EP0951510A1

EP0951510A1 - Tough reinforced polyesters with improved flow

Info

Publication number: EP0951510A1
Application number: EP97951762A
Authority: EP
Inventors: Bruce Connard Bell; Thomas Eduard Flora; Larry Allen Minnick
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 1996-12-19
Filing date: 1997-12-17
Publication date: 1999-10-27
Also published as: WO1998027159A1; JP2002509565A; CN1247551A; BR9713952A

Abstract

This invention relates to polymer molding composition, containing: (a) a first polymer, including a polyester, a polycarbonate, or a mixture thereof; (b) a second polymer including at least one first α-olefin, at least one first alkyl acrylate, and at least one unsaturated epoxide; and (c) a third polymer including at least one second α-olefin and at least one second alkyl acrylate. The invention further relates to a thermoplastically-formed article prepared from the polymer molding compositions described above.

Description

TOUGH REINFORCED POLYESTERS WITH IMPROVED FLOW

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority upon provisional application serial no.

60/032,452, filed December 19, 1996, and the 60/032,452 application is herein incorporated by this reference in its entirety.

FIELD OF THE INVENTION

The present invention relates to a polymer composition comprising a polycarbonate or a polyester, which preferably comprises terephthalic acid and is optionally reinforced with glass fibers. This polymer composition has improved flow, improved toughness and impact resistance, and a high heat deflection temperature.

BACKGROUND OF THE INVENTION

It is well known that plastics can be substantially toughened by incorporation of a dispersed rubbery phase in the polymer matrix. The rubbery phase acts to absorb the energy of impact or deformation. Adhesion between the rubbery phase and the matrix is important to the transfer of energy. A common example is high impact polystyrene (HIPS) wherein the rubbery polybutadiene (PBD) phase adheres to the brittle polystyrene matrix by virtue of graft copolymers PS-g-PBD that tie the two incompatible phases together. For toughening of polyester compositions, as taught in U.S. Patent 4,172,859; U.S. Patent 4,753,980; and U.S. Patent 5,436,296, very good adhesion between the incompatible rubbery particles and the polyester matrix is achieved by including an epoxy (or oxirane) functionalized comonomer in the rubbery polymer that can react directly with the polyester. Reinforcing fillers can have significant negative effects on toughness and impact resistance. Therefore, adhesion between the surfaces of the matrix and the impact modifier is important. As is common practice in the industry, glass fibers are coated with coupling agents and thin films (sizing) that specifically promote adhesion to polyesters and epoxies. The result is good adhesion between all three phases.

It is well recognized by those practiced in the art that interphase adhesion can lead to very poor melt flow, that is, high melt viscosities, and thus, difficulties in processing, especially injection molding to form intricate thin-walled parts. C. B. Bucknall, Toughened Plastics, Applied Science Publishers Ltd., London, 1977, on page 313, recites that "The addition of rubber particles produces a shaφ increase in the viscosity of a polymer melt. Many manufacturers offset this increase by reducing the molecular weight of the matrix polymer, accepting a small reduction in fracture resistance . . . in return for better molding behavior in the rubber- toughened product." It is therefore one object of this invention to improve the melt viscosity (or mold flow) while maintaining toughness, impact resistance and heat deflection temperature (HDT) of a molding composition.

U.S. Patent 4,172,859 pertains to the toughening of polyesters. Although U.S. Patent 4,172,859 recognizes the necessity of interphase adhesion with the recited criteria of "sites which adhere to the matrix resin," the detrimental effect of this adhesion on the important property of mold flow or melt viscosity is not taught therein. U.S. Patent 4,172,859 recites the phrase "at least one random copolymer."

However, the patent clarifies this phrase in col. 3 stating that, "other components can be present in the toughened composition provided that the basic and essential characteristics of the toughened composition are not materially affected thereby." U.S. Patent 4,753,980 discloses the use of a terpolymer, ethylene-alkyl acrylate-glycidyl methacryols for toughening polyesters. With the inclusion of glycidyl methacrylate (GMA), the terpolymer contains an oxirane (or epoxy) functionality which adheres to or reacts with polyesters, which increases the melt viscosity as more of this toughening agent is added to the polyester. U.S. Patent

4,753,980 fails, however, to recognize the detrimental effect of this treatment on melt flow.

U.S. Patent 5,436,296 teaches the use of a copolymer of ethylene and glycidyl methacrylate (PE-GMA) as a compatibilizer to modify blends of poly(alkylene terephthalate) (PET) and polyethylene (PE), illustrating that by adding a compatibilizer from between 8 and 15 % based on the weight of the blend, the Izod impact strength and the ductility of the blends increases substantially. U.S. Patent 5,436,296 recites the role "adhesion between different thermoplastic polymer phases" plays in toughening the blend. However, U.S. Patent 5,436,296 does not show or relate the detrimental effect that this adhesion inducing compatibilizer has on melt flow, except to mention that it is "believed that the addition of the glycidyl group containing copolymer above the preferred range increases the viscosity of the resulting blend such that the viscosity increase causes the inversion of the two polymer matrix" (col. 6).

U.S. Patent 4,461,871 addresses the issue of poor melt flow for toughened polyesters, reciting "the flow properties upon injection molding" of toughened polyester compositions "are very poor because of high melt viscosity." The polyester composition claimed in U.S. Patent 4,461 ,871 comprises three components, (a) an aromatic polyester, (b) a copolymer containing glycidyl groups and (c) a copolymer consisting of ethylene and an α-olefin which is defined as an unsaturated hydrocarbon "selected from the group consisting of propylene, 1- butene, 1-pentene, 3-methyl-l-pentene, 1-hexene, 1-octene, and the like." None of the references described above discloses the particular benefits of substantially decreasing melt viscosity of polyesters or copolyesters for better melt flow while maintaining toughness, impact resistance and high heat deflection temperatures.

SUMMARY OF THE INVENTION

In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a polymer molding composition, comprising:

(a) a first polymer, comprising a polyester, a polycarbonate, or a mixture thereof;

(b) a second polymer comprising at least one first α-olefin, at least one first alkyl acrylate, and at least one unsaturated epoxide; and

(c) a third polymer comprising at least one second α-olefin and at least one second alkyl acrylate.

