicarboxylate comprises at least about 75 parts by weight of the trans-enantiomer and the remainder comprises the cis-enantiomer based upon 100 parts by weight of cis- and trans-enantiomers combined.

11. A composition as defined in Claim 1 wherein said aromatic diacid (C) is selected from the group consisting of isophthalic acid, terephthalic acid, or a mixture thereof.

12. A composition as defined in Claim 11 wherein said aromatic diacid (C) comprises terephthalic acid.

13. A composition as defined in Claim 1 wherein said aromatic diacid chemical equivalent (C) comprises a dialkyl ester of the diacid.

14. A composition as defined in Claim 13 wherein said aromatic diacid chemical equivalent (C) compcises dimethyl terephthalate.

15. A composition as defined in Claim 1 wherein the molar ratio of cycloaliphatic diacid or chemical equivalent thereof to aromatic diacid or chemical equivalent thereof is such that the impact strength of said copolyester is independently increased over the impact strength of the homopolymer of said cycloaliphatic diacid or chemical equivalent thereof and said diol and of the homopolymer of said aromatic diacid or chemical equivalent thereof and said diol.

-36- 336-2222 (8CV-5125)

16. A composition as defined in Claim 1 wherein the molar ratio of cycloaliphatic diacid or chemical equivalent thereof to aromatic diacid or chemical equivalent thereof ranges from 1:9 to 9:1.

17. A composition as defined in Claim 16 wherein the molar ratio of cycloaliphatic diacid or chemical equivalent thereof to aromatic diacid or chemical equivalent thereof ranges from about 1:5 to about 5:1.

18. A composition as defined in Claim 1 wherein the molar ratio of cycloaliphatic diacid or chemical equivalent thereof to aromatic diacid for chemical equivalent thereof ranges from about 1:1 to about 1:9.

19. A composition as defined in Claim 6 wherein the molar ratio of cycloaliphatic diacid or chemical equivalent thereof to aromatic diacid or chemical equivalent thereof ranges from about 1:1 to about 1:9.

20. A composition as defined in Claim 10 wherein the molar ratio of cycloaliphatic diacid or chemical equivalent thereof to aromatic diacid or chemical equivalent thereof ranges from about 1:1 to about 1:9.

21. A copolyester composition comprising the reaction product of (A) 1,4-butane diol, (B) a mixture of dimethyl-cis- and trans-1,4-cyclohexane dicarboxylate, said mixture comprising predominantly the trans-enantiomer and (C) dimethyl terephthalate.

22. A composition comprising a copolyester as defined in Claim 1 and (a) one or more of the same or a different thermoplastic resin from said copolyester, (b) reinforcing filler, (c) impact modifier, (d) flame retardant, (e) pigment, or (f) a combination of any of the foregoing.

-37- 336-2222 (8CV-5125)

23. A composition as defined in Claim 22 wherein said thermoplastio resin (a) is selected from the group consisting of a vinyl resin, a polyester resin, a polyamide resin, a polycarbonate resin, a polyacetal resin, a polyether resin, a polyphenylene ether resin, a poly(etherester) resin, a poly(etherimide) resin, a poly(etherimide ester) resin, a poly(ethersulfone) resin, a poly(sulfone) resin, interpolymers comprising units of any of the foregoing resins, and compositions comprising blends of any of the foregoing, or a combination of any of the foregoing.

24. A composition as defined in Claim 22 wherein said impact modifier (c) comprises a multi-stage core-shell polymer having a rubbery core derived from an acrylate or a (meth)acrylate, a diene or a mixture of the foregoing; and a vinyl-based polymer or a copolymer outer shell.

25. A composition as defined in Claim 22 wherein said modifier (c) comprises a multi-stage core-shell polymer having a core comprising polymerized butadiene/styrene, an intermediate shell comprising polymerized styrene, and an outer shell comprising polymerized methylmethacrylate and 1,3-butylene-glycol dimethacrylate.

26. A composition as defined in Claim 22 wherein said impact modifier (c) comprises a vinyl cyanide-conjugated diolefin-alkenyl aromatic terpolymer.

27. A composition as defined in Claim 26 wherein said modifier (c) comprises a terpolymer of acrylonitrile, butadiene and styrene.

28. A composition as defined in Claim 27 wherein said impact modifier (c) comprises a terpolymer of acrylonitrile, butadiene and styrene having a styrene to acrylonitrile ratio ranging from about 3.5 to 1 to about 2.5 to 1 and a butadiene to styrene/acrylonitrile ratio of 7 to 3.

29. A composition as defined in Claim 28 wherein said ratio of styrene to acrylonitrile is selected from the group consisting of 3.5 to 1, 3 to 1 and 2.5 to 1.

-38- (8CV-5125)

30. A article thermoformed from a composition as defined in Claim 1.

31. An article extruded from a composition as defined in Claim 1.

32. An article molded from a composition as defined in Claim 1.

33. The invention as defined in any of the preceding claims including any further features of novelty disclosed.