JPS638144B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is characterized in that the carboxylic acid component can be an aromatic dicarboxylic acid or an aliphatic saturated dicarboxylic acid, such as oxalic acid or adipic acid; Regarding blending. Linear aromatic polyesters made from aromatic dicarboxylic acids and bisphenols are well known because of their suitability for molding, extrusion, casting and film forming. For example, U.S. Pat. No. 3,216,970 to Conix describes linear aromatic polyesters made from isophthalic acid, terephthalic acid, and bisphenolic compounds. Such high molecular weight compositions are known to be useful in the production of various films and fibers. Additionally, these compositions, when formed into useful articles using conventional methods, provide superior properties over articles formed from other linear polyester compositions. For example, aromatic polyesters are known to have various useful properties such as good tensile strength, impact strength and flexural strength, high heat distortion and pyrolysis temperatures, resistance to ultraviolet light and good electrical properties. It is being Aromatic polyesters which are particularly well suited for molding purposes can also be made by reacting organic diacid halides with difunctional aliphatic reactive modifiers such as glycols and subsequently reacting this product with bisphenol compounds. . The polyester formed has a reduced melt viscosity and a reduced melting point, which is achieved at temperatures within the operating limits of conventional molding equipment (i.e., approximately
It enables molding at temperatures below 300℃. Glycol modified polyesters of this type are more fully described in U.S. Pat. No. 3,471,441 to Hindersinn. In order to successfully make molding resins on an economic scale, the polymer should have the ability to be conveniently molded without significant deterioration of physical properties. In this regard, although the aromatic polyesters mentioned above generally exhibit excellent physical and chemical properties, their susceptibility to hydrolytic degradation at high temperatures poses an inherent complication. This sensitivity to the combined effects of heat and moisture has also been demonstrated in commercially available polycarbonate resins, as evidenced by the desirability of reducing the moisture content of the resin to below about 0.05% prior to molding. There is. Unfortunately, however, aromatic polyester resins often exhibit a stronger tendency to deteriorate and become brittle more rapidly than polycarbonate resins. This is evidenced by the loss of tensile strength that can occur when aromatic polyesters are molded and then immersed in boiling water. This trend can be explained in part by the hydrolysis of ester bonds under these conditions. In any case, it should be recognized that sensitivity to moisture is a major problem for aromatic polyester resins which severely limits their usefulness in applications such as at high temperatures in humid atmospheres or in autoclaves. The main object of the present invention is therefore to make aromatic polyester compositions which have not only excellent physical and chemical properties but also improved flame retardancy and hydrolytic stability, and which have enhanced dielectric properties. be. The inventors herein have disclosed a polyester molding composition having improved flame retardancy and hydrolytic stability and enhanced dielectric properties by blending a linear aromatic polyester with polyphenylene sulfide. I discovered that I could make things. Preferred aromatic polyesters of the present invention are made from bisphenols and at least one aromatic dicarboxylic acid, most preferably selected from the group consisting of isophthalic acid, terephthalic acid or mixtures thereof. The linear aromatic polyester of the present invention consists of a diacid halide of a dicarboxylic acid dissolved in an organic liquid that is the solvent for the polyester to be formed, and a bisphenol dissolved in a liquid that is immiscible with the solvent for the diacid halide. can be made by condensation with metal phenolates. This method is fully described in Konics US Pat. No. 3,216,970, which is hereby incorporated by reference. The bisphenols that can be used in this method are known to those skilled in the art and correspond to the general formula below. In the formula, Ar is preferably an aromatic group containing 8 to 16 carbon atoms (including phenyl group, biphenyl group and naphthyl group), and G is an alkyl group, haloalkyl group, aryl group, haloaryl group, alkylaryl group. , a haloalkylaryl group, an arylalkyl group, a haloarylalkyl group, a cycloalkyl group, or a halocycloalkyl group, and E is a divalent (or disubstituted) alkylene group, a haloalkylene group, a cycloalkylene group, a halocycloalkylene group, Arylene group or haloarylene group, -O-, -S-, -SO-, -SO ₂ -,
―SO ₃ ―, ―CO―,

[Formula] or GN<, T and T' are each independently selected from the group consisting of halogen (e.g., chlorine or bromine), G, and OG, and m is from 0 to the number of substitutable hydrogen atoms on E. , b is an integer from 0 to the number of substitutable hydrogen atoms on Ar, and x is 0
or 1. When there is more than one G substituent in the bisphenol, such substituents may be the same or different. The T and T' substituents can be in the ortho, meta or para position to the hydroxyl group. Preferably, the hydrocarbon radicals mentioned above have the following carbon atoms: 1 to 14 carbon atoms.