The invention further provides a polymer molding composition comprising

(a) a polycarbonate or a polyester wherein said polyester comprises repeat units derived from:

a dicarboxylic acid component comprising one or more dicarboxylic acids selected from the group consisting of aliphatic dicarboxylic acids having a total of from 3 to 16 carbon atoms, alicyclic dicarboxylic acids having 7 to 12 carbon atoms, aromatic dicarboxylic acids containing a total of from 8 to 16 carbon atoms, and combinations thereof, and

a glycol component comprising one or more glycols having from 2 to 18 carbon atoms, one or more glycol ethers having from 4 to 12 carbon atoms, and combinations thereof,

(b) about 1 to about 20% by weight of a random terpolymer based on one or more α-olefins, one or more alkyl acrylates and one or more unsaturated epoxides having from 4 to 11 carbon atoms, and

(c) about 2 to about 20% by weight of a random copolymer comprising one or more α-olefins and one or more alkyl acrylates,

wherein said weight percentages are based on the total weight percentages of the components of said polymer molding composition equaling 100 weight %.

The invention further relates to a thermoplastically- formed article formed from the polymer molding composition.

The object of the invention is to improve the usefulness of the polymers, and preferably, the thermoplastic polyesters poly(l,4-cyclohexane terephthalate) (PCT) and poly(ethylene terephthalate) (PET) as molding plastics by substantially decreasing the melt viscosity for better melt flow while maintaining the toughness, impact resistance and high heat deflection temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the Examples included therein.

Before the present compositions of matter are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

In this specification, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise.

(c) a third polymer comprising at least one second α-olefin and at least one second alkyl acrylate. This invention relates to a polymer molding composition having at least three components. The first component is a polymer. Preferably, the polymer is one or more polycarbonates or one or more polyesters or combinations thereof.

The polyesters referred to herein include thermoplastic, crystalline or amorphous polyesters produced by conventional polymerization techniques from one or more diols and one or more dicarboxylic acids. In one embodiment, the polyesters normally are molding or fiber grade and have an inherent viscosity (I.V.) of about 0.2 to about 2.4 (dL/g), preferably about 0.4 or 0.5 to about 1.2, measured at 25 °C in a 60/40 ratio by weight of phenol/tetrachloroethane at a concentration of

0.5 g/100 mL as determined at 25 °C.

The polyesters preferably comprise repeat units derived from a dicarboxylic acid component comprising one or more dicarboxylic acids selected from the group consisting of aliphatic dicarboxylic acids having a total of from 3 to 16 carbon atoms, alicyclic dicarboxylic acids having from 7 to 12 carbon atoms, aromatic dicarboxylic acids containing a total of from 8 to 16 carbon atoms, or a combination thereof, and a glycol component comprising one or more glycols having from 2 to 18 carbon atoms, one or more glycol ethers having from 4 to 12 carbon atoms or a combination thereof.

The term "aliphatic-dicarboxylic acid" is used to denote straight or branched chain alkanedicarboxylic acids preferably containing from 3 to 16 carbons. Typical aliphatic dicarboxylic acids include, but are not limited to, succinic acid, giutaric acid, adipic acid, sebacic acid, suberic acid, 2,2,4-trimethyladipic, 1,12- dodecanedioic acid and the like.

The term "alicyclic dicarboxylic acid" is used to denote cycloalkane dicarboxylic acids which preferably contain a total of from 7 to 12 carbon atoms preferably 1,2-, 1,3- and 1,4-cyclohexanedicarboxylic acids. The term "aromatic dicarboxylic acid" is used to denote dicarboxylic acid derivatives of benzene, naphthalene, biphenyl, diphenylether, diphenylsulfone and these substituted with C, - C₄ alkyl or halogen (fluorine, chlorine, bromine or iodine). Useful aromatic dicarboxylic acids include, but are not limited to, terephthalic acid, isophthalic acid, phthalic acid, 1 ,4-naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic, 4,4'-biphenyldicarboxylic acid, 2-bromoterephthalic acid, 2,5-dibromoterephthalic acid, tetrachlorophthalic acid and the like.

In one embodiment, examples of dicarboxylic acids useful in forming the polyester or copolyester of the invention include, but are not limited to terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, 1 ,4-cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylate, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and the like. Of these, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid and naphthalenedicarboxylate are preferred.

When cyclohexanedicarboxylic acid is used in the context of the invention, cis-, trans-, or cisl trans mixtures may be used. Any of the naphthalenedicarboxylic acid isomers or mixtures of isomers may be used. In a preferred embodiment, naphthalenedicarboxylic acid isomers include 2,6-, 2,7- 1,4- and 1,5- isomers.

Suitable diol components of the described polyesters may be selected from ethylene glycol, 1 ,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 1,4- butanediol, 2,2-dimethyl-l,3-propanediol, 1 ,6-hexanediol, 1,2-cyclohexanediol,

1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, Z,8- bis(hydroxymethyl)-tricyclo-[5.2.1.0]-decane wherein Z represents 3, 4, or 5; and diols containing one or more oxygen atoms in the chain, e.g., diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like. In general, these diols contain preferably from 2 to 8 carbon atoms. Cycloaliphatic diols can be employed in their cis or trans configuration or as mixtures of both forms. In a preferred embodiment, the diol is ethylene glycol, 1,4-cyclohexanedimethanol, or a combination thereof.

Preferred polyesters comprise at least about 50 mole % terephthalic acid residues and/or at least about 50 mole % ethylene glycol and/or 1,4- cyclohexanedimethanol residues.

Particularly preferred polyesters are those containing from about 75 to 100, more preferably, 90 to 100 mole %, and even more preferably, 95 to 100 mole % terephthalic moieties based on the total mole percentages of the acid components of the polyester equaling 100 mole %. Examples of terephthalic moieties include, but are not limited to, terephthalic acid and esters thereof.

Particularly preferred polyesters also include those containing from about

65 to 100 mole % ethylene glycol residues.

Also, preferred polyesters are those containing from about 90 to 100 mole % terephthalic acid residues and from about 85 to 100 mole %, preferably 90 to 100 % ethylene glycol residues. Also, particularly preferred polyesters are those containing from about 90 to 100 mole % terephthalic acid and 65 to 75 mole % ethylene glycol.

In one preferred embodiment of the invention, terephthalic acid is preferably present in the amount of 60 to 90 mole %.

