CA1124918A - Polymer blends with improved hydrolytic stability - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
This invention relates to polymer blends having improved hydrolytic stability, moldability and fire retardancy which com-prise, in admixture. (1) a linear aromatic polyester prepared from an aromatic dicarboxylic acid and a bisphenol, and (2) poly-phenylene sulfide.

Description

~124~18 BACKGROUND OF THE INVENTION
This invention relates to blends of polyphenylene sulfides and linear aromatic carboxylic polyesters comprising a bisphenol wherein the carboxylic acid component can be an aromatic dicar-boxylic acid or an aliphatic saturated dicarboxylic acid such asoxalic or adipic acids.
Linear aromatic polyesters prepared from aromatic dicarboxylic acids and bisphenols are well known for their suitability for mold-ing, extrusion, casting, and film-forming applications. For ex-ample, U.S. Patent 3,216,970 to Conix, disclose linear aromatic polyesters prepared from isophthalic acid, terephthalic acid, and a bisphenolic compound. Such high molecular weight compositions are known to be useful in the preparation of various films and fibers. Further, these compositions, when molded into useful articles using conventional techniques, provide properties super-ior to articles molded from other linear polyester compositions.
For instance, aromatic polyesters are known to have a variety of useful properties, such as good tensile, impact, and bending strengths, high thermal deformation and thermal decomposition temperatures, resistance to UV irradiation and good electrical properties.
Aromatic polyesters which are particularly well suited for molding applications may also be prepared by reacting an organic diacid halide with a difunctional aliphatic reactive modifier, such as a glycol, and subsequently reacting this product with a bisphenol compound. The resulting polyesters have reduced melt viscosities and melting points which permits molding at temper-atures within the operable limits of conventional molding ap-paratus (i.e. less than about 300C.) This type of glycol-modified polyester is more fully disclosed in U.S. Patent3,471,441, to Hindersinn.

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~12~18 In order to form a successful molding resin on a commercial scale, a polymer should be capable of being molded conveniently without significant degradation in physical properties. In this respect, although the aforementioned aromatic polyesters generally display excellent physical and chemical properties, a persistent and troublesome problem has been their sensitivity to hydrolytic degradation at elevated temperatures. This sensitivity to the com-bined effects of heat and moisture is also exhibited in conlmercial-ly available polycarbonate resins as evidenced by the desirability of reducing the water content of the resin to less that about 0.05%
prior to molding. Unfortunately, however, the aromatic polyester resins often display a more pronounced tendency to rapidly degrade and embrittle than do polycarbonate resins. This is demonstrated by the loss of tensile strength which can occur when an aromatic polyester resin is molded and subsequently immersed in boiling water. This tendency may be explained, in part, by the hydrolysis of the ester linkages under these conditions. In the event, it is to be appreciated that sensitivity to moisture represents a sig-nificant problem in aromatic polyester resins that would signif-icantly limit their commercial utility in applications such as inautoclaves or at elevated temperatures in humid atmospheres.
Accordingly, it is a principal object of this invention to prepare aromatic polyester compositions having superior physical and chemical properties as well as improved hydrolytic stability.
SUMMARY OF THE INVENTION
It has now been found that polyester molding compositions having improved hydrolytic stability may be prepared by blending a linear aromatic polyester with polyphenylene sulfide. In other words, the invention is directed to a thermoplastic polymeric com-position coMprising, in admixture, (a) a linear aromatic polyester of components comprising a bisphenol and a dicarboxylic acid, and ~J

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(b) polyphenylene sulfide. The preferred aromatic polyesters of this invention, are prepared from bisphenols and at least one aro-matic dicarboxylic acid, most preferably selected from the group consisting of isophthalic acid, terephthalic acid, or mixtures thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The linear aromatic polyesters of the present invention can be prepared by condensing a diacid halide of a dicarboxylic acid, dissolved in an organic liquid which is a solvent for the polyes-ter to be formed, with a metal phenolate of a bisphenol, dissolvedin a liquid which is immiscible with the solvent for the diacid halide. This process is more fully described in US Patent 3,216,970 to Conix.
The bisphenols which can be used in this process are known in 5 the art and correspond to the general formula:
HO - Ar - (E)x ~ Ar - OH
Tb Gm Tb wherein Ar is aromatic, preferably containing 6-18 carbon atoms (including phenyl, biphenyl and napthyl); G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkyaryl, arylalkyl, haloarylalkyl, cycloalkyl, or halocycloalkyli E is a divalent (or di-substituted) alkylene, haloalkylene, cycloalkylene, halocycloalkylene, arylene, or haloarylene, -O-, -S-, -SO-, -S02-, -S03-, -CO-, GP=O or GN
T and T' are independently selected from the group consisting of halogen, such as chlorine or bromine, G and OG; m is an integer from O to the number of replaceable hydrogen atoms on E; b is an integer from O to the number of replaceable hydrogen atoms on Ar, and x is O or 1. When there is plurality of G substituents in the bisphenols, such substituents may be the same or different. The T
and T' substituents may occur in the ortho, meta or para-positions with respect to the hydroxyl radical. The foregoing hydrocarbon radicals preferably have carbon atoms as follows:

alkyl, haloalkyl, alkylene and haloalkylene of 1 to 14 carbons;
aryl, haloaryl, arylene and haloarylene of 6 to 14 carbons; alkyl-aryl, haloalkylaryl, arylalkyl and haloarylalkyl of 7 to 14 carbons;
and cycloalkyl, halocycloalkyl, cycloalkylene and halocycloalkylene of 4 to 14 carbons. Additionally, mixtures of the above described bisphenols may be employed to obtain a polymer with especially desired properties. The bisphenols generally contain 12 to about 30 carbon atoms, and preferably 12 to about 25 carbon atoms.
Typical examples of bisphenols having the foregoing formula include bis(4-hydroxyphenyl)methane, bis(2-hydroxyphenyl)methane, (4-hydroxyphenyl-, 2-hydroxyphenyl)-methane, and mixtures thereof;
bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy-3,5-di-bromophenyl)methane, bis(4-hydroxy-3,5-difluorophenyl)methane, bisphenol-A [bis(4-hydroxyphenyl)-2,2-propane] bis-(4-hydroxy-3, 5-dichlorophenyl)-2,2-propane. bis(3-chloro-4-hydroxyphenyl)-2,2-propane, bis(4-hydroxynaphthyl)-2,2-propane, bis(4-hydroxynaphthyl)-

2,2-propane, bis(4-hydroxyphenyl)-phenyl methane, bis(4-hydroxy-phenyl) diphenyl methane, bis(4-hydroxyphenyl)-4'-methyl phenyl methane, bis(4-hydroxyphenyl)-4'-chlorophenyl methane, bis(4-hydroxyphenyl)-2,2,2-trichloro-1,1,2-ethane, bis(4-hydroxyphenyl)-l,l-cyclohexane, bis(4-hydroxyphenyl)cyclohexyl methane, 4,4-di-hydroxyphenyl, 2,2'-dihydroxydiphenyl, dihydroxynaphthalenes, bis (4-hydroxyphenyl)-2,2-butane, bis(2,6-dichloro-4-hydroxyphenyl)-2,2-propane, bis(2-methyl-4-hydroxyphenyl)-2,2-propane, bis(3-methyl-4-hydroxyphenyl)-1,1-cyclohexane, bis(2-hydroxy-4-methyl-phenyl)-l,l-butane, bis(2-hydroxy-4-tertiary butylphenyl)-2,2-propane, bis(4-hydroxyphenyl)-1-phenyl-1,1-ethane, 4,4'-dihydroxy-

3-methyl diphenyl-2,2-propane, 4,4'-dihydroxy-3-methyl-3'-iso-propyl diphenyl-2,2-butane, bis(4-hydroxyphenyl)sulfide, bis (4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-~Z49 ~8 hydroxyphenyl)sulfonate, bis(4-hydroxyphenyl)amine, bis(4-hydroxyphenyl)phenyl phosphine oxide. 2,2-bis(3-chloro-4-hydroxyphenyl) propane, 4,4'-(cyclomethylene) bis-(2,6-dichloro-phenoli 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-3,5-dibromo-4-hydroxyphenyl)-propane, 1,1-bis-(3,5-dichloro-4-hydroxyphenyl)-l-phenylethane, 2,2-bis-(3,5-dibromo-4-hydroxy-phenyl-hexane, 4,4'-dihydroxy-3,3',5,5'-tetra-chlorodiphenyl, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-

4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, tetra-chlorodiphenylolsulfone, bis(3,5-dibromo-4-hydroxy phenyl)-phenyl phosphine oxide, bis(3,5-dibromo-4-hydroxyphenyl) sulfoxide, bis(3,5-dibromo-4-hydroxyphenyl)sulfone, bis(3,5-di-bromo-4-hydroxyphenyl)-sulfonate, bis(3,5-dibromo-4-hydroxyphenyl)-sulfide, bis(3,5-dibromo-4-hydroxyphenyl)-amine, bis(3,5-dibromo-4-hydroxyphenyl)-ketone, and 2,3,5,6,2',3',5',6',-octochloro-4-4'-hydroxy biphenyl. Representative biphenols are o,o'-biphenol, m,m'-biphenol; p,p'-biphenol; bicresols, such as 4,4'-bi-o-cresol, 6,6'-bi-o-cresol, 4,4'-bi-m-cresol; dibenzyl biphenols such as a,a'-di-phenol-4,4'-bi-o-cresol; diethyl biphenols such as 2,2'-diethyl-p,p'-biphenol, and 5,5'-diethyl-o,o'-biphenol; dipropyl biphenols such as 5,5'-dipropyl-o,o'-biphenol and 2,2'-diisopropyl-p,p'-bi-phenol; dially biphenols such as 2,2'-diallyl-p,p'-biphenol; and dihalobiphenols, such as 4,4'-dibromo-o,o'-biphenol. Mixtures of isomers of the foregoing bisphenols can be used.
The dicarboxylic acids which are useful in this process are also well known and are represented by the formula:
O O
HX - C ~ (Z)n ~ C XH
in which X is oxygen or sulfur, Z is alkylene, -Ar- or -Ar-Y-Ar-where Ar has the same definition as given with respect to the bis-phenols, Y is a alkylene, of 1 to 10 carbons, haloalkylene, -0-, -S-, -S0-, -S02-, -S03-, -C0-, GP=0 or GN = ; and n is 0 or 1.
Suitable dicarboxylic acids include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, bis(4-carboxy)-diphenyl, bis(4-carboxyphenyl)-ether, bis(4-car-boxyphenyl)-sulfone, bis(4-carboxyphenyl)-carbonyl, bis(4-carboxy-phenyl)-methane, bis(4-carboxyphenyl)-dichloromethane,1,2- and l-bis(4-carboxyphenyl)-ethane, 1,2- and 2,2-bis(4-carboxyphenyl)-propane, 1,2- and 2,2-bis(3-carboxyphenyl)-propane, 2,2-bis(4-car-boxyphenyl)-l, l-dimethyl propane, 1,1- and 2,2-bis(4-carboxyphenyl)-butane, 1,1- and 2,2-bis(4-carboxyphenyl)-pentane, 3,3-bis(4-car-boxyphenyl)-heptane, 2,2-bis(4-carboxyphenyl)-heptane, and alipha-tic acids such as oxalic acid, adipic acid, succinic acid, malonic acid, sebacic acid, glutaric acid, azelaic acid and the like. Iso-phthalic acid and terephthalic acid are preferred due to their availability and low cost. Most preferably, the dicarboxylic acid component comprises a mixture of about 75 to about 100 mol percent isophthalic acid and about 25 to about 0 mole percent terephthalic acid.
When the dicarboxylic acids used in preparing a polyester of the invention consist of both isophthalic and terephthalic acids in accordance with an especially preferred embodiment of the in-vention, a weight proportion of isophthalic to terephthalic acid residues in the polyester ranging from about 75:25 to about 90:10 provides an especially satisfactory result.
An alternate process for preparing suitable aromatic polyes-ters, disclosed in US Patent 3,471,441, to Hindersinn et al., com-prises the homogeneous reaction of an aliphatic modifier, prefer-ably a glycol of 2 to about 100 carbon atoms, with a diacid halide of a dicarboxylic acid, followed by an interfacial polymerization of the resultant prepolymer with a bisphenol. Compositions pre-pared by this process have an aliphatic modifier, i.e. a glycol, .:~