alkyl groups, haloalkyl groups, alkylene groups and haloalkylene groups; aryl groups, haloaryl groups, arylene groups and haloarylene groups having 6 to 14 carbon atoms; alkylaryl groups, haloalkylaryl groups, aryl having 7 to 14 carbon atoms; Alkyl groups and haloarylalkyl groups; and cycloalkyl groups, halocycloalkyl groups, cycloalkylene groups and halocycloalkylene groups having 4 to 14 carbon atoms. Furthermore, mixtures of the bisphenols mentioned above may be used in order to obtain polymers with particularly desired properties. Bisphenols generally contain from 12 to about 30 carbon atoms, preferably from 12 to about 25 carbon atoms. Representative examples of bisphenols having the above general formula include bis-(4-hydroxyphenyl)-methane, bis-(2-hydroxyphenyl)-methane, and (4-hydroxyphenyl-,2-hydroxyphenyl). bis-(4-hydroxy-3,5-dichlorophenyl)-methane; bis-(4-hydroxy-3,5-dichlorophenyl)-methane;
-dibromophenyl)-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)-phenylmethane, bis-(4-hydroxyphenyl)-diphenylmethane, bis-(4-hydroxyphenyl)-4 '-Methylphenylmethane, bis-(4-hydroxyphenyl)-4'-chlorophenylmethane, bis-(4-hydroxyphenyl)
-2,2,2-trichloro-1,1,2-ethane, bis-(4-hydroxyphenyl)-1,1
-Cyclohexane, bis-(4-hydroxyphenyl)-cyclohexylmethane, 4,4-dihydroxyphenyl, 2,2'-dihydroxydiphenyl, dihydroxynaphthalene, 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-methylphenyl)-1,1-butane, bis-(2-hydroxy-4-t-butylphenyl)-2,2-propane, bis-(4-hydroxy phenyl)-1-phenyl-1,1-ethane,
4,4'-dihydroxy-3-methyldiphenyl-
2,2-propane, 4-4'dihydroxy-3-methyl-3'-isopropyldiphenyl-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-hydroxyphenyl)-sulfonate, bis-(4-hydroxyphenyl)-amine, bis-(4-hydroxyphenyl)-phenylphosphine oxide, 2,2
-Bis-(3-chloro-4-hydroxyphenyl)-propane, 4,4'-(cyclomethylene)-
Bis-(2,6-dichlorophenol), 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)-1-phenylethane, 2,
2-bis-(3,5-dibromo-4-hydroxyphenyl)-hexane, 4-4'-dihydroxy-
3,3',5,5'-tetrachlorodiphenyl, 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, tetrachlorodiphenylsulfone, bis-(3,5-dibromo-4-
hydroxyphenyl)-phenylphosphine oxide, bis-(3,5-dibromo-4-hydroxyphenyl)-sulfoxide, bis-(3,
5-dibromo-4-hydroxyphenyl)-sulfone, bis-(3,5-dibromo-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'-octachloro-4,4'-hydroxybiphenyl. Typical biphenols are o,o'-biphenol; m,
m'-biphenol;p,p'-biphenol; bicresol e.g. 4,4'-bi-o-cresol,
6,6'-G-o-cresol, 4,4'-B-m-
Cresol; dibenzylbiphenol e.g. a,
a′-diphenol-4,4′-bi-o-cresol; diethylbiphenol such as 2,2′-diethyl-p,p′-biphenol and 5,5′-diethyl-o,o′-biphenol; Phenols such as 5,5'-dipropyl-o,o'-biphenol and 2,2'-diisopropyl-p,p'-
Biphenol; diallyl biphenol e.g. 2,
2'-diallyl-p,p'-biphenol; and dihalobiphenol such as 4,4'-dibromo-o,
o′-biphenol. Mixtures of the biphenol isomers mentioned above can be used. Dicarboxylic acids useful in this method are also well known and are represented by the general formula below. In the formula, X is oxygen or sulfur, Z is an alkylene group, -Ar- or -Ar-Y-Ar-,
Ar has the same definition as above for bisphenol, Y is an alkylene group having 1 to 10 carbon atoms, a haloalkylene group, -o-, -s-, -SO
―, ―SO ₂ ―, ―SO ₃ ―, ―CO―,

[Formula] 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-carboxyphenyl)-sulfone, bis-
(4-carboxyphenyl)-carbonyl, bis-(4-carboxyphenyl)-methane, bis-
(4-carboxyphenyl)-dichloromethane,
1,2- and 1,1-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-carboxyphenyl)-1,1-dimethylpropane, 1,1- and 2,2 -bis-(4-carboxyphenyl)-butane, 1,1- and 2,2
-Bis-(4-carboxyphenyl)-pentane, 3,3-bis-(4-carboxyphenyl)
-heptane, 2,2-bis-(4-carboxyphenyl)-heptane; and aliphatic acids such as oxalic acid, adipic acid, succinic acid, malonic acid, sebacic acid, glutaric acid, azelaic acid, suberic acid, and the like. Isophthalic acid and terephthalic acid are preferred because they are easily available and inexpensive.