It is more preferable that the polyester have repeat units derived from terephthalic acid or dimethyl terephthalate and a glycol selected from the group consisting of ethylene glycol and 1 ,4-cyclohexanedimethanol. When isophthalic acid is present, it is preferably present in the amount of 0.1 to 50 mole %, preferably 0.1 to 25 mole %, based the mole percentages of all acids in the acid component of the copolyester equaling 100 mole %. In another embodiment, the dicarboxylic acid comprises terephthalic acid or dimethyl terephthalate in the amount of 80 to 99.9 mole % and isophthalic acid in the amount of 0.1 to 20 mole % based on the total mole percentages of the acid component of the polyester equaling 100 mole %.

It is also preferable that when the acid component includes terephthalic acid and naphthalenedicarboxylic acid, it is preferable that the naphthalenedicarboxylic acid is present in the amount of 0.1 to 50 mole % and that terephthalic acid is present in the amount of 50 to 99.9 mole %.

Copolyesters may be prepared from one or more of the above dicarboxylic acids.

It should be understood that "dicarboxylic acids," includes the corresponding acid anhydrides, esters, and acid chlorides of these acids. In the acid component of this invention, the mole percentages of the acids referred to herein equal a total of 100 mole %.

In the glycol component of this invention, the mole percentages of the glycols referred to herein equal a total of 100 mole %. In one embodiment, the glycol component is from 80 to 100 mole % ethylene glycol based on the total percentages of the glycol component equaling 100 mole %.

In the invention, it is preferred that the glycol component of the polyester of the invention contain from about 50 to 100 mole %, preferably, 60 to 100 mole, more preferably 80 to 100 mole %, and even more preferably 90 to 100 mole % of one of the isomers of 1 ,4-cyclohexanedimethanol. Preferably, the polyesters of this invention may be based on cis-. trans-, or cisl trans mixtures of 1,4-cyclohexanedimethanol. It is preferable that the 1,4- cyclohexanedimethanol useful in the invention have a cisl trans ratio in the range of 60/40 to 10/90, preferably 50/50 to 15/85, and more preferably 40/60 to 25/75. If the level of cis isomer is greater than about 60 mole %, the melting point of the polyester is reduced too much for use in heat resistant applications. If the level of trans isomer is greater than about 90 mole %, the melting point increases too close to the degradation point and molding becomes impractical.

In one embodiment, the glycol component is aliphatic or alicyclic. The glycol component may comprise up to 40, preferably up to 20 mole %, and more preferably, up to 10 mole %, of one or more additional aliphatic or alicyclic glycols where 1,4-cyclohexanedimethanol is the other glycol as described herein.

When the copolyester contains 1,4-cyclohexanedimethanol and ethylene glycol, it is preferable that the ethylene glycol be present in an amount less than 20 mole %, more preferably, less than 10 mole %.

The polyester resins useful in the blend of this invention are well known and are commercially available. Methods for their preparation are described, for example, in United States Patent Nos. 2,465,319; 2,901,466 and 3,047,539.

In one embodiment, the polyester is preferably from 40 to 90 % or preferably from 40 to 60% when no glass fiber is present, by weight of the total polymer molding composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.

Commercially available polycarbonates useful within the scope of this invention are normally made by reacting glycols with a carbonate source such as phosgene, dibutyl carbonate and diphenyl carbonate. The polycarbonates of the present invention are preferably based on 4,4'-ispropylidenediphenol (bisphenol-A) reacted with either phosgene, dibutyl carbonate or diphenyl carbonate. The bisphenol A polycarbonate component of these blends is available and would be useful in a wide range of molecular weights. In another embodiment, the polycarbonate comprises a polycarbonate of 4,4'-isopropylidenediphenol, 2,2,4,4- tetramethyl-l,3-cyclobutanediol, or a mixture thereof.

Suitable examples of commercially available bisphenol A polycarbonates include LEXAN^®, from General Electric, and MAKROLON^®, from Miles, Inc.

Another example of a useful polycarbonate is the polycarbonate of 2,2,4,4- tetramethyl-l,3-cyclobutanediol.

The polycarbonate portion of the present blend can be prepared in the melt, in solution, or by interfacial polymerization techniques well known in the art.

Suitable preparation methods are disclosed in U. S. Patent Nos. 4,982,014 and 5,104,723. Commercially available polycarbonates are normally made by reacting glycols with a carbonate source such as phosgene, dibutyl carbonate and diphenyl carbonate.

The inherent viscosity of the polycarbonate portion of the blends according to the present invention is preferably about 0.3 to about 2.0 dL/g, more preferably from about 0.5 to about 1.2 dL/g, as determined at 25 °C in 60/40 wt/wt phenol tetrachloroethane at a concentration of 0.5 g/100 mL as determined at 25 °C.

In one embodiment, the polycarbonate is preferably from 50 to 95 % or preferably from 70 to 95% when no glass fibers are present, by weight of the total polymer molding composition based on the total weight percentages of the first, second, and third polymers equaling 100 %. Mixtures of polyester/polycarbonate may also be used within the context of this invention. These mixtures may be made by conventional techniques, including melt processing techniques. For example, pellets of the polyester may be mixed with pellets of the polycarbonate and subsequently melt blended in either a single or twin screw extruder to form a homogenous mixture. In one embodiment, the polyester/polycarbonate mixture is preferably from 40 to 95 % by weight of the total polymer molding composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.

The second polymer of the polymer molding composition comprises a copolymer based on the monomeric units of at least one α-olefin, at least one alkyl acrylate, and at least one unsaturated epoxide.

The α-olefins useful in the second polymer of this invention have from 2 to 10 carbon atoms and can be unsubstituted or substituted with one or more alkyl, cycloaliphatic or aryl moieties. Examples of useful α-olefins include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l-pentene, or 1-octene. In a preferred embodiment, the α-olefin is ethylene or propylene, more preferably ethylene. It is preferred that the α-olefin portion of the second polymer be present in the amount of about 40 to about 90%, even more preferably about 55 to about 75%, by weight based on the total weight of the components of the second polymer.

Acrylates useful in the second polymer of this invention include, but are not limited to, alkyl acrylates. As defined herein, the term "alkyl acrylate" also includes methacrylates. The alkyl group of the alkyl acrylate preferably contains from 1 to 10 carbon atoms, more preferably from 1 to 6 carbon atoms. The alkyl portion of the alkyl acrylate includes, but is not limited to, methyl, ethyl, propyl. isopropyl, n-butyl, isobutyl and 2-ethylhexyl. The alkyl portion is preferably methyl, n-butyl and 2-ethylhexyl, more preferably methyl. It is preferred that the alkyl acrylate portion of the second polymer be present in the amount of about 10 to about 40%, preferably, about 15 to about 35 weight %, by weight based on the total weight of the terpolymer.