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incorporated into the structure of the reaction product of the bisphenol and diacid halide, and possess excellent engineering properties such as high impact strength, high modulus, improved moldability, and high softening points.
The bisphenol and dicarboxylic acid components which may be employed in the Hindersinn et al., preparatory process correspond to those described above. The aliphatic modifier is a reactive difunctional component which may be represented by the formula:
HnD - A - D'Hn wherein D and D' are independently selected from the group consis-ting of 0, S, and N; A is a bivalent or disubstituted aliphatic radical, free of tertiary carbon atoms, selected from the group consisting of alkylene, cycloalkylene, arylalkylene, alkyleneoxy-alkyl, poly(alkyleneoxy)alkyl, alkylene-carboxyalkalene-carboxy-alkyl, and poly(alkylene carboxylakylene-carboxy)alkyl; n is an integer from 1 to 2 with n being 2 when D and D' is N. Typical examples of aliphatic modifiers having the foregoing formula in-clude ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexane, dimethanol, l,4-butane dithiol, dipropylene glycol, polypropylene glycol, l,l-isopropylidene bis(p-phenyleneoxy)di-2-ethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, bis(4-hydroxy-cyclohexane)-2,2-propane, di(hydroxyethyl)adipate, di(hydroxy-propyl) glutarate, di(hydroxyethyl) poly(ethylene glycol) adipate, ethane dithiol, ethanolamine, methylethanolamine, hexamethylene-diamine, 1,3-propanediol, 2-mercaptoethanol, and 2-aminopropane-diol. Combinations of the above-described aliphatic modifiers can also be employed, usually to obtain special properties.
Solution processes can also be employed in the preparation of suitable aromatic polyesters, such as disclosed in US Patents 4,051,107 and 4,051,106.

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The polyester components of the invention are preferably prepared by a process, described as melt polymerization, involving an ester interchange, i.e. transesterification reaction, between a diphenolic reactant and a diaryl ester of a dicarboxylic acid car-ried out in the melt (i.e. without use of a reaction solvent or diluent). Such a process is described in British Patent 924,607, to Imperial Chemical Industries Limited.
A further melt polymerization process which can be used to prepare a linear aromatic polyester suitable for use in this in-vention is described and claimed in Belgian Patent 837,725, issued July 20, 1976. This process basically comprises first mixing a bisphenol, a diaryl ester of a dicarboxylic acid and diol, then reacting the resulting mixture in the presence of a transester-ification catalyst.
The polyphenylene sulfide component of the instant invention is a crystalline polymer with a repeating structural unit compri-sing a para-substituted benzene ring and a sulfur atom which may be described by the formula, where n has a value of at least about 100. _ .

~ S - l The preparation of polyphenylene sulfide is illustrated in US
Patent 3,354,129, to Edmonds, Jr., et al., wherein at least one E

1 i24~18 polyhalo-substituted cyclic compound is reacted with an alkali metal sulfide in a polar organic solvent reaction medium. Suit-able polyphenylene sulfide compositions are available commercial-ly under the trademark RYTON of the Phillips Petroleum Company, and include compositions which are either unfilled, or filled with glass or some such conventional material. Preferably, the poly-phenylene sulfide component has a melt flow index, measured at 600~F. using a 5 Kg. weight and a standard orifice, within the range of from about 40 to about 7000.
The novel resin compositions of the instant invention are prepared by blending the linear aromatic polyester with polyphenyl-ene sulfide. The blending or mixing process can be performed using conventional mixing equipment such as, for example, a Banbury* mix-er, mixing roll, kneader, screw extruder, or injection molding machine. Although the mixing ratio may vary depending on the physical properties desired in the resultant polymer blend, the polyphenylene sulfide component is present preferably in an amount of about 5 parts to about 95 parts by weight of blended polymer, and most preferably, about 5 parts to about 30 parts by weight of polyblend.
The novel polymer compositions of the present invention may also include various additives such as organic or inorganic fillers, stabilizers, antistatic agent, and flame retardants.
According to a particular embodiment of the invention, the novel polymer compositions of the present invention contain an effective flame retardant proportion of a halogen-containing Diels Alder adduct of (A) a cyclopentadiene wherein all of the hydrogen atoms of the carbon atoms joined by carbon-to-carbon double bonds have been replaced by halogen, e.g. fluorine, chlorine, or bromine and (B) an ethylenically unsaturated organic compound containing one or two carbon-to-carbon double bondsi the molar proportion of the cyclopentadienyl residue to unsaturated compound residue in said adduct being 1:1 when the unsaturated compound contains one *trademark 1~24918 "
carbon-to-carbon double bond, and 2:1 when the unsaturated com-pound contains two carbon-to-carbon double bonds.
Preferably the Diels Alder adduct employed as flame retardant agents according to the invention is derived from a cyclic com-pound having two intracyclic carbon-to-carbon double bonds and has the structural formula:
X X

XX ~ Q V ~ Xx X X
wherein X is selected from chlorine, bromine and fluorine, V is selected from chlorine, bromine, fluorine, alkyl of 1 to 10 carbon atoms, alkyloxy wherein the alkyl group contains 1 to 10 carbon atoms, haloalkyl and haloalkyloxy wherein the alkyl groups contain 1 to 10 carbon atoms and halo is chloro, bromo, or fluoro; Q is a tetravalent saturated cyclic radical having at least 4 carbon atoms which may be substituted by alkyl groups of 1 to 6 carbon atoms, chlorine, bromine or fluorine. The alkyl and alkoxy radicals preferably have 1 to 6 carbon atoms. Q is preferably a tetravalent homocyclic radical of 5 to 18 carbon atoms or a tetravalent heterocyclic radical of 4 to 18 carbon atoms and preferably has 1 to 5 cyclic structures. When Q is a plurality of cyclic structures, they are fused, that is, share carbon atoms.
In especially preferred halogen-containing fire retardant agents of the invention Q is a homocyclic radical, more preferably a homocyclic monocyclic radical and especially is a homocyclic, monocyclic radical containing only hydrogen substituents. In especially preferred adducts of the invention Q has no more than 10 carbon atoms.

11249iL8 The fire retardant additives of the invention are known com-pounds prepared by the Diels Alder reaction of halogenated cyclo-pentadiene and an open chain unsaturated compound (such as ar-tetrabromostyrene), a di-unsaturated homocyclic aliphatic compound (such as 1,5-cyclooctadiene, cyclopentadiene, 1,4-cyclohexadiene, bicyclo(2.2.1)heptadiene and 1,2,3-trichloro-1,4-cyclohexadiene) or a di-unsaturated heterocyclic aliphatic compound containing divalent sulfur or oxygen as the hetero-ring atom constituent as exemplified by furan or thiophene. Also there may be employed as the heterocyclic reactant a mono alkyl or di-alkyl derivative of furan or thiophene wherein one or both of the carbon atoms attached to the hetero-ring atom contain an alkyl substituent of 1 to 6 carbon atoms such as l-methyl furan, l-hexyl furan, 1,4 dipropyl furan, l-methyl thiophene, 1,4-dihexyl thiophene and the like.
Illustrative of halogenated cyclopentadiene compounds suitable for preparing the fire retardant additive are hexachlorocyclopenta-diene, 5,5-dimethoxytetrachlorocyclopentadiene, hexabromocyclo-pentadiene, 5,5-difluorotetrachlorocyclopentadiene, 5,5-dibromo-tetrachlorocyclopentadiene and 5,5-diethoxytetrachlorocyclopenta-diene.
Typical of the Diels Alder adducts described hereinabove which can be used in the practice of the invention are: ~ ~
1,2,2,4,7,8,9,10,13,13,14,14-dodecachloro-1,4,4a,5,6,6a,7,10, lOa,11,12,12a-dodecahydro-1,4:7,10-dimethanodibenzo[a,e] cyclo-octene;
1,2,3,4,6,7,8,9,13,13,14,14-dodecachloro-1,4:5,10:6,9-tri-methano-llH-benzo[b]-fluorene;
1,2,3,4,5,6,7,8,10,11,11-dodecachloro-1,4:5,8-dimethano-fluorene;
1,2,3,4,5,6,7,8,12,12,13,13-dodecachloro-1,4:5,8:9,10-tri-methano-anthracene;

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1,2,3,4,5,6,7,8,11,11,12,12-docecachloro-1,4,4a,5,8,8a,9,9a, lO,lOa,decahydro-1,4,5,8-demethanoanthracene;
1,2,3,4,6,7,8,9,10,10,11,11-dodecachloro-1,4,4a,5,5a,6,9,9a, 9b-octahydro-1,4:6,9-demethanodibenzothiophene; and 1,2,3,4,6,7,8,9,10,10,11,11-dodecachloro-1,4,4a,5,5a,6,9,9a, 9b-octahydro-1,4:6,9-dimethanodibenzofuran.
Mixtures of these and equivalent adducts can also be employed.
The preparation of the aforementioned known halogen-containing Diels Alder adducts is more particularly described in R.D. Carlson et al., US Patent 3,711,563 (especially at Column 8), W. Seydl, US
Patent 3,923,728 (to B.A.S.F.-A.G.), I. Gordon et al., US Patent 4,000,114, R.R. Hindersinn et al., US Patent 3,535,253 and J.L.
Dever et al., US Patent 3,687,983.
The proporation of the halogen-containing flame retardant adduct compound employed according to the invention is generally from about 1 to less than about 50 weight percent, preferably about 2 to about 30 weight percent, based on the combined weight of the polyester and polyphenylene sulfide. An especially good result is obtained employing about 3 to about 15 weight percent of the halogen-containing adduct based on the combined weight of the polyester and the sulfide polymer components.
According to another embodiment of the invention the flame retardant properties of the present polyester-polyphenylene sul-fide mixtures are enhanced when the bisphenol reactant employed to prepare the polyester comprises from about 1 to less than about 50 mole percent of a bisphenol wherein at least one carbon atom is substituted with halogen the balance of said bisphenol reactant be-ing bisphenol devoid of halogen substitution.
The halogen-containing bisphenol of the invention corresponds to the above generic structural formula which defines the bis-phenol or bisphenols employed in preparing the polyesters of the 112~918 invention. According to a preferred embodiment of the invention the halogen substituents are chlorine or bromine. Preferably the halogen-substituted bisphenol component contains 1 to 20, more preferably 2 to 8, and especially 4 halogen substituents. Pre-ferably at least one of the T and T' in the aforementioned genericbisphenol structural are halogen. In an especially preferred em-bodiment of the invention all of the halogen substituents of the halogen-substituted bisphenol component are present as T and T'.
The bisphenol component of the invention which is devoid of halogen substitution corresponds to the aforementioned generic structural, (which is pointed out above, broadly defines bis-phenols of the invention) when G in the generic formula is alkyl-aryl, alkylaryl, arylalkyl or cycloalkyl, E is divalent alkylene, cycloalkylene or arylene, -O-, -S-, -SO-, -S02-, -S03-, -CO-, GP _ =0, or GN _ , and T and T' are independently selected from the group consisting of G and OG, (with Ar, m, b, and x of said generic formula having the previously assigned meanings).
While residues of the halogen-substituted bisphenol and the halogen free bisphenol can be present in the same polyester con-stitutent of the present blend it is preferred that the residue of the halogen-containing bisphenol and the residue of the halogen-devoid bisphenol be present in different polyester components of the polyester-sulfide polymer mixture, i.e. the polyester component, of the blend preferably comprises:
A) a polyester of said halogen-substituted bisphenol, and B) a polyester of said bisphenol devoid of halogen sub-stituents.
Generally when the aforementioned mixture of polyesters is employed according to the foregoing preferred embodiment, the halogen-containing bisphenol polyester is present in an amount of from about 3 to about 40 weight percent, and especially from about 5 to about 20 weight percent, based on the combined weight of the polyphenylene sulfide and all of the polyesters of the present polymer blend.
In the mixture of polyesters preferably employed as the poly-ester component of the invention, either or both the halogen-containing bisphenol polyester and the halogen polyester may contain residues of aliphatic hydroxy compounds as modifying constituents. However, in accordance with an especially preferred embodiment of the invention the halogen-containing bisphenol poly-ester constituent of said mixture contains said aliphatic modifier whereas the halogen-free bisphenol polyester constituent is devoid of said aliphatic modifier.
The presence of the above-described halogen-containing Diels Alder adduct and/or the halogen-substituted bisphenol in the linear aromatic polyesters according to the invention greatly enhances the flame retardancy of the polyester-sulfide polymer blend without detrimentally affecting the other desirable properties of these compositions. The flame retardance is enhanced to the extent that excellent fire retardant performance is achieved even when the compositions are molded in extremely thin sections, (e.g. of thick-nesses less than about 1/16 of an inch). This excellent flame retardance performance makes the present composition especially suitable for the fabrication of electrical components such as miniature circuit boards and the like.
The additive-containing resin mixture of the invention may be prepared, if desired, by charging the polyester and sulfide polymer with the additive to a conventional mixing apparatus, such as a premix mixer, or melt extruder. The resultant addi-tive-containing composition can then be molded directly in an injection molding apparatus or an extruder. The molded articles thus formed have excellent hydrolytic stability and tensile strength.

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The fillers which may be employed in the invention are pre-ferably particulate fillers such as particulate glass (e.g. chopped glass fiber, glass rovings, glass microballoons or microspheres and pulverulent glass) particulate clay, talc, mica, inorganic natural fibers, alimina, graphite, silica, calcium carbonate, carbon black, magnesia and the like. Generally such fillers are added to re-inforce the structural integrity of a polymer, e.g. to inhibit sagging and/or to improve the tensile strength and stiffness of the polymer composition and also to reduce shrinkage, minimize crazing, lower material costs, impart color or opacity, and im-prove the surface finish of the polymer composition. Generally the amount of particulate filler employed in the composition of the invention is in the range of about 5 to about 70 weight per-cent, preferably about 5 to about 40 weight percent and espec-ially about 8 to about 30 weight percent based on the combinedweight of the polyester and the phenylene sulfide polymer. The filler employed is preferably inorganic.
It is found according to the invention that use as filler of particulate glass, advantageously glass fibers, is especially desirable since the presence of the particulate glass filler further enhances the fire retardancy of polymer mixture of the invention.
The presence of the particulate glass component in the com-positions of the invention generally enhances the flame retardance of the polyester-sulfide polymer blend to the extent that excell-ent fire retardant performance is achieved even when the compo-sitions are molded in extremely thin sections, (e.g. of thick-nesses less than about 1/16 of an inch). This excellent flame retardance performance makes the glass filled compositions of the invention especially suitable for the fabrication of elect-rical components such as miniature circuit boards and the like.

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The glass filling, especially glass fiber filling, employed in the invention preferably contains an organic coupling agent as a very thin coating on the glass particles. The coupling agent forms an adhesive bridge between the glass and the polymer blend thereby enhancing the strength properties of the filled polymer blend. Typically, organic coupling agents employed in the art in-clude transition metal complexes of unsaturated aliphatic acids such as the methacrylate chromic chloride complex as well as var-ious organic silane compounds including vinyl trichlorosilane, vinyl triethoxysilane, gamma amino-propyl triethoxysilane, ally trichlorosilane resorcinol, vinyltrimethoxysilane, amyltrimeth-oxysilane, phenyltriethoxysilane, B-cyclohexylethyltrimethoxy-silane, ~-methacryloxypropyltrimethoxysilane, ~-iodopropyltrimeth-oxysilane, ~-chloropropyltrimethoxysilane, ~-chloroisobutyltrieth-oxysilane, ~-glyxidoxypropyltrimethoxysilane, N-~-aminoethyl-~-aminopropyltrimethoxysilane, N-bis-(~-bydroxyethyl)-~-amino-pro-pyltriethoxysilane, and ~-(3,4-epoxycyclohexylethyltrimethoxysilane.
Preferably the coupling agent employed with the glass filler according to the invention is a silane coupling agent.
Glass fillers are frequently manufactured and sold so as to contain the coupling agent as a proprietary ingredient on the sur-face of the glass. The coupling agents and their uses with glass fillers are discussed in more detail in W.V. Titow and B.J. Lanham, "Reinforced Thermoplastics", Halstead Press, 1975, pp. 83-88 and L. Mascia, "The Role of Additives in Plastics", J.Wiley and Sons, 1974, pp. 89-91.
It has been found according to the invention that the presence of antimony additives (such as metallic antimony and compounds of antimony) is generally undesirable since the presence ~249i~

of the antimony constituent generally is detrimental to the flame retardance of the polymer mixture as is illustrated in the examples below.
The following examples further illustrate the various aspects of the invention but are not intended to limit it. Various modi-fications can be made in the invention without departing from the spirit and scope thereof. Where not otherwise specified in this specification and claims, temperatures are given in degrees centi-grade, and all parts and percentages are by weight.

A) By Solution Polymerization A mixture of 165.7 parts isophthaloyl chloride, 29.2 parts terephthaloyl chloride, and 223.5 parts bisphenol-A ~2.2-bis(4-hydroxyphenyl)propane) were dissolved in 2270 parts methylene chloride (having a moisture content of 10 ppm of water) in a reactor at 25C. 200.7 parts triethyl amine were added at a constant rate to the reaction mixture over a period of 7.5 hours, under nitrogen purge with stirring. The reacti~on mixture was maintained at 15C. After completion of the triethylamine addi-tion, the mixture was stirred for two hours at 20C. 6.8 partsof benzoyl chloride were then added to react with the end-groups of the polymer. After one hour, 13.7 parts of isopropanol were added to react with any excess benzoyl chloride. After 1/2 hour, dilute aqueous hydrogen chloride (570 parts of a 0.5 wt.% sol.) was added to react with any excess triethylamine for an additional 1/2 hour with stirring. The two phases were then allowed to separate by gravity, and the water phase was removed. Additional washes of the polymer solution with equal amounts of water were carried out until the chloride ion in the polymer solution measured less than 0.1 ppm. The polymer was then precipitated from solution and dried in a vacuum oven until the moisture concentration was less - l9 -than 0.1 wt.%. The resultant high molecular weight polynler had an intrinsic viscosity of 0.74 dl/g in sym. tetrachloroethane (at 30C.) B) By Melt (transesterification) Polymerization : Bisphenol-A (1319.1 g), diphenyl terephthalate (275.9 9) and diphenyl isophthalate (1562.9 g) were dried for several hours at 75 in a vacuum oven and charged with 0.07 9. of anhydrous lithium hydroxide transesterfication catalyst to a 5-liter resin kettle under nitrogen. The kettle was equipped with a thermometer, a nitrogen inlet on a Y-tube, a mechanical stirrer, a short Vigreaux column, a distillation head and 3 necked flask receiver.
The kettle was heated to 210 to melt the reactants and vacuum was applied gradually to the stirred molten mass. The temperature of the reaction mass was increased gradually to re-move phenol overhead to the receiver. After 1.4 hours the tem-perature of the reaction mass reached 228 and the reaction mass pressure was about 0.5 mm Hg. The reaction mass was then flooded with dry nitrogen to relieve the vacuum and the viscous reaction mass was poured into a foil-lined glass tray and allowed to cool to ambient temperature.
The bisphenol A-isophthalate-terephthalate prepolymer thus obtained was broken up and dried overnight at 70 in a vacuum oven. The dried prepolymer (1070 9.) was changed to a two gallon oil-heated stainless steel reactor equipped with agitation means under dry nitrogen and heated with agitation to 210. Agitation of the molten mass was commenced after 1 hour. After 1.3 hours from the commencement of heating, vacuum (about 0.6 mm of ~Ig.) was applied to the agitated mass. The reaction temperature was raised gradually over a period of about 2 hours to 305. The 30 agitated reaction mass was then maintained under vacuum at 305 for 6.7 hours. The reactor was opened and the polyester obtained was discharged from the reactor and allowed to cool to ambient temperature. A clear yellow bisphenol A-isophthalate-terephthalate polyester having a relative viscosity of 1.36 (measured in tetra-chloroethane at 30) was obtained.
The foregoing procedure was repeated with 1100 9. of pre-polymer being employed in the polymerization reaction. A similar polymer was obtained having a relative viscosity of 1.35 (measured in tetrachloroethane at 30).

A linear aromatic polyester was prepared according to the procedure of Example 1 (A) and dried for four hours at 120C.
100 parts of polyphenylene sulfide (commercially sold under the trademark RYTON V-l by the Phillips Petroleum Company), having a melt flow index of 6,000 as determined at 600F. with a 5 Kg.
weight using a standard orifice, was added to 900 parts of poly-ester and tumble mixed for 0.5 to 1 hour. The blend was milledon a two roll Farrell Mill (front roll heated to 480C., back roll heated to 425F.) for 1.5-3.0 minutes at 45 r.p.m. The blend was then sheeted, and ground to 4 mm. granule size on a granulator. The granules were dried for 1-2 hours at 120C. and injection molded to produce tensile and flex bars. The injection molding conditions were as follows:
MOLDING PARAMETERS
Barrel Temperature (F) 600 Nozzle Temperature (F) 580 Mold Temperature (F) 250 Screw Speed (rpm) 120 Back Pressure (psi) 625 Injection Pressure (psi)11,200 Plasticating Time (secs) 8 Fill Time (secs) 3 Total Injection Time (secs) 10 The tensile bars thus prepared were tested and found to have the following physical properties. By way of comparison, a control which does not include polyphenylene sulfide, is also shown.

PROPERTIES
Example 2 Control Tensile Strength (psi) 10,150 10,000 Tensile Modulus (psi x 105)3.09 3.34 After 7 days immersion in boiling H20:
Tensile Strength (psi) 10,800 1,700 Tensile Modulus (psi x 105)3.34 2.75 A linear aromatic polyester was prepared according to the procedure of Example l(A) and dried for four hours at 120C. The procedure of Example 2 was followed to produce 4 mm. granules.
The granules were dried for 4 hours at 120C. and were then blended with polyphenylene sulfide pellets (commercially sold by the Phillips Petroleum Corp. under the trademark RYTON 6), having a melt flow index of 50 as determined at 600F. with a 5 Kg. weight using a standard orifice in various mixing ratios. Tensile bars were prepared and tested, and the results are summarized in Table 1 below.
The aromatic polyesters of the invention generally have an intrinsic viscosity of at least l.S dl/g when measured in sym.
tetrachloroethane at 30C., and preferably at least 1.6 dl/g.