Unsaturated epoxides useful in the second polymer preferably have from 4 to 1 1 carbon atoms. Examples of unsaturated epoxides having from 4 to 1 1 carbon atoms include, but are not limited to, glycidyl itaconate, allyl glycidyl ether, vinyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate.

A preferred class of unsaturated epoxides having from 4 to 1 1 carbon atoms are one or more glycidyl esters of one or more α,β-ethylenically unsaturated carboxylic acids.

It is preferred that one or more glycidyl esters of an α, β-elhylenically unsaturated carboxylic acid have the structure I:

wherein, R is hydrogen; an alkyl group having from about 1 to about 10 carbon atoms; or an alkyl group having from about 1 to about 10 carbon atoms and which comprises a substituted glycidyl ester radical.

Examples of glycidyl esters having the structure I include, but are not limited to, glycidyl acrylate, glycidyl mcihacrylalc, and glycidyl itaconate. In a preferred embodiment, structure 1 is glycidyl methacrylate or glycidyl acrylate. moie piefcr.ihh glycidyl methacryhie. For the unsaturated epoxides of the second polymer, it is preferred the epoxide be present in the amount of about 1 to 20, preferably 2 to 10 % by weight based on the total weight of the second polymer.

The second polymer of the polymer molding composition comprises about 1 to about 20%), preferably about 1 to about 15%, more preferably 2 to about 12%, and even more preferably, about 2 to about 10% by weight of the polymer molding composition based on the total weight percentages of the first, second and third polymers equaling 100 weight %. In one embodiment, the second polymer is a random terpolymer.

In one embodiment, the molecular weight of the second polymer is greater than 20,000. In a preferred embodiment, the molecular weight of the second polymer is a from about 70,000 to about 100,000.

In one embodiment, the second polymer is E-MA-GMA (ethylene-methyl acrylate-glycidyl methacrylate), wherein,

(a) E is the radical formed from ethylene comprising from 40 to 90 weight % of the second polymer E-MA-GMA;

(b) MA is the radical formed from methyl acrylate comprising from 10 to 40 weight %, preferably 15 to 35 weight %, and most preferably, 20 to 35 weight % of the second polymer E-MA-GMA; and

(c) GMA is the radical formed from glycidyl methacrylate and comprising from 1 to 20 weight %, preferably 2 to 10 weight %, and most preferably, 3 to 8 weight % of the second polymer E-MA- GMA. In a preferred embodiment, the third polymer is from about 2 to about 20% by weight of the polymer molding composition, wherein the third polymer comprises the monomeric units of at least one α-olefin and at least one alkyl acrylate. In one embodiment, the third polymer is a random copolymer.

The α-olefins useful in the third polymer of this invention have from 2 to 10 carbon atoms and can be unsubstituted or substituted with one or more aliphatic, cycloaliphatic or aryl moieties. Examples of useful α-olefms include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-l-pentene, or 1-octene. In a preferred embodiment, the α-olefin for the third polymer is ethylene or propylene, more preferably ethylene. The α-olefin portion of the third polymer is present in the amount of about 50 to about 90 %, preferably about 65 to about 85 % by weight based on the total weight of the third polymer.

The alkyl group of the alkyl acrylate contains from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms. The alkyl portion of the alkyl acrylate portion of the third polymer is preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and 2-ethylhexyl. The alkyl portion is preferably methyl, n-butyl and 2-ethylhexyl, more preferably methyl. The alkyl acrylate portion of the third polymer is present in the amount of about 10 to about

50%), preferably about 15 to about 40% by weight, based on the total weight of the third polymer.

In one embodiment, the molecular weight of the third polymer is greater than 20,000. In another embodiment, the molecular weight of the second polymer is from about 70,000 to about 100,000.

In another embodiment, the alkyl acrylate and α-olefin portion of the third polymer are the same or substantially the same as the alkyl acrylate and α-olefin portion of the second polymer. In one embodiment, the polymer molding composition of the present invention contains from about 2 to about 20 weight %, preferably about 2 to about 15 weight %, and most preferably about 3 to about 10 weight % of the third polymer E-RA, wherein,

(a) E is the radical formed from ethylene comprising from 50 to 90 weight % of the third polymer E-RA; and

(b) RA is the radical formed from alkyl acrylate comprising from 10 to

50 weight %, preferably 15 to 40 weight %, and most preferably, 20 to 35 weight % of the third polymer E-RA, wherein the alkyl moiety may be methyl, ethyl, n-butyl, isobutyl, 2-ethylhexyl, or the like.

The ethylene copolymers used in the compositions of the present invention can be prepared by direct copolymerization, for example, copolymerization of ethylene, glycidyl methacrylate, and the methyl acrylate in the presence of a free- radical polymerization initiator at elevated temperatures, preferably from 100 to 270°C, and most preferably from 130 to 230°C, and at elevated pressures, preferably at least 70 MPa, and most preferably from 140 to 350 Mpa.

In one embodiment, the polymer molding composition comprises a first polymer that is from 40 to 90 % by weight of the total composition, a second polymer that is from 9 to 40 % by weight of the total composition, and a third polymer that is from 1 to 20 % by weight of the total composition, based on the total weight percentages of the first, second, and third polymers equaling 100 %.

In another embodiment, the polymer molding composition comprises a first polymer, wherein the first polymer comprises a polyester and/or a polycarbonate; the second polymer comprises an α-olefin of from 40 to 90 % by weight of the second polymer, an alkyl acrylate of from 9 to 40 % by weight of the second polymer, and an unsaturated epoxide of from 1 to 20 % by weight of the second polymer; and a third polymer comprising an α-olefin of from 50 to 90 % by weight of the third polymer and an alkyl acrylate of from 10 to 50 % by weight of the third polymer, wherein the sum of the first, second, and third polymers equals 100%.