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~l~249~,.8 EXAMPLt 7 About 450 parts of a bisphenol A-isophthalate polyester resin having an isophthalate:terephthalate ratio of 5.67 which was pre-pared substantially as described in Example 1 (A) was dried for about 4 hours at 120 and charged gradually to the Farrell Mill described in Example 2 which was operated with its front roll at 450F. and its back roll at 410F. until fusion of the resin was completed and a band of clear resin formed on the front roll.
About 50 parts of the polyphenylene sulfide resin of Example 2 was then added until a homogeneous resin band formed on the front roll.
The mixture of resins was milled for about 1.5 to 3 minutes and then sheeted from the mill. The milled resin blend was ground to granules of about 4 mm granule size as described in Example 2 which were then dried at about 120 for about 4 hours.
The dried resin mixture granules were mixed with 58.3 parts of chopped glass fiber (3/16 inch length, manufactured by Owens Corning Fiberglass Corporation under the designation 419AA, which contains a proprietary silane coupling agent). The resultant mix-ture was then added to an Arburg Alrounder 200 injection molding machine operated at a barrel temperature of 600F., a mold temper-ature of 215-225 F. and an injection pressure of about 14,000 psi.
The mixture was molded as bar specimens which were subsequently reground and dried substantially as described hereinabove to insure that a homogeneous blend was obtained. The dried reground glass fiber-resin mixture was then charged to an Arburg 221E/150 Injection molding machine operated at a barrel temperature of 550F., a mold temperature of about 290-295 F., and an injection pressure of about 16,760 psi to injection mold the resin-glass fiber blend into specimen bars of about 5 inches length, 1/2 inch width and 1/16 inch thickness. Several of the 1/16 inch thickness specimen bars were reserved for the flame retardant test described herein below.

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The remainder of the 1/16 inch thick specimen bars were dried at 120 for about 2 hours and compression molded between steel plate backed aluminum sheets in a Carver Four Paten Laboratory Press operated at 400-430 F. and a pressure of about 30,000 to 35,000 psi to obtain specimen bars 5 inches in length, 1/2 inch in width and 1/32 inch in thickness.
The 1/16 inch- and 1/32 inch-thick bar specimens are evaluated in flame retardant properties according to the Vertical Burning Test described in "UL-94-Standards for Safety", Underwriters Laboratory Inc., Second Revised Edition, May 2, 1975, pages 6-8.
In accordance with the evaluation technique of the aforementioned test the specimens are rated V-O, V-l or V-2, with V-O indicating the greatest degree of flame retardancy and V-2 indicating the poorest degree of flame retardancy. The Oxygen Index of a sample of the injected resin product obtained from the latter Arburg mold-ing apparatus was also determined.
The results of the aforementioned flame retardant tests upon the excellent glass fiber-filled resin blend obtained in this Example are reported in Table 2 below.

To provide a basis for comparing the flame retardancy of the aforementioned glass fiber-filled resin blend with tha~ of an un-filled resin blend of the invention, an unfilled resin blend of the invention containing the polyester of Example l-A was milled and injected molded substantially as described hereinabove at Examples 2 and 7 to provide the 1/16 inch- and 1/32 inch-bar specimens described in Example 7~ As a glass-fiber component was not employed, it was unnecessary to regrind and remold the product as described in Example 7 to provide a homogeneous blend of the product components.

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~24C~8 The specimen bars were evaluated for flame retardance according - to the UL-94 Vertical Burning Test and their Oxygen Index was deter-mined as described in Example 7. The resultant test data is com-pared with that of the Example 7 product in Table 2.

The procedure of Example 7 was repeated substantially as described except that the bisphenol A-isophthalate-terephthalate polyester employed was prepared by melt polymerization as described in Example l(B) and the flame retardance of a 1/16 inch thickness specimen and the Oxygen Index of the product were not measured.
The results of this example are also presented in the Table below.

The procedure of Example ~ was repeated substantially as described with the same proportions of polyester and polyphenylene sulfide as in Example ~ except that the bisphenol-A-isophthalate-terephthalate polyester employed was prepared by melt polymerization as described in Example l(B) and the flame retardance of a 1/16 inch thickness specimen and the product Oxygen Index were not determined.
The results of this Example are also presented in the Table below.
EXAMPLES 11-13 (Controls) Examples 11-13, which employ the polyester of Example l(A) and which are summarized in Table 2 below, are Control Examples substan-tially comparable to Examples 7 and ~. The products of Examples 11-13 are compositions substantially comparable to those described in Examples 7 and 8 except that one or more of the components of the Examples 7 and 8 products were omitted. Control Examples 11-12 illustrate the effect on flame retardance resulting from addition of an antimony compound ~Sbz03J to the resin compositions of the invention.

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1L9i8 Where a glass fiber filler constituent is employed in these Control Examples, the mixtures were milled, molded and tested for flame retardancy substantially in accordance with the procedure of Example 7. Where glass fiber filler is not employed, the Con-trol Example was carried out by the procedure of Example 8 sub-stantially as described. The antimony additive employed in Examples 11-12 was added to the resin mixture during the milling of the lat-ter in the Farrell Mill (substantially in accord with the method of addition of the polyphenylene sulfide constituent described in Example 7 and subsequent to the addition of the latter polymer).

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~2~.8 In Example 8 of Table 2 the proportion of polyester and poly-phenylene sulfide is 9:1 corresponding to the proportions of these constituents in Examples 7, 10, 12 and 13.
As is evident from the data of Table 2 by comparison of the results of Example 7 with those of Example 8, the use of a parti-culate glass filler in the present resin blend enhances significant-ly the flame retardant property of the resin blend according to both the UL-04-test evaluation described above and Oxygen Index.
The results of Examples 9 and 10 indicate that a similar 1~ effect from use of filler is obtained when the polyester is pre-pared by melt polymerization.
By comparison of the test results of the product of Example 8 with those of the product of Example 11, the unfilled product of the invention as prepared in Example 8 has a flame retardance su-perior to that of its polyester component.
Comparison of the test results of Examples 7 and 8 with those of Examples 12 and 13 indicate that the presence of an antimony constituent in the resin blends of the invention (both filled and unfilled) is deleterious to the flame retardance of the blends.
It will be appreciated by those skilled in the art that procedural modifications of the above-described experimental - technique can be made without departing from the spirit and scope of the invention.
For example, in Example 7 a similar result providing a homo-geneous glass filler-resin mixture can be obtained without the necessity of regrinding the molded glass fiber-containing resin product. In this alternative procedure the Farrell Mill resin product, after being ground to granules and dried, is added to the hopper end of a screw resin extruder (such as a Haake Polytest 45 single screw extruder or a Werner Pfleider ZDS-K28 twin screw extruder) which the particulate glass component is added downstream on the extruder. (Alternatively, the particulate glass can be ~ ~;
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~ 24918 mixed with the dried ground granules with the resultant mixture being added to the hopper end of the extruder). The resultant extruded resin containing a homogeneous dispersion of the glass component is then sliced into pellets which are then injection molded as described in Examples 2 and 8.
Also, instead of separate addition of the particulate glass constituent as described in Example 7, the latter constituent can be homogeneo~sly blended with the sulfide polymer constituent of the resin blend before the said sulfide polymer is added to the polyester.
In place of the chopped glass fiber employed in the above Examples, other forms of particulate glass filler agents such as uncut glass strands, glass rovings, glass pellets, pulverulent glass, and glass micro-balloons can be used.

About 450 parts of bisphenol A-isophthalate-terephthalate polyester resin having an isophthalate:terephthalate ratio of 5.67 which is prepared substantially as described in Example 1 (A) was dried for about 4 hours at 120 and charged gradually to the Farrell Mill described in Example 2 which is operated with its front roll at 450F. and its back roll at 410F. until the fusion of the resin was complete and a band of clear resin formed on the front roll. About 50 parts of the polyphenylene sulfide resin of Examp~e~ ~
2 was then added until a homogeneous resin band was formed on the front roll. In a similar manner, 20 parts of 1,2,3,4,7,8,9,10,13, 14,14-dodecachloro-1,4,4a,5,6,6a,7,10,10a,11,12,12a-dodecahydro-1,4:7,10-dimethanodobenzo[a,e~cyclooctene herein referred to for brevity as "C.O.D." was added to the resin mixture in the mill.
The mixture of resins and C.O.D. was milled for about 1.5 to 3 minutes and was then sheeted from the mill, ground to granules of about 4 mm. granule size as described in Example 2 and dried at 120 for 4 hours.

gi8 The dried resin blend granules were charged to an Arburg 221E/150 Injection molding machine operated at a barrel temperature of 550F., a mold temperature of 275-280F. and an injection pres-sure of 20,000 psi to injection mold the C.O.D.-containing blend into specimen bars of about 5 inch length, 1/2 inch width and 1/16 inch thickness. Several of 1/16 inch thickness specimen were re-served for the flame retardant test described hereinbelow. The remainder of the 1/16 inch thick specimen bars were dried at 120 for 2 hours and compression molded between steel plate-backed aluminum sheets in a Carver Four Paten Laboratory Press operated at 400-430F. at a pressure of 30,000 to 35,000 psi to obtain specimen bars 5 inches in length, 1/2 inch in width and 1/32 inch in thickness.
The 1/16 inch- and 1/32 inch-thick bar specimens were evaluated in fire retardant properties according to the Vertical Burning Test described in "UL94-Standards For Safety", Underwriters Laboratories, Inc., Second Revised Edition, May 2, 1975, pages 6-8. In accordance with evaluation technique of the aforementioned test, the specimens were rated V-O, V-l, or V-2 with V-O indicating the greatest degree of flame retardancy and V-2 indicating the poorest degree of flame retardancy. The Oxygen Index of a sample of injected molded resin blend obtained from Arburg Injection molding machine is also de-termined.
The results of these experiments are reported in Table 3 below.

:
The procedure of Example 14 was followed substantially as des-cribed through the step wherein the sheet of the blend of C.O.D., polyester and polyphenylene sulfide was obtained from the Farrell Mill was ground to granules of 4 m.m. granule size and dried at 120 for 4 hours.
The dried granules were mixed with 58.3 parts of chopped glass fiber (3/16 inch length, manufactured by Owens Corning Fiberglass 1~24918 Corporation under the designation 419AA). The resultant mixture was then added to an Arburg Alrounder 200 injection molding machine operated at a barrel temperature of 550F., a mold temperature of 215-225F., and an injection pressure of about 20,000 psi.
The mixture was molded as bar specimens which were subsequently reground and dried substantially as described hereinabove to ensure that a homogeneous mixture of the glass fibers with the resin blend was obtained. The dried reground mixture was then charged to the Arburg 221E1150 Injection molding machine (operated at a barrel temperature of 550F., at a mold temperature of 290-295F., and an injection pressure of about 20,000 psi) and molded as 5 inch x 1/2 inch x 1/16 inch specimen bars as described in Example 7. As in Example 14, a portion of the latter specimen bars were reserved for flame retardant testing and the remainder were compression molded to obtain 5 inch x 1/2 inch x 1/32 inch bar specimens. Both the 1/16 inch and 1/32 inch bar samples were tested for flame retard-ance as described in Example 14. The results of this Example are reported in Table 3 below.
EXAMPLE 16 (Control) The procedure of Example 15 was repeated substantially as des-cribed except that following the addition of polyphenylene sulfide and C.O.D. to the Farrell Mill 5 parts of particulate antimony tri-oxide were added and the determination of Oxygen Index was omitted.
The resultant molded product was characterized by an unsatisfactory degree of brittleness, i.e. its bar specimens could be broken manually with only a slight flexing pressure. The flame retardant testing results of this product are reported in Table 3 below.
EXAMPLES 17-27 (Controls) In these Examples there were prepared and tested for flame re-tardance compositions which were substantially comparable to those ~2~918 of Examples 14, 15, and 16 except that one or more of the consti-tuents of the compositions described in Examples 14, 15, and 16 were omitted. Where glass fibers were present as a constituent in these compositions, the procedure of Example 15 was employed substantially as described. Where glass fiber was absent, the procedure of Example 14 was employed substantially as described.
The flame retardant results of these comparative Examples are compared to those of Examples 14-16 in Table 3 below.

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llZ4918 Of the examples presented in foregoing Table 3, Control Examples 17, 19, and 21 are identical to Control Examples 11, 13, and 12 above respectively, and Control Examples 18 and 20 are identical to illus-trative Examples 8 and 7 above, respectively. (The data of the earlier Examples 7, 8, 11, 12 and 13 is presented in Table 2 above).
In Control Example 18 the proportion of the polyester and the polyphenylene sulfide is 9:1 corresponding to the proportions of these constituents in Examples 14 and 15 and Control Examples 16, 19-21.
As is evident from the data of Table 3, Examples 14 and 15 pro-vide excellent resin compositions according to the invention which by virtue of their C.O.D. constituent are additionally characterized by excellent flame retardance even at low specimen thickness, i.e. at specimen thicknesses less than 1/16 inch, as compared to comparable compositions devoid of C.O.D. (Control Examples 18-21).
The data of Control Examples 16, 19, and 21 indicate that the presence of an antimony constituent in admixture with the polyester and polyphenylene sulfide is undesirable either because the antimony constituent increases the flammability of the compositions so as to render their low thickness flame retardancy unsatisfactory (as in Control Examples 19 and 21) or because the antimony oxide renders the composition undesirably brittle (as in Control 16).
The flammability behavior of resin mixtures containing both Bisphenol A-isophthalate-terephthalate polyester and polyphenylene sulfide is indicated by the data of Table 3 to be distinctive from~
the flammability behavior of resin compositions devoid of the poly-phenylene sulfide component. Thus, for example, the introduction of the halogenated organic flame retardant additive into the polyester-polyphenylene sulfide blend enhances the flame retardancy of the blend to provide satisfactory flame retardance at low specimen thick-ness (as is indicated by a comparison of Examples 14 and 15 andControl Example 16 with Control Example 18). In contrast, the intro-duction of the halogenated organic flame retardant into the poly-ester in the absence of the sulfide polymer fails to enhance the 1~24~18 resin flame retardance sufficiently to provide a satisfactory flame retardance at low specimen thickness (as is evident from a compari-son of the data of Control Examples 22 and 23 with the results of Control Example 17).
It will be appreciated by those skilled in the art that pro-cedural modifications of the above-described experimental technique in Examples 14-27 can be made without departing from the spirit and scope of the invention.
For example, in Example 14 a similar result providing a homo-geneous glass filler-resin mixture can be obtained without the necessity of regrinding the molded glass fiber-containing resin pro-duct. In this alternative procedure the Farrell ~ill resin product, after being ground to granules and dried, is added to the hopper end of a screw resin extruder (such as Haake Polytest 45 single screw extruder or a Werner Pfleider ZDS-K28 twin screw extruder) while the particulate glass component is added downstream on the extruder (alternatively, the particulate glass can be mixed with the dried ground granules with the resultant mixture being added to the hopper end of the extruder). The resultant extruded resin containing a homogeneous dispersion of the glass component is then sliced into pellets which are then injection molded as described in Example 14.
In place of the chopped glass fiber employed in the above Ex-amples 14-27, other forms of particulate glass reinforcement agents such as uncut glass strands, glass rovings, glass pellets, pulveru- , lent glass, and glass microballoons can also be used.
Instead of separate addition of the particulate glass constit-uent as described in Example 15, the latter constituent can be homo-geneously blended with the sulfide constituent of the resin blend before the said sulfide polymer is added to the polyester.
In place of the halogenated organic additive C.O.D. substan-tially similar results in the above Examples are obtained employing another halogenated organic additive of the same generic structural formula as C.O.D. (said generic structural being delineated in the ~12491~

specification above), for example:
1,2,3,4,5,6,7,8,9,13,13,14,14-dodecachloro-1,4:5, 10:6, 9-trimethano-llH-benzo[b] fluorene, 1,2,3,4,5,6,7,8,10,10,11,11,-dodecachloro-1,4:5, 8-dimethano-fluorene, 1,2,3,4,5,6,7,8,12,12,13,13-dodecachloro-1,4:5, 8:9, 10-trimethanoanthracene, 1,2,3,4,5,6,7,8,11,11,12,12-doclecachloro-1,4,4a,5,8-, 8a,9,9a,10,1Oa,decahydro-1,4,5,8-dimethanoanthracene;
1,2,3,4,6,7,8,9,10,11,11-dodecachloro-1,4,4a,5-, 5a,6,9,9a,9b-octahydro-1,4:6,9-dimethanodibenzothiophene;
and 1,2,3,4,6,7,8,9,10,11,11-dodecachloro-1,4,4a,5-, 5a,6,9,9a,9b-octahydro-1,4:6,9-dimethanodibenzofuran, and The Diels Alder adduct of hexachlorocyclopentadiene and (ar) tetrabromostryene.
These and similar halogenated organic compounds within the fore-going generic structural formula can be employed alone or in admixture with each other or the aforementioned C.O.D.

A HALOG N-CONTAINING BISPHENOL _ _ A mixture of 7.443 kg. of isophthaloyl chloride, 7.443 ky. of terephthaloyl chloride and 227 kg. of methylene chloride were charged under an atmosphere oF dry nitrogen to a 100 gallon glass lined Pfaudler reactor equipped with agitation means. In a 50 gallon glass lined Pfaudler reactor also equipped with agitation means and con-nected by a delivery tube to the previously described reactor, a mixture oF 29.91 kg. of 2,2-bis(4-hydroxy-3,5 dibromophenyl) propane, 2.17 kg. of 1,6-hexane diol and 136 kg. of methylene chloride under an atmosphere of dry nitrogen was agitated to dissolve the halogen-containing bisphenol in the methylene chloride solvent. A 2 gallon addition tank also connected by a delivery tube to the larger Pfaudler reactor was charged with 22.5 liters of triethylamine under ~124918 an atmosphere of dry nitrogen. The triethylamine and the bisphenol solution were added simultaneously over a period of 2 hours and 10 minutes to the mixture in the larger Pfaudler reactor, which was maintained at a temperature of about 13 to 19 under vigorous agitation. On completion of the addition of the bisphenol solution, the smaller PFaudler reactor was rinsed with 45.4 kg. of methylene chloride and the methylene chloride rinse was added to the mixture in the larger Pfaudler reactor. The agitation of the reaction mixture in the larger Pfaudler reaction vessel was continued for about 1~ hours.
About 2 liters of concentrated aqueous hydrochloric acid which had been diluted by addition of about 25 gallons of distilled water was then added to the reaction mixture in the larger Pfaudler reactor to terminate the esterification reaction. The resultant reaction mixture which consisted of a lower organic liquid phase containing the polyester product and an upper aqueous phase was removed from the reaction vessel and the layers thereof were separated. The recovered organic layer was washed clean of chloride anion with water.
The polyester product was recovered by drowning the washed organic layer gradually in about 50 gallons of vigorously agitated water at about 60 to 70 in a vessel equipped with a bottom outlet.
During the drowning operation the methylene chloride was flashed from the drowned mixture and the polyester precipitated as a white solid;
The product was withdrawn from the aforementioned bottom outlet as an aqueous slurry which was centrifuged to separate the water from the solid product. The product was dried with agitation in vacuo at about 100 for about 16 hours. The recovered polyester was obtained in a yield of about 90% of theory.
The resultant polyester product contains halo bisphenol hexane diol isophthalate and terephthalate residues in the molar propor-tions 0.75:0.25:0.5:0.5, has an intrinsic viscosity of 0.41, a glass transition temperature of 198-207, a weight average molecular weight of 60,200 and a number average molecular weight oF 21,400.

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By analysis the actual bromine content of the polyester product is 41.89,o (theoretical: 42.2//o).

About 324 parts of a bisphenol A-isophthalate polyester resin having an isophthalate:terephthalate ratio of 5.67 which was pre-pared substantially as described in Example l (A) was dried for about 4 hours at 120 and charged gradually to the Farrell Mill des-cribed in Example 2 which was operated with its front roll at 450 F.
and its back roll at 410 F. until fusion of the resin was completed and a band of clear resin formed on the front roll.
On completion of the addition of the halogen-free bisphenol polyester, 40 parts of the halogen-containing bisphenol polyester of Example 28 which had been dried for about 4 hours at 80 C. were gradually charged to the mill until fusion of the resin was completed and a band of clear resin formed on the front roll.
On completion of addition of the halogen-containing bisphenol polyester about 36 parts of the polyphenylene sulfide oF Example 2 were added to the mill.
The mixture of resins was milled for about 1.5 to 3 minutes and then sheeted from the mill. The milled resin blend was ground to granules of about 4 m.m. granule size as described in Example 2 which were then dried at about 120 for about 4 hours.
The dried resin blend granules were charged to an Arburg 221E/150 Injection molding machine operated at a barrel temperature of 590 F., a mold temperature of 250 F. and an injection pressure of about 25,000 psi to injection mold the resin blend into specimen bars of about 5 inch length, l/2 inch width and 1/16 inch thickness. Several of 1/16 inch thickness specimen were reserved for the flame retardant test described hereinbelow. The remainder of the l/16 inch thick specimen bars were dried at 120 for 2 hours and compression molded in a Carver four Paten Laboratory Press operated at 400-420 F. at a pressure of 30,000 to 35,000 psi to obtain specimen bars 5 inches in length, 1/2 inch in width and 1/32 inch in thickness.

~24918 The l/16 inch- and l/32 inch-thick bar specimens were evaluated in flame retardant properties according to the Vertical Burning Test described in "UL94-Standards For Safety", Underwriters Laboratories, Inc., Second Revised Edition, May 2, 1975, pages 6-8. In accordance with the evaluation technique of the aforementioned test, the speci-mens were rated V-O, V-l, or V-2 with V-O indicating the greatest degree of flame retardancy and V-2 indicating the poorest degree of flame retardance. The Oxygen Index of a sample of injected molded resin blend obtained from the Arburg Injection molding machine is also determined.
The results of these experiments are reported in Table 4 below.

The procedure of Example 29 was repeated substantially as des-cribed except that the amount of the halogen-free bisphenol polyester, the halogen containing bisphenol polyester and the polyphenylene sul-fide were 288 parts, 80 parts and 32 parts, respectively. The results of this Example are also presented in Table 4 below.