In a preferred embodiment of the invention, the polymer molding composition comprises:

(a) a first polymer comprising a polyester containing repeat units derived from terephthalic acid and 1 ,4-cyclohexanedimethanol and having an inherent viscosity from about 0.5 to 2.0 g/dL;

(b) a second polymer based on ethylene, glycidyl methacrylate and methyl acrylate, wherein the second polymer is preferably about 9 to

40%_> by weight; and

(c) a third polymer of ethylene and an alkyl acrylate, where the alkyl moiety is preferably methyl, ethyl, n-butyl, isobutyl, 2-ethylhexyl, or the like, wherein the third polymer is preferably about 1 to 20% by weight, wherein

the sum of components (a)-(c) equals 100 %.

The invention further relates to a polymer molding composition comprising

(a) a polycarbonate or a polyester wherein said polyester comprises repeat units derived from: a dicarboxylic acid component comprising one or more dicarboxylic acids selected from the group consisting of aliphatic dicarboxylic acids having a total of from 3 to 16 carbon atoms, alicyclic dicarboxylic acids having 7 to 12 carbon atoms, aromatic dicarboxylic acids containing a total of from 8 to 16 carbon atoms, and combinations thereof, and

(b) about 1 to about 20% by weight of the random terpolymer based on one or more α-olefins, one or more alkyl acrylates and one or more unsaturated epoxides having from 4 to 11 carbon atoms, and

Glass fibers that are used in the present invention conventionally have an average standard diameter of greater than 5 μ. The length of the glass filaments and whether or not they are bundled into fibers and the fibers bundled, in turn, into yarns, ropes or rovings, and the like, are not critical to this invention. However, for the purpose of preparing the present compositions, it is preferable to use filamentous glass in the form of chopped strands of from about 1.5 mm to about 10 mm long, and preferably less than about 6 mm long. In the pellets and molded articles of the compositions on the hand, even shorter lengths will be encountered, because during compounding, considerable fragmentation occurs. This is, however, desirable because the best properties are exhibited by injection molded articles in which the filament lengths are between 0.03 mm and 1 mm. Especially preferred are glass fibers having an average standard diameter in the range of greater than 5μ, preferably 5 to 14 μ, and the average filament length dispersed in the molded articles being between 0.15 mm and 0.4 mm.

Consequently, glass filaments are dispersed uniformly and the molded articles exhibit uniform and balanced mechanical properties, especially surface smoothness.

The amount of the glass fibers can vary broadly from 10 to 50 % by weight, and most preferably 10 to 40 % by weight, based on the total composition. These glass fibers are conventionally sized with coupling agents, such as aminosilanes and epoxysilanes and titanates, and adhesion promoters, such as epoxies, urethanes, cellulosics, starch, cyanurates, and the like.

In one embodiment, when the glass fiber is present in the polymer molding composition, the polyester is preferably from 75 to 85 % by weight of the total composition based on the total weight percentages of the first, second, and third polymers equaling 100 %. In another embodiment, when the glass fiber is present in the polymer molding composition, the polycarbonate is preferably from 50 to 80 % by weight of the total composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.

In a preferred embodiment of the invention, the polymer molding composition comprises: (a) a first polymer comprising a polyester containing repeat units derived from terephthalic acid and 1 ,4-cyclohexanedimethanol and having an inherent viscosity from about 0.5 to 2.0 g/dL;

(b) glass fibers, preferably about 10 to 40% by weight of the total composition;

(c) a random second polymer based on ethylene with glycidyl methacrylate and methyl acrylate, wherein the second polymer is preferably about 1 to 20% by weight; and

(d) a random third polymer of ethylene and an alkyl acrylate, where the alkyl moiety is preferably methyl, ethyl, n-butyl, isobutyl, 2- ethylhexyl, or the like, wherein the third polymer is preferably about 2 to 20% by weight, wherein

the sum of components (a)-(d) equals 100 %.

It is understood that other additives such as stabilizers; inhibitors of degradation (i.e. oxidative, hydrolytic, thermal and ultraviolet light); flame retardants; fibrous and particulate fillers; reinforcing agents; lubricants; mold release agents; nucleating agents; and colorants (i.e. dyes and pigments) might also be desirable in such formulations. Such additives are generally present at 0.1 to about 20 weight % based on the total weight of said polymer composition.

Useful flame retardants, include, but are not limited, to brominated polystyrene; decabromodiphenyl oxide; and l,2-bis(tetrabromophthaIimide)ethane combined in combination with sodium antimonate or antimony oxide. Examples of other reinforcing agents that might be useful in addition to glass fibers, include, but are not limited to, carbon fibers, mica, clay, talc, wollastonite, calcium carbonate or a combination thereof. The polymer compositions of the invention may be reinforced with a mixture of glass and other reinforcing agents as described above, such as mica or talc, and/or with other additives.

The polymer compositions of the invention containing reinforcing agents may be molded at mold temperatures from about 30 to 120°C and, therefore, easily molded without the need for expensive mold heating equipment. The preferred molding temperature of the glass filled polymer compositions of the invention is in the range of from 50 to 110°C.

The compositions with improved flow described in this invention can be prepared by melt blending, in a closed system, the matrix resin PCT and the two copolymers into a uniform mixture in a multi-screw extruder such as a Werner- Pfleiderer extruder having generally kneading blocks, mixing elements and at least one reverse pitch to generate high shear. Other conventional plasticating devices such as a Brabender, Banbury mill, or the like, may be used for blending the composition. Alternatively the blends may be made by dry mixing together components followed by melt fabrication of the dry mixture by extrusion.

A wide range of useful articles can be made from the toughened polymer compositions of this invention by conventional molding methods employed in the fabrication of thermoplastic articles, for example, molded parts such as electrical and electronic connectors; and extruded shapes such as tubing, films, sheets, fibers and laminates.

This invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for puφoses of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated. The starting materials are commercially available unless otherwise indicated. Percentages as referred to herein are percentages by weight unless otherwise specified.