A glass fiber filled polyester-polyphenylene sulfide blend was prepared by charging 450 parts o-f the halogen-free bisphenol poly-ester of Example l (A), 55.6 parts of the halogen-containing bisphenol polyester of Example 28 and 50 parts of the polyphenylene sulfide oF
Example 2 to the Farrell Mill operated at the conditions described in Example 29. The addition and milling procedure used was sub-stantially that described in Example 29. The sheet of resin blendrecovered from the mill was ground to granules and dried substan-tially as described in Example 29.
The dried granules were mixed with 61.7 parts of chopped glass fiber (3/16 inch length, manufactured by Owens Corning Fiberglass Corporation under the designation 419AA). The resultant mixture was then added to an Arburg Alreounder 200 injection molding machine operated at a barrel temperature of 590 F., a mold temperature of 210-220 F., and an injection pressure of about 18,000 psi.

~124~18 The mixture was molded as bar specimens which were subsequently reground and dried substantially as described hereinabove to ensure that a homogeneous mixture of the glass fibers with the resin blend was obtained. The dried reground mixture was then charged to the Arburg 221E/150 Injection molding machine (operated at a barrel tem-perature of 580 F., at a mold temperature of 250 F., and an in-jection pressure of about 20,000 psi) and molded as 5 inch x l/2 inch x 1/16 inch specimen bars as described in Example 29. As in Example 29, a portion of the latter specimen bars were reserved for glame retardant testing and the remainder were compression molded to obtain 5 inch x l/2 inch x 1/32 inch bar specimens. Both the 1/16 inch and 1/32 inch bar samples were tested for flame retardance as described in Example 29. The Oxygen Index of the product was also determined as in Example 29. The results of this Example are reported in Table 4 below.

The procedure of Example 31 was repeated substantially as des-cribed except 63.0 parts of the glass filler was employed and ll parts of antimony trioxide were added to the resin mixture in the Farrell Mill following the addition of the polyphenylene sulfide. The re-sultant molded product was tested for flame retardance substantially as described in Example 29. The results of this Example are also presented in Table 4 below.

In these Examples there were prepared and tested for flame re-tardance compositions which were substantially comparable to those of Examples 29, 31, and 32 except that one or more of the constituents of the compositions described in the latter Examples were omitted.
Where glass fibers were present as a constituent in the compositions of the present Examples, the preparatory procedure of Example 31 was employed substantially as described. Where antimony trioxide was present as a constituent in the compositions of the present Examples, the antimony compound addition procedure of Example 32 was followed substantially as described. Where a glass constituent and an anti-mony additive were not employed, the compositions of the present Examples were prepared substantially as described in Example 29.
The results of these experiments are also presented in Table 4 below.

- ~124~18 _ In ~ I ~ N 1~
_ O . N N C~l t-_ Ltl ~ I N I , ~ > O C
_ In n I u~ ol o' ~ ~_ Cl 1n o W 01 01 D C
~0" 0,, tO . ~ O C

tr NO 00 O . O N E
. ~ t~ ~0 0~, ~, ll 0, O, _~ _O
C ~ O n N N r O

_ _ O ~ Ir> t N N :7~ ~ ~
d ; t~ t~ ~t ) UO~ ~ ~ V ~ o X _ , O~ N O L ~

V _ O . ~ ~ N ~ ~ L

t~ N O ~ O '~ O O O V V ~
x tO UO~ O O ~ ~ ~:1 L
~Oq t tO t ~ ~ ~ O O O ~O U C L

cn ~-- .a ~VI ICJ V D v O O N ~ tJ

L c. o ~ O c rO ~ .a tu ~ tu tu . t~ CJ ~:: ~ O
~ tO ~ L ,C cu c c~ v~. tu C ~ ~C . C ~ ' o c~
o _ ~ ~ ~ ~ _ _ _ !

', ~i 2~9~8 Of the Examples presented in foregoing Table 4, Control Examples 33, 36, 37, 43, 44 and 45 are identical to Control Examples 17, 19, 21, 25, 26 and 27, above, respectively (of the latter, Control Ex-amples 17, 19 and 21 are equivalent to the earlier Control Examples 11, 13 and 12, respectively, as noted on page 35). Control Examples 34 and 35 are equivalent to Control Examples 18 and 20 above, re-spectively, (which, in turn, are equivalent to the earlier illustra-tive Examples 8 and 7, respectively, as noted on page 35). The data of the earlier Examples 17, 18, 19, 20, 21, 25, 26 and 27 is pre-sented in Table 3 above while the data of the earlier Examples 7, 8, 11, 12 and 13 is presented in Table 2 above.
The invention has been described in the above specification and illustrated by reference to specific embodiments in the illustrative examples. However it is to be understood that these embodiments are not intended to limit the invention since, as illustrated, changes and modifications in the specific details disclosed hereinabove can be made without departing from the scope or spirit of the invention.

1~249~8 SUPPLEMENTARY DISCLOSURE
This disclosure and the Principal Disclosure are concerned with blends of polyphenylene sulfides and linear aromatic carboxylic polyesters.
Polyester molding compositionsof the invention have improved hydrolytic stability. In addition to enhanced resistance to hydrolytic degradation the blends of the latter application are characterized by excellent molding properties, i.e., the admixing of polyphenylene sulfide with the polyester improves the processability of the poly-ester, excellent tensile properties, excellent impact strength and excellent electrical properties such as volume resistivity, dielectric strength, dielectric constant, arc resistance and dissipation factors.
It has now been found that when a blend of the polyester and polyphenylene sulfide contains the con-stituents in particular proportions within the originally described ranges, the blend exhibits an unexpected, sub-stantial enhancement in an important electrical property, namely dielectric strength.
The invention particularly contemplates a thermo-plastic polymeric composition comprising, in admixture, (a) a linear aromatic polyester of components comprising a bis-phenol and a dicarboxylic acid, and (b) a polyphenylene sulfide present in a proportion of more than about 5 weight percent to less than about 60 weight percent based on the combined weight of said polyester and said polyphenylene sulfide with the proviso that when particulate glass filler -~ 7 llZ4918 is present in the composition, the proportion of said glass is sufficient to provide a weight ratio of poly-phenylene sulfide to the glass of at least about 1.5 to 1. The invention also contemplates molded articles formed from the composition.
As is illustrated by the data set forth in Tables 3, 4 and 5 below, these particular compositions, within the described class of the Principal Disclosure exhibit a substantial enhancement in dielectric strength.
The preferred aromatic polyesters of the invention, are prepared from bisphenols and at least one aromatic dicarboxylic acid, most preferably selected from the group consisting of isophthalic acid, tere-phthalic acid or mixtures thereof.

~ 5 i_ The preparation of polyphenylene sulfide is illustrated in U.S.
Patent 3,354,129, to Edmonds, Jr. et al., the disclosure of which is incorporated herein by reference, wherein at least one polyhalo-substituted cyclic compound is reacted with an alkali metal sulfide in a polar organic solvent reaction medium. Suitable polyphenylene sulfide compositions are ava;lable commercially under the trademark RYTON of the Phillips Petroleum Company, and include compositions I lo which are eithér unfilled, or filled with glass or some such con-ventional material. Preferably, the polyphenylene sulfide component has a melt flow index, measured at 600F. using a 5 Kg. weight and a standard orifice, within the range of from about 40 to about 7000.
The novel resin compositions of the invention are suitably pre-pared by blending the linear aromatic polyester with polyphenylene sulfide. The blending or mixing process can be performed us;ng conventional mixing equipment such as, for example, a~ anbury mixer, I mixing rolls, kneader, screw extruder, or injection molding machine.
! Although the mixing ratio may vary depending on the physical pro-erties desired in the resultant polymer blend, to achieve enhance-ment of dielectric strength according to the invention, the poly-! phenylene sulfide component is present in an amount of above about ¦ 5 weight percent to less than about 60 weight percent. Preferably, the polyphenylene sulfide component is present in an amount of about ¦ 25 7 to less than about 45 weight percent and especially in an amount I of about 8 to about 35 weight percent, the aforementioned proportions of polyphenylene sulfide being based on the combined weight of the polysulfide and the polyester present in the blend.

When the polyester of the blend is prepared by the afore-mentioned solution polymerization technique, i.e.
by reaction of a diacid halide of a dicarboxylic acid with a bisphenol, an especially good result is achieved in employing in the blend about 10 to about 30 weight per-cent of polyphenylene sulfide based on the combined weight of the polysulfide and the polyester.
When the polyester of the blend is prepared by the afore-mentioned preferred transesterification or melt polymerization technique an especially good result is achieved in accordance with the invention in employing about 8 to about 25 weight percent of polyphenylene sul-fide based on the combined weight of the polysulfide and the polyester.
The novel polymer compositions of the invention may also include various additives such as organic or inorganic fillers, stabilizers, antistatic agents and flame retardants.

D~

~249~3 Suitable halogen-containing flame retardant agents are described in the Principal Disclosure.
The additive-containing resin mixture of the invention may be prepared, if desired, by charging the polyester and sulfide polymer with the additive to a con-ventional mixing apparatus, such as a premix mixer, or melt extruder. The resultant additive-containing com-position can then be molded directly in an injection molding apparatus or an extruder. The molded articles thus formed have excellent hydrolytic stability and tensile strength.
The fillers which may be employed in the invention are preferably particulate fillers such as particulate glass (e.g. chopped glass fiber, glass rovings, glass microballoons or microspheres and pulverulent glass) particulate clay, talc, mica, inorganic natural fibers, synthetic organic fibers, alumina, graphite, silica, calcium ~Z4918 carbonate, carbon black, magnesia and the like. Generally such fillers are added to reinforce the structural integrity of a polymer, e.g. to inhibit sagging and/or to improve the tensile strength and stiffness of the polymer composition and also to reduce shrinkage, minimize crazing, lower material costs, impart color or opacity, and improve the surface finish of the polymer composition. No filler need be employed, but generally the amount of particulate filler employed in the compositions of the invention is in the range of about 5 to about 70 weight percent, preferably about 5 to about 40 weight percent and especially about 8 to about 30 weight percent based on the combined weight of the polyester and the phenylene sulfide polymer. The filler employed is preferably inorganic.
It is found that use as a filler of particulate glass, advanta-geously glass fibers, is desirable in the composition of the invention since the presence of the particulate glass filler further enhances the fire retardancy of polymer mixture of the invention.
The presence of the particulate glass component in the com-positions of the invention generally enhances the flame retardance of the polyester-sulfide polymer blend to the extent that excellent fire retardant performance is achieved even when the compositions are molded in extremely thin sections, (e.g. of thicknesses less than about l/16 of an inch). This excellent flame retardance performance makes the glass filled compositions of the invention especially suit-able for the fabrication of electrical components such as miniture circuit boards and the like.
While the use of particulate glass as filler in the blend of ¦ the invention is generally desirable for enhancing the fire retar-dancy of the blend, the use of particulate glass as filler generally lowers the dielectric strength of the present polymer mixture. How-ever it is found that when the proportion of the particulaté glass filler in the blend is sufficient to provide a weight ratio of particu1ete 91ass to polyphenylene sulfide ir the present blend of !