EXAMPLES

In order to map out the melt viscosity, impact resistance, tensile and flexural toughness and HDT over the entire composition space of preferred interest, A statistically designed experiment was done. A variation of the two variable central composite design was generated and randomized using RS/Discover (BBN Domain Software, MA). The level of the matrix polyester, poly(l,4-cyclohexane terephthalate), was varied, from 74% to 54%, dependently on the total amount of added toughening system, which was varied from 0 to 20% and the composition of the toughening system was varied independently from 100% ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) teφolymer (Lotader 8900, a random teφolymer with 25% MA and 8% GMA, from Elf-Atochem) and 0% E-MA (Lotryl 24MA07, a random copolymer that is 24% MA from Elf-Atochem) to 0% E-MA- GMA and 100% E-MA. The prepared compositions had fixed 20% glass fiber 492AA from Owens-Coming; 5.75% Uniplex 809 plasticizer (a polyalkylene ether which is a hydroxyl functional polyethylene glycol endcapped with ethyl hexanoate or reacted so that the ends of the polyethylene glycol is an ethyl hexanoate ester); a bis(2-ethylhexanoate) of poly(ethylene glycol) from Unitex; and 0.25 % carbon black, Black Pearls 800. Twenty compositions were compounded at 300°C in a Werner-Pfleiderer ZSK-30 corotating, intermeshing twin screw extruder with 5 kneading elements, a Berstorff mixing element and 3 turbines, using calibrated loss in weight feeders. The hot strand exiting the die was quenched in water, pelletized, then dried overnight at 100°C in desiccating ovens and molded in a Boy 50-S injection molding machine with the barrel temperature set at 300 °C and the test bar mold at lOO°C. The molded bars were tested at about 25 °C and 50% relative humidity using the following test procedures:

(1) Izod Impact Strength, unnotched: ASTM D-256 (2) Tensile Testing: ASTM D-638

(3) Flexural Testing: ASTM D-790

(4) Heat Deflection Temperature (HDT) under 264 psi load: ASTM D- 648

(5) Melt Viscosity on pellets dried overnight in a vacuum oven at 100°C, using a Gottfert rheometer, at 305 °C, after 5 min., under

400 s^"1 shear, through a 1.0 mm diameter capillary 15 mm long.

The actual test results in run order are in Table 1. The numbers reported are the average of 5 bars for each Izod, tensile and flexural test; two bars for the HDT. All failures under Izod impact conditions for unnotched bars were complete breaks, thus average values can be used with confidence.

Beside the Izod impact strength, another well-recognized measure of toughness (see Bucknall) is the area under the stress-strain curve resulting from tensile and flexural testing. This area (in units of Joules x 10^"2 or cJ) represents the energy or work required to achieve the elongation of tensile bars or the bend of flex bars to where breakage occurs under the ASTM specified testing conditions.

COMPOSITION: poly(l,4-cyclohexane terephthalate); Toughening System = E-MA-GMA E-MA-GMA System that is Uniplex 809, a

The pri of and equatio be generated a

1.

2.

which describe compositional

1.

2.

This analysis o (BBN Domain generated to th

Bl

First, as a comparison, the examples in Table 2 show the effect of straight E-MA-GMA on properties of primary interest.

Comparative Table 2 Properties of GFR PCT with E-MA-GMA

As can be seen in comparative Table 2, increasing levels of E-MA-GMA in a polyester, such as a glass reinforced poly(l,4-cyclohexane terephthalate) (GFR PCT), increase Izod impact; and tensile and flexural toughness.

Comparative Table 3 Properties of GFR PCT with E-MA

In comparative Table 3, where the property values from adding only the copolymer E-MA to GFR PCT are given, toughemng by the rubbery E-MA is also evident, though to a much lower extent. Values of the Izod impact toughness beyond 11.4 ft-lbs/in (or tensile toughness > 36 cJ, or flex toughness > 55 cJ) are not attainable by adding only E-MA.

Solving the simultaneous equations describing the behavior of the toughening system that is the subject of this patent for all compositions that give a certain level of toughness, for example, Izod impact strength = 14 ft-lbs/in, provides a suφrising result. Table 4 Properties of GFR PCT with the Toughening System

Unexpectedly, a minimum in the melt viscosity and a maximum HDT are attainable for this given level of toughness by combining E-MA-GMA and E-MA in a "toughening package." Although the other measures of toughness, tensile and flex, are not at their respective maxima, the values are close due to the relative flatness of these responses in this part of composition space defined by Izod impact = 14 ft-lbs/in.

Table 5 Properties of GFR PCT with the Toughening System

Again, E-MA-GMA and E-MA together give an unexpected benefit not derived with either of these components alone.

Looking to the contour plots and fitted equations for the behavior of other properties for the compositions that give a tensile toughness of 40 or 45 cJ., Table 6 shows an optimal compositions with regard to melt viscosity and HDT that include both E-MA-GMA and E-MA.

Table 6 Properties of GFR PCT with the Toughening System

With regard to the third measure of toughness, the flexural energy or work to break in cJ, compositions that are optimal with regard to melt viscosity and HDT include both E-MA-GMA and E-MA. Table 7 Properties of GFR PCT with the Toughening System

There are occasions when an intricate mold cannot be filled with a material whose melt viscosity is greater than a certain allowable maximum value without inducing degradation and loss of mechanical properties. In such an instance, it would be valuable to know the optimum toughness that could be achieved for that limiting melt viscosity. Table 8 gives such an example, again drawn from the results of the central composite design experiment. Table 8 Properties of GFR PCT with the Toughening System

As shown above, PCT containing both E-MA-GMA and E-MA provides the best results with respect to toughness and Izod impact strength.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. Moreover, all patents, patent applications (published and unpublished, foreign or domestic), literature references or other publications noted above are incoφorated herein by reference for any disclosure pertinent to the practice of this invention.

Claims

WHAT IS CLAIMED IS:

1. A polymer molding composition, comprising:

2. The composition of Claim 1, wherein the polyester comprises repeat units derived from

(i) a dicarboxylic acid component comprising one or more dicarboxylic acids of an aliphatic dicarboxylic acid having a total of from 3 to 16 carbon atoms, an alicyclic dicarboxylic acid having a total of from 7 to 12 carbon atoms, an aromatic dicarboxylic acid having a total of from 8 to 16 carbon atoms, or a mixture thereof; and

(ii) a glycol component comprising one or more glycols having a total of from 2 to 18 carbon atoms, a glycol ether having a total of from 4 to 12 carbon atoms or a mixture thereof.

3. The composition of Claim 2, wherein the aliphatic dicarboxylic acid comprises succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, 2,2,4-trimethyladipic or 1,12-dodecanedioic acid; the alicyclic dicarboxylic acid comprises 1,2-, 1,3- or 1 ,4-cyclohexanedicarboxylic acid, and the aromatic dicarboxylic acid comprises terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6- naphthalenedicarboxylic, 4,4'-biphenyldicarboxylic acid, 2- bromoterephthalic acid, 2,5-dibromoterephthalic acid or tetrachlorophthalic acid.

4. The composition of Claim 2, wherein the repeat units (i) are derived from terephthalic acid or dimethyl terephthalate.

5. The composition of Claim 2, wherein the repeat units are derived from 75 to 100 mole % terephthalate moieties based on the total mole percentages of the acid component of the polyester equaling 100 mole %.

6. The composition of Claim 2, wherein the repeat units are derived from 95 to 100 mole % terephthalate moieties based on the total mole percentages of the acid component of the polyester equaling 100 mole %.

7. The composition of Claim 2, wherein the dicarboxylic acid comprises terephthalic acid or dimethyl terephthalate in the amount of 80 to 99.9 mole % and isophthalic acid in the amount of 0.1 to 20 mole % based on the total mole percentages of the acid component of the polyester equaling 100 mole %.

8. The composition of Claim 2, wherein the glycol component is aliphatic or alicyclic.

9. The composition of Claim 8, wherein the glycol component comprises up to 20 mole % of one or more other aliphatic or alicyclic glycols based on the total mole percentages of the glycol component of the polyester equaling 100 mole %.

10. The composition of Claim 8, wherein the glycol component comprises up to 10 mole % of one or more other aliphatic or alicyclic glycols based on the total mole percentages of the glycol component of the polyester equaling 100 mole %.

11. The composition of Claim 2, wherein the glycol component comprises ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2- dimethyl-l,3-propanediol, 1,6-hexanediol, pentanediol, neopentyl glycol, 1,2-cyclohexanediol, 1 ,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3- cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, (3,8)- bis(hydroxymethyl)-tricyclo-[5.2.1.0]-decane, (4,8)-bis(hydroxymethyl)- tricyclo-[5.2.1.0]-decane, (5,8)-bis(hydroxymethyl)-tricyclo-[5.2.1.0]- decane, tetramethylcyclobutanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol or a mixture thereof.

12. The composition of Claim 2, wherein the glycol component comprises ethylene glycol or 1,4-cyclohexanedimethanol.

13. The composition of Claim 2, wherein the glycol component is ethylene glycol.

14. The composition of Claim 2, wherein the glycol component is 1,4- cyclohexanedimethanol.

15. The composition of Claim 2, wherein the glycol component is from 80 to 100 mole % ethylene glycol based on the total percentages of the glycol component equaling 100 mole %.

16. The composition of Claim 2, wherein the glycol component is from 90 to 100 mole % ethylene glycol based on the total mole percentages of the glycol component of the polyester equaling 100 mole %.

17. The composition of Claim 2, wherein the glycol component is from 50 to 100 mole % 1,4-cyclohexanedimethanol based on the total percentages of the glycol component equaling 100 mole %.

18. The composition of Claim 2, wherein the glycol component is from 80 to 100 mole % 1,4-cyclohexanedimethanol based on the total mole percentages of the glycol component of the polyester equaling 100 mole %.

19. The composition of Claim 2, wherein the glycol component comprises 1 ,4- cyclohexanedimethanol in a cisl trans ratio from 60/40 to 10/90.

20. The composition of Claim 2, wherein the glycol component comprises 1,4- cyclohexanedimethanol in a cisl trans ratio from 40/60 to 25/75.

21. The composition of Claim 2, wherein the repeat unit comprises terephthalic acid or dimethyl terephthalate and a glycol selected from the group consisting of ethylene glycol and 1,4-cyclohexanedimethanol.

22. The composition of Claim 1, wherein the polyester has an inherent viscosity of from about 0.2 to about 2.4 dL/g as determined in a 60/40 (wt./wt.) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml as determined at 25 °C.

23. The composition of Claim 1, wherein the polyester has an inherent viscosity of from about 0.5 to about 1.2 dL/g as determined in a 60/40 (wt./wt.) phenol/tetrachloroethane at a concentration of 0.5 g/100 ml as determined at 25 °C.

24. The composition of Claim 1, wherein the polyester is from 40 to 90 % by weight of the total composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.

25. The composition of Claim 1 , wherein the polycarbonate comprises a polycarbonate of 4,4'-isopropylidenediphenol, 2,2,4,4-tetramethyl-l,3- cyclobutanediol, or a mixture thereof.

26. The composition of Claim 1, wherein the polycarbonate has an inherent viscosity of from about 0.3 to about 2.0 dL/g as determined at 25 °C in 60/40 wt/wt phenol tetrachloroethane at a concentration of 0.5 g/100 ml as determined at 25 °C.

27. The composition of Claim 1, wherein the polycarbonate has an inherent viscosity of from about 0.5 to about 1.2 dL/g as determined at 25 °C in 60/40 wt/wt phenol tetrachloroethane at a concentration of 0.5 g/100 ml as determined at 25 °C.

28. The composition of Claim 1, wherein the polycarbonate is from 50 to 95 % by weight of the total composition based on the total weight percentages of the first, second, and third polymers equaling 100 %.

29. The composition of Claim 1, wherein the first and second α-olefin comprises, independently, an unsubstituted α-olefin or an α-olefin substituted with one or more alkyl, cycloaliphatic or aryl moieties.

30. The composition of Claim 29, wherein the first and second α-olefin independently comprises ethylene, propylene, 1-butene, 1-hexene, 1- pentene, 3 -methyl- 1-pentene, 1-octene or a mixture thereof.

31. The composition of Claim 29, wherein the first and second α-olefin independently comprises propylene or ethylene.

32. The composition of Claim 29, wherein the first and second α-olefin are both ethylene.

33. The composition of Claim 1, wherein the first α-olefin is ethylene and the first alkyl acrylate is methyl acrylate.

34. The composition of Claim 1, wherein the first α-olefin of the second polymer is from 40 to 90 % by weight of the second polymer.

35. The composition of Claim 1, wherein the first α-olefin of the second polymer is from 55 to 75 % by weight of the second polymer.

36. The composition of Claim 1, wherein the second α-olefin of the third polymer is from 50 to 90 % by weight of the third polymer.

37. The composition of Claim 1, wherein the second α-olefin of the third polymer is from 65 to 85 % by weight of the third polymer.

38. The composition of Claim 1, wherein the first and second alkyl acrylate comprises, independently, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate or a mixture thereof.

39. The composition of Claim 1, wherein the first and second alkyl acrylate is methyl acrylate.

40. The composition of Claim 1, wherein the first alkyl acrylate of the second polymer is from 10 to 40 % by weight of the second polymer.