11~4'3~8 at least about 1.5 to 1 and preferably at least about 1.8 to 1, the dielectric strength of the blend is enhanced in accord with the invention.
The glass filling, especially glass fiber filling, employed in the invention preferably contains an organic coupling agent as very thin coating on the glass particles. The coupling agent forms an adhesive bridge between the glass and the polymer blend thereby enhancing the strength properties of the filled polymer blend.
Typically, organic coupling agents employed in the art include tran-sition metal complexes of unsaturated aliphatic acids such as meth-acrylate chromic chloride complex as well as various organic silane compounds including vinyl trichlorosilane, vinyl triethoxysilane, gamma amino-propyl triethoxysilane, ally trichlorosilane resorcinol, vinyltrimethoxysilane, amyltrimethoxysilane, phenyltriethoxysilane, ~-cyclohexylethyltrimethoxysilane, `n-methaacryloxypropyltrimethoxy-silane, ~-iodopropyltrimethoxysilane, ~-chloropropyltrimethoxysilane, ~-chloroisobutyltriethoxysilane,`n-glycidoxypropyltrimethoxysilane, N-~-aminoethyl-~-aminopropyltriethoxysilane, N-bis-(~-hydroxyethyl)-~-aminopropyltriethoxysilane, and ~-(3,4-epoxycyclohexylethyltri-methoxysilane.
Preferably the coupling agent employed with the glass filleraccording to the invention is a silane coupling agent.
Glass fillers are frequently manufactured and sold so as to contain the coupling agent as a proprietary ingredient on the surface of the glass. The coupling agents and their use with glass I fillers are discussed in more detail in W. V. Titow and B. J. Lanaham, ¦ "Reinforced Thermoplastics", Halstead Press, 1975, p. 83-88 and L.
- Mascia, "The Role of Additives in Plastics", J. Wiley & Sons, 1974, p. 89-91.

~D
.. .

` ~%49~8 It has also been found according to the invention that the presence of antimony additives (such as metallic antimony and com-pounds of ant;mony) is generally undesirable since the presence of the antimony constituent generally is detrimental to the flame re-tardance of the polymer m;xture as is illustrated in the examplesbelow.
Because of the enhanced dielectric strength achieved in the ~ blends of the invention, these blends are excellent electrical ; insulators, and as such, are particularly useful in manufacture of electrical apparatus.
The following examples further illustrate the var;ous aspects of the invention but are not intended to limit it. Various modifi-cations can be made in the invention without departing from the spirit and scope theréof. Where not otherwise specified in this specification and claims, temperatures are given in degrees centi-grade, and all parts and percentages are by weight.

q~24~18 In Examples 46 and 47, employing the blending and molding techniques described in the Principal Disclosure there were prepared blends of the polyphenylene sulfide of Example 2 (i.e. RYT0~ V-l (trademark), manu-factured by Phillips Petroleum Co.) and a bisphenol-A-isophthalate-terephthalate polyester having about a 1:1 molar ratio of isophthalic and terephthalic acid residues which was prepared by a solution polymerization technique similar to that described in Example lA. The proportions of the polyphenylene sulfide in the blends of Examples 46 and 47 were about 10 weight percent and about 20 weight per-cent, respectively, based on the combined weight of the sulfide polymer and the polyester.
In example 48, as a control, a sample of a bis-phenol-A-isophthalate-terephthalate polyester of about a 1:1 molar ratio of terephthalic and isophthalic acid residue which was also prepared by solution polymerization was molded under substantially the same condition employed in Examples 46 and 47.
Molded disc samples of about 1/8 inch thickness of the product of Examples 46, 47 and 48 were tested under the same conditions for short time dielectric strength, step by step dielectric strength (employing-the test methods for short time and step by step dielectric strength described in ASTM D-149); the volume resistivity, arc resistance, dielectric constant, and dissipation factor.

'i' "~' d .

, ~1~4918 _ 54 -The afore-mentioned electrical properties of the blends of Examples 46 and 47 and the polyester con-trol of Example 48 are compared in Table 3 below with the corresponding electrical properties of the polyphenylene sulfide employed in preparing these blends. The afore-mentioned dielectric strength of the latter polyphenylene sulfide, according to the manufacturer of the "RYTON"*
series of polyphenylene sulfides is substantially the same as the short time dielectric strength of a similar polyphenylene sulfide, RYTON R-6, as determined by sub-stantially the same testing method as that described above. The latter dielectric strength is given in the bulletin "Technical Information on RYTON Polyphenylene Sulfide Resins - 100 - Properties --- Processing`' of Phillips Petroleum Co., page 2, next to the last line.

trademark ..~ ~

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~ 49~8 _ 56 -In Examples 49-53 blends of the polyester of : Examples 46-48 and the polyphenylene sulfide of Examples 46-47 were prepared with various weight proportions of the proprietary particulate glass filler of Example 7 employing a blending and molding technique substantially similar to that described in Example 7.
The filled blends were tested for short time dielectric strength and the other electrical properties described in Examples 46-48 substantially as described in the latter Examples. The results of these tests are presented i~ Table 4 below.

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U') LS') QJ ~ O

LLI ¦ O C-- ~) I~ 0~ C~l t~ ~ O D ~ ~ ~ O O O
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7"'~

~1249~8 In Examples 54-57 the procedure of Examples 46-47 is repeated substantially as described in preparing and molding polyester-polyphenylene sulfide blends contain-ing 5%~ 10%~ 15% and 20% of the polyphenylene sulfide of Example 2 ~ based on the combined weight of the polyester and polyphenylene sulfide. As the polyester there was employed a bisphenol-isophthalate-terephthalate polyester having a molar ratio of isophthalate to terephthalate residues of about 75/25 which was prepared by a melt, i.e.
transesterification, polymerization procedure similar to that described in Example lB.
In Example 58 ~ as a control, a sample of the above-described melt polymerization prepared polyester which was employed in the foregoing blends was molded under substantially the same molding conditions as were employed in molding the blends of Examples 54-57.
The short time dielectric strength and other electrical properties were determined for the compositions of Examples 54-58 substantially in accord with the ~ro--cedure in Examples 46-471 except that the dielectric constant and dissipation factor were measured at lOHz instead of at 60 Hz as in Examples 46-47, These results are presented in Table 5 below.

~' llZ4918 _ 59 _ o u _, o o o~ ~ ,... . . . .

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~i~4918 Comparison of the short time dielectric strength data in Table 3 above indicates that the present blends of the polyphenylene sulfide and the polyester are characterized by an unexpected synergistic enhancement in short time dielectric strength compared to the poly-ester and the polyphenylene sulfide components. As illustrative ofsaid enhancement the blend of Example 46 containing 90.7% by volume of a polyester (comparable to a polyester of a short time dielectric strength of 391 volts/mil) and 9.3% by volume of a phenylene sulfide of a short time dielectric strength of 380 volts/mil would be expected to have a short time dielectric strength of 391 ~0.907~ + 380 (0.093)=
390 volts/mil. However as shown in Table 3 the actual or measured short time dielectric strength of the Example 46 is 613 volts/mil.
This is indicative that a substantial synergistic enhancement of the dielectric strength is achieved by blending the polyester and the polyphenylene sulfide in accordance with the invention.
By similar evaluation the blend of Example 47is calculated to have an expected dielectric strength of 389 volts/mil, whereas the data of Table 3 indicates the Example 47blend to have an actual short time dielectric strength of 560 volts/mil. This result also indicates a substantial synergistic enhancement in the aforementioned dielectric strength property.
Comparison of the short time dielectric strength data of the particulate glass filled blends of Table 4 with the corresponding data of Table 3 indicates that the addition of particulate glass, e.g. as a reinforcement filler, generally lowers the short time dielectric strenght of the polyester-polyphenylene sulfide blend.
However, the aforementioned substantial enhancement of the short time dielectric strength in accordance with the invention is achieved when the weight ratio of polyphenylene sulfide component to the particulate glass component in the blend is at least about 1.5:1, e.g. about 1.8:1 as in Example 51.

1~24~18 _ 61 -Evaluation of the short time dielectric strength data in Table

5 in accord with the procedure illustrated above for the Table 3 data indicates that an unexpected synergistic enhancement in the dielectric strength (corresponding to that described with respect to the blends of Table 3) also is achieved in blends of melt poly-merization-prep~red polyester and the polyphenylene sulfide which contain more than about 5 weight percent of the latter component.
For example, the blend of Example 56containing 86~ by volume of polyester of a short time dielectric strength of 468 volts/mil and 14 % by volume of the polyphenylene sulfide of a short time di-electric strength of 380 volts/mil would be expected to have a short time dielectric strength of 468 (0.86) + 380 (0.14) = 456 volts/
mil. However, as is seen from the Table 5 data, the measured short time dielectric strength is 579 volts/mil indicative of an unexpected synergistic enhancement in the aforementioned dielectric strength property.
It will be appreciated by those skilled in the art that pro-cedural modifications of the above-described experimental technique can be made without departing from the spirit and scope of the in-vention.
For example, in Example 7 a similar result providing a homo-geneous glass filler-resin mixture can be obtained without the necessity of regrinding the molded glass fiber-containing resin product. In this alternative procedure the Farrell-Mill resin product, after being ground to granules and dried, is added to the hopper end of a screw resin extruder ~such as a Haake Polytest 45*
single screw extruder or a ~erner Pfleider ZDS-K2~ twin screw ex-truder) while the particulate glass component is added downstream on the extruder. (Alternatively, the particulate glass can be mixed with the dried ground granules with the resultant mixture being added to the hopper end of the extruder). The resultant * trademark ~124918 extruder resin containing a homogeneous dispersion of the glass component is then sliced into pellets which are then injection molded as described in Examples 2 and 8.
Also, instead of separate addition of the particulate glass constituent as described in Example 7, the latter constituent can be homogeneously blended with the sulfide polymer constituent of the resin blend before the said sulfide polymer is added to the polyester.
In place of the chopped glass fiber employed in the above Examples, other forms of particulate glass filler agents such as ¦ 10 uncut glass strands, glass rovings, glass pellets, pulverulent glass, and glass micro-balloons can be used.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED IS DEFINED AS FOLLOWS:

A thermoplastic polymeric composition comprising, in admixture, (a) a linear aromatic polyester of components comprising a bisphenol and a dicarboxylic acid, and (b) polyphenylene sulfide.

The composition of Claim 1 wherein said dicarboxylic acid has the formula:

wherein Z is alkylene, -Ar- or -Ar-Y-Ar- where Ar is aromatic, Y is alkylene, haloalkylene, -O-, -S-, -SO2-, -SO3-, -CO-, or GN , wherein G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkyl-aryl, arylalkyl, haloarylalkyl, cycloalkyl or cyclohaloalkyl; and n is 0 or 1.

The composition of Claim 2 wherein said dicarboxylic acid is an aromatic dicarboxylic acid.

The composition of Claim 3 wherein said aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, terephthalic acid, and mixtures thereof.

The composition of Claim 1 wherein said bisphenol has the formula:

wherein Ar is aromatic, G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkylaryl, arylalkyl, haloarylalkyl, cycloalkyl, or cyclohaloalkyl; E is divalent alkylene, haloalkylene, cyclo-alkylene, halocycloalkylene, arylene, or haloarylene, -O-, -S-, -SO-, -SO2-, -SO3-, -CO-, or GN ? ; T and T' are independ-ently selected from the group consisting of halogen, G and OG; m is an integer from 0 to the number of replaceable hydrogen atoms on E;
b is an integer from 0 to the number of replaceable hydrogen atoms on Ar, and x is 0 or 1.

The composition of Claim 5 wherein the bisphenol is bisphenol-A.

The composition of Claim 1 wherein said linear aromatic poly-ester includes an aliphatic modifier.

The composition of Claim 7 wherein said aliphatic modifier is a glycol of 2 to 100 carbon atoms.

The composition of Claim 8 wherein said glycol is selected from the group consisting of neopentyl glycol, diethylene glycol, ethy-lene glycol, and mixtures thereof.

The composition of Claim 1 wherein said polyphenylene sulfide has a melt flow index in the range of from about 40 to about 7000.

The composition of Claim 1 wherein the aromatic polyester is prepared by a melt polymerization technique.

The composition of Claim 1 which also includes a filler material.