41. The composition of Claim 1, wherein the first alkyl acrylate of the second polymer is from 15 to 35 % by weight of the second polymer.

42. The composition of Claim 1, wherein the second alkyl acrylate of the third polymer is from 10 to 50 % by weight of the third polymer.

43. The composition of Claim 1, wherein the second alkyl acrylate of the third polymer is from 15 to 40 % by weight of the third polymer.

44. The composition of Claim 1, wherein the unsaturated epoxide comprises 4 to 11 total carbon atoms.

45. The composition of Claim 1, wherein the unsaturated epoxide comprises one or more glycidyl esters of one or more α,β-ethylenically unsaturated carboxylic acids.

46. The composition of Claim 1, wherein the unsaturated epoxide is of the structure of formula I:

CH„=C f —- .ftP^"_0_ -CCHH₂₂—- CCςH--

/^CH2

wherein, R is hydrogen, an alkyl radical having from about 1 to about 10 carbon atoms or an alkyl radical having from about 1 to about 10 carbon atoms with a substituted glycidyl ester radical.

47. The composition of Claim 1 , wherein the unsaturated epoxide comprises glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, allyl glycidyl ether, vinyl glycidyl clhcr or a mixture thereof.

48. The composition of Claim 1 , wherein the unsaturated epoxide is glycidyl methacrylate.

49. The composition of Claim 1, wherein the unsaturated epoxide is from 1 to 20 % by weight of the second polymer.

50. The composition of Claim 1, wherein the unsaturated epoxide is from 2 to 10 % by weight of the second polymer.

51. The composition of Claim 1 , wherein the second α-olefin is ethylene and the second alkyl acrylate is methyl acrylate.

52. The composition of Claim 1, wherein the molecular weight of the second and third polymer is greater than 20,000.

53. The composition of Claim 1, wherein the molecular weight of the second and third polymer is from 70,000 to 100,000.

54. The composition of Claim 1, wherein the first polymer is from 40 to 90 % by weight of the total composition, the second polymer is from 9 to 40 % by weight of the total composition, and the third polymer is from 1 to 20 % by weight of the total composition, based on the total weight percentages of the first, second, and third polymers equaling 100 %.

55. The composition of Claim 1, wherein the polyester comprises the reaction product between terephthalic acid or dimethyl terephthalate and ethylene glycol or 1,4-cyclohexanedimethanol, the second polymer comprises a teφolymer of ethylene, methyl acrylate and glycidyl methacrylate, and the third polymer comprises a copolymer of ethylene and methyl acrylate.

56. The composition of Claim 1 , wherein the composition comprises

(a) a first polymer comprising a polyester containing repeat units derived from terephthalic acid and 1 ,4-cyclohexanedimethanol and having an inherent viscosity from about 0.5 to 2.0 g/dL; (b) a second polymer based on ethylene, glycidyl methacrylate and methyl acrylate; and

(c) a third polymer of ethylene and an alkyl acrylate.

57. The composition of Claim 1 , further comprising glass fibers.

58. The composition of Claim 57, wherein the glass fibers are from 10 to 50% by weight of the total composition.

59. The composition of Claim 57, wherein the glass fibers are from 10 to 40% by weight of the total composition.

60. The composition of Claim 57, wherein the glass fibers have an average standard diameter of greater than 5μ.

61. The composition of Claim 57, wherein the average standard diameter of the glass fibers is from 5μ to 14μ.

62. The composition of Claim 57, wherein the length of the glass fibers is from 0.15 to 0.4 mm.

63. The composition of Claim 57, wherein the composition comprises:

(a) a first polymer comprising a polyester containing repeat units derived from terephthalic acid and 1,4-cyclohexanedimethanol and having an inherent viscosity from about 0.5 to 2.0 g/dL;

(b) glass fibers; (c) a random second polymer based on ethylene, glycidyl methacrylate and methyl acrylate; and

(d) a random third polymer of ethylene and an alkyl acrylate.

64. The composition of Claim 57, wherein the first polymer is a polyester of from 75 to 85 % by weight of the total composition based on the total weight percentages of the first polymer, second polymer, third polymer and glass fiber.

65. The composition of Claim 57, wherein the first polymer is a polycarbonate of from 50 to 80 % by weight of the total composition based on the total weight percentages of the first polymer, second polymer, third polymer and glass fiber.

66. The composition of Claim 57, wherein the glass fibers are from about 10 to 40% by weight, the second polymer is from about 1 to 20% by weight, and the third polymer is from about 2 to 20% by weight; wherein the weight percentages are of the total composition based on the total weight percentages of the first polymer, second polymer, third polymer and glass fiber.

67. The composition of Claim 1, further comprising an additive of a stabilizer; an inhibitor of oxidative, hydrolytic, thermal or ultraviolet light degradation; a flame retardant, a fibrous and particulate filler; a reinforcing agent; a lubricant; a mold release agent; a nucleating agent; a colorant; or a mixture thereof.

68. The composition of Claim 67, wherein the additive is from 0.1 to 20% by weight of the total composition.

69. The composition of Claim 67, wherein the flame retardant comprises a brominated polystyrene, decabromodiphenyl oxide, 1,2- bis(tetrabromophthalimide)ethane in combination with sodium antimonate or antimony oxide.

70. The composition of Claim 67, wherein the reinforcing agent comprises carbon fibers, mica, clay, talc, wollastonite, calcium carbonate or a mixture thereof.

71. The composition of Claim 1, wherein the composition has a molding temperature of from 30 to 120°C.

72. The composition of Claim 1, wherein the composition has a molding temperature of from 50°C to 110°C.

73. A polymer molding composition comprising

a glycol component comprising one or more glycols having from 2 to 18 carbon atoms, one or more glycol ethers having from 4 to 12 carbon atoms, and combinations thereof, (b) about 1 to about 20% by weight of a random teφolymer based on one or more α-olefins, one or more alkyl acrylates and one or more unsaturated epoxides having from 4 to 11 carbon atoms, and

wherein said weight percentages are based on the total weight percentages of the components of said polymer molding composition equalling 100 weight %.

74. A thermoplastically- formed article formed from the composition of Claim 1.

75. The article of Claim 74, wherein the article is an electrical conductor, an electronic conductor, a tube, a film, a sheet, a fiber or a laminate.