The composition of Claim 12 wherein said filler material is particulate glass.

The composition of Claim 13 wherein the filler material is glass fiber present in an amount of about 5 to about 70 weight percent based on the combined weight of the polyester and the phenylene sulfide polymer.

The composition of Claim 14 wherein the glass fiber contains an organic coupling agent.

The composition of Claim 15 wherein said organic couplic agent is a silane.

The composition of Claim 1 wherein said polyphenylene sulfide is present in an amount of from about 5 to about 95 parts by weight based on 100 parts by weight of admixture.

The composition of Claim 17 wherein said polyphenylene sul-fide is present in an amount of from about 5 to about 30 parts by weight based on 100 parts by weight of admixture.

A molded article formed from the composition of Claim 1.

The composition of Claim 1 wherein there is present an effective flame retardant proportion of a halogen-containing Diels Alder adduct of:

(A) a cyclopentadiene wherein all of the hydrogen atoms of the carbon atoms joined by carbon-to-carbon double bonds have been replaced by halogen, selected from the group consisting of fluorine, chlorine, and bromine, and (B) an ethylenically unsaturated organic compound containing one or two carbon-to-carbon double bonds;
the molar proportion of the cyclopentaidenyl residue to unsaturated compound residue in said adduct being 1:1 when the unsaturated com-pound contains one carbon-to-carbon double bond, and 2:1 when the unsaturated compound contains two carbon-to-carbon double bonds, said composition being substantially free of an antimony constituent.

The composition of Claim 20 wherein the halogen-containing adduct has the structural formula:

wherein X is selected From chlorine, bromine and fluorine, V is selected from chlorine, bromine, fluorine, alkyl of l to 10 carbon atoms, alkyloxy wherein the alkyl group contains 1 to 10 carbon atoms, haloalkyl and haloalkyloxy wherein the alkyl groups contain l to 10 carbon atoms and halo is chloro, bromo, or fluoro; Q is a tetravalent saturated cyclic radical having at least 4 carbon atoms which may be substituted by alkyl groups of l to 6 carbon atoms, chlorine, bromine or fluorine.

The composition of Claim 21 wherein the halogen containing adduct is present in an amount of about l to about 50 weight percent based on the combined weight of the polyester and sulfide polymer, and Q is a homocyclic ring of 5 to 18 carbon atoms.

The composition of Claim 22 wherein the halogen-containing adduct is present in an amount of about 2 to about 30 weight percent based on the combined weight of the polyester and the polyphenylene sulfide and Q is a monocyclic ring.

The composition of Claim 23 wherein Q is a ring of 5 to 10 carbon atoms, and X and V are chlorine.

The composition of Claim 24 wherein the halogen-containing adduct is present in an amount of about 3 to about 15 weight percent based on the combined weight of the polyester and the polyphenylene sulfide.

The composition of Claim 25 wherein the halogen-containing adduct is 1,2,3,4,7,8,9,10,13,13,14,14-dodecachloro-1,4,4a,5,6,6a, 7,10,10a,11,12,12a-dodecahydro-1,4:7,10-dimethanodibenzo [a,e]
cyclooctene.

The composition of Claim 20 which also includes a reinforcement effective amount of filler material.

The composition of Claim 27 wherein said filler material is particulate glass present in an amount of about 5 to about 70 weight percent based on the combined weight of the polyester and the poly-phenylene sulfide.

The composition of Claim 28 wherein said particulate glass filler is glass fiber present in an amount of about 5 to about 40 weight percent based on the combined weight of the polyester and the polyphenylene sulfide.

A flame retardant composition according to Claim 20 comprising in admixture a linear bisphenol A-isophthalate-terephthalate poly-ester wherein the ratio of isophthalate and terephthalate groups is from about 75:25 to about 90:10, about 5 to about 30 weight percent of polyphenylene sulfide based on the combined weight of the polyes-ter and the polyphenylene sulfide about 2 to about 30 weight percent based on the combined weight of the polyester and the polyphenylene sulfide of 1,2,3,4,7,8,9,10,,13,13,14-dodecahalo-1,4,4a,5,6,5a,7, 10,10a,11,12,12a-dodecahydro-1,4:7,10-dimethanodibenzo-[a,e] cyclo-octene, the halo substituent being selected from the group consist-ing of chlorine and bromine and the composition being substantially free of an antimony constituent.

The composition of Claim 30 wherein the halo substituent is chlorine.

The composition of Claim 30 which also includes about 10 to about 40 weight percent of glass fibers based on the combined weight of the polyester and the polyphenylene sulfide.

The composition of Claim 32 wherein the halo-substituent is chlorine.

A thermoplastic polymeric composition according to Claim 1 wherein the bisphenol component comprises both a bisphenol wherein at least one carbon atom is substituted with halogen, and a bis-phenol devoid of said halogen, said halogen-containing bisphenol being present in the amount of about 1 to less than about 50 mole percent based on the total bisphenol component.

The composition of Claim 34 which comprises a mixture of poly-esters comprising:
A) a polyester of said bisphenol devoid of halogen, and B) a polyester of said halogen-containing bisphenol, said halogen-containing bisphenol polyester being present in an amount of from about 3 to about 40 weight percent based on the com-bined weight of the polyesters and the polyphenylene sulfide.

The composition of Claim 35 wherein the dicarboxylic acid is an aromatic dicarboxylic acid, and said halogen-containing bisphenol contains up to 20 halogen substituents and is present in an amount of about 5 to about 20 weight percent based on the weight of the polyesters and the sulfide polymer.

The composition of Claim 36 wherein said bisphenol devoid of halogen has the formula:

wherein Ar is aromatic, G is alkyl, aryl, alkylaryl, arylalkyl, or cycloalkyl; E is divalent alkylene, alkylene, cycloalkylene, or arylene, -O-, -S-, -SO-, -SO2-, -SO3-, -CO-, ; T and T' are independently selected from the group consisting of G and OG;
m is an integer from O to the number of replaceable hydrogen atoms on E; b is an integer from O to the number of replaceable hydrogen atoms on Ar, and x is O or 1, and said halogen-containing bisphenol has the formula:

wherein G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, halo-alkylaryl, arylalkyl, haloarylalkyl, cycloalkyl, or halocycloalkyl;
E is divalent alkylene, haloalkylene, cycloalkylene, halocyclo-alkylene, arylene, or haloarylene, -O-, -S-, -SO-, -SO2-, -SO3-, -CO-, or ; T and T' are independently selected from the group consisting of halogen, G and OG; and Ar, x, m, and b have the aforementioned meanings.

The composition of Claim 37 wherein the halogen-containing bis-phenol contains up to 8 halogen substituents on different carbon atoms of said bisphenol.

The composition of Claim 38 wherein the halogen is chlorine or bromine with at least one of T and T' being halogen.

The composition of Claim 39 wherein said linear aromatic poly-ester of the halogen-containing bisphenol includes an aliphatic modifier and all of the halogen substituents are present as T and T'.

The composition of Claim 40 wherein said aliphatic modifier is a glycol, of 2 to about 100 carbon atoms.

The composition of Claim 41 wherein said glycol is selected from the group consisting of neopentyl glycol, diethylene glycol, 1,6-hexane diol ethylene glycol, and mixtures thereof.

The composition of Claim 42, wherein the bisphenol devoid of halogen is bisphenol A, T and T' in the halogen-containing bisphenol are bromine and the aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, terephthalic acid and mixtures thereof.

The composition of Claim 43 wherein the halogen-containing bis-phenol is 2,2-bis-(4-hydroxy-3,5-dibromophenyl) propane, the dicar-boxylic acid is a mixture of isophthalic and terephthalic acids and the polyphenylene sulfide is present in an amount of about 5 to about 30 weight percent based on the weight of the polyesters and the poly-phenylene sulfide.

The composition of Claim 34 wherein an antimony component is substantially absent.

CLAIMS SUPPORTED BY SUPPLEMENTARY DISCLOSURE

46. A thermoplastic polymeric composition comprising, in admixture, (a) a linear aromatic polyester of components comprising a-bisphenol and a dicarboxylic acid, (b) polyphenylene sulfide present in a pro-portion of more than about 5 weight percent to less than about 60 weight percent, and (c) O to about 70 weight percent of particulate glass filler, said proportions being based on the combined weight of the polyphenylene sulfide and the polyester with the proviso that when particulate glass is present in the composition, the weight ratio of the polyphenylene sulfide to the glass is at least about 1.5:1.

47. The composition of Claim4~ wherein said dicarboxylic acid has the formula:

wherein Z is alkylene, -Ar- or -Ar-Y-Ar- where Ar is aromatic, Y is alkylene, haloalkylene, -O-, -S-, -SO2-, -SO3-, -CO-, or , wherein G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkylaryl, arylalkyl, haloarylalkyl, cycloalkyl or cyclohalo-alkyl; and n is 0 or 1.

48. The composit;on of Claim47 wherein said dicarboxylic acid is an aromatic dicarboxylic acid.

49. The composition of Claim48 wherein said aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, tere-phthalic acid, and mixtures thereof.

50. The composition of Claim 46 wherein said bisphenol has the formula:
wherein Ar is aromatic, G is alkyl, haloalkyl, aryl, haloaryl, alkylaryl, haloalkylaryl, arylalkyl, haloarylalkyl, cycloalkyl, or cyclohaloalkyl, E is a divalent alkylene, haloalkylene, cycloalkylene, halocycloalkylene, arylene, or haloarylene, -O-, -S-, -SO2-, -SO3-, -CO-, , or ; T and T' are indepen-dently selected from the group consisting of halogen, G and OG;
m is an integer from 0 to the number of replaceable hydrogen atoms on Ar, and x is 0 or 1.

51. The composition of Claim 50 wherein the bisphenol is bisphenol-A.

52. The composition of Claim 46 wherein said linear aromatic polyester includes an aliphatic modifier.

53. The composition of Claim 52 wherein said aliphatic modifier is a glycol of 2 to 100 carbon atoms.

54. The composition of Claim 53 wherein said glycol is selected from the group consisting of neopentyl glycol, diethylene glycol, ethylene glycol, and mixtures thereof.

55. The composition of Claim 46 wherein said polyphenylene sulfide has a melt flow index in the range of from about 40 to about 7000.

56. The composition of Claim 46 wherein the aromatic polyester is prepared by a melt polymerization technique.

57. The composition of Claim46 wherein the aromatic polyester is prepared by a solution polymerization technique.

58. The composition of Claim46 which also includes a filler material.

59. The composition of Claim 58 wherein said filler material is particulate glass.

60. The composition of Claim 59 wherein the filler material is glass fiber present in an amount of about 5 to about 70 weight percent based on the combined weight of the polyester and the polyphenylene sulfide.

61. The composition of Claim 60 wherein the glass fiber contains an organic coupling agent.

62. The composition of Claim 61 wherein said organic couplic agent is a silane.

63. The composition of Claim 56 wherein said polyphenylene sulfide is present in an amount of from about 8 to about 25 weight percent based on the combined weight of the polyphenylene sulfide and the polyester and the weight ratio of the polyphenylene sulfide to the glass is at least about 1.8:1.

64. The composition of Claim 57 wherein said polyphenylene sulfide is present in an amount of from about 10 to about 30 weight percent based on the combined weight of the polyphenylene sulfide and the polyester and the weight ratio of the polyphenylene sulfide to the glass is at least about 1.8:1.

65. A molded article formed from the composition of Claim 46.

66. A molded article formed from the composition of Claim 56.

67. A molded article formed from the composition of Claim 57.

68. A molded article formed from the composition of Claim 59.