The most preferred dicarboxylic acid component consists of a mixture of about 75 to about 100 mole percent isophthalic acid and about 25 to about 0 mole percent terephthalic acid. When the dicarboxylic acid used in making the polyester of the present invention comprises both isophthalic acid and terephthalic acid according to a particularly preferred embodiment of the present invention, the dicarboxylic acid used in the polyester is in the range of about 75:25 to about 90:10. gives particularly satisfactory results when the weight ratio of isophthalic acid residues to terephthalic acid residues is . Another method for making suitable aromatic polyesters is described in U.S. Pat. No. 3,471,441 to Hindershin et al., the disclosure of which is incorporated herein by reference. It involves the homogeneous reaction of a glycol containing from 2 to about 100 carbon atoms with a diacid halide of a dicarboxylic acid, followed by interfacial polymerization of the formed prepolymer with a bisphenol. Compositions made in this manner have an aliphatic modifier, i.e., a glycol, introduced into the structure of the bisphenol and diacid halide reaction product, resulting in high impact strength, high modulus, and improved formability. and has excellent mechanical properties such as a high softening point. The bisphenol and dicarboxylic acid components and manufacturing methods that can be used in the Hindershin et al. patent correspond to those described above. Aliphatic modifiers are reactive difunctional components that can be represented by the general formula below. HnD-A-D'Hn In the formula, D and D' are each independently selected from the group consisting of O, S and N, and A is an alkylene group,
A tertiary carbon selected from the group consisting of a cycloalkylene group, an arylalkylene group, an alkyleneoxyalkyl group, a poly(alkyleneoxy)alkyl group, an alkylene-carboxyalkylene-carboxyalkyl group, and a poly(alkylene-carboxyalkylene-carboxy)alkyl group. It is a divalent or disubstituted aliphatic group containing no atoms, n is an integer of 1 or 2, and when D and D' are N, n is 2. Representative examples of aliphatic modifiers having the above general formula include ethylene glycol, diethylene glycol, neopentyl glycol,
1,4-cyclohexanedimethanol, 1,4-
Butanedithiol, dipropylene glycol, polypropylene glycol, 1,1-isopropylidene-bis-(p-phenyleneoxy)-di-2
-Ethanol, 2,2,4,4-tetramethyl-
1,3-cyclobutanediol, bis-(4-hydroxycyclohexane)-2,2-propane,
Di-(hydroxyethyl)-adipate, Di-
(hydroxypropyl)-glutarate, di-
(hydroxyethyl)-poly(ethylene glycol)-adipate, ethanedithiol, ethanolamine, methylethanolamine, hexamethylenediamine, 1,3-propanediol, 2-
Contains mercaptoethanol and 2-aminopropanediol. Combinations of the aliphatic modifiers mentioned above may also be used, usually to obtain particular properties. Solution methods such as those described in U.S. Pat. Nos. 4,051,107 and 4,051,106, which are incorporated herein by reference, may also be used to prepare suitable aromatic polyesters. The polyester component of the present invention is produced as a melt polymerization involving transesterification, i.e., a transesterification reaction between a diphenolic reactant and a diaryl ester of a dicarboxylic acid, carried out in the melt form (i.e., without the use of reaction solvents or diluents). Preferably, it is made by known methods. Such a method is described in British Patent No. 924607 of Imperial Chemical Industries Limited, which is incorporated herein by reference. Another melt polymerization process that may be used to make linear aromatic polyesters suitable for use in the present invention is disclosed in U.S. Patent Application No. 542,635, filed January 20, 1975.
No. 818,493, filed July 25, 1977 as a continuation-in-part application of No. The process basically consists of first mixing bisphenols, diaryl esters of dicarboxylic acids and diols and then reacting the mixture formed in the presence of a transesterification catalyst. The contents of this specification are hereby incorporated by reference. The polyphenylene sulfide component of the present invention has the following general formula: It is a crystalline polymer having a repeating structural unit containing a p-substituted benzene ring and a sulfur atom, which can be represented by the formula (where n has a valence of at least about 100). The preparation of polyphenylene sulfide is shown in U.S. Pat. No. 3,354,129 to Edmonds Jr. et al. At least one type of polyhalo-substituted cyclic compound is reacted with an alkali metal sulfide. Suitable polyphenylene sulfide compositions are commercially available from Philips Petroleum Company under the trade name RYTON, which are unfilled or filled compositions with glass or such conventional materials. Preferred polyphenylene sulfide components have a melt flow index of about 40 to about 7000, measured at 600ⓓ using a standard orifice and a 5 kg weight. The novel resin compositions of this invention are made by mixing linear aromatic polyesters with polyphenylene sulfide. The mixing process can be carried out using conventional mixing equipment such as Banbury mixers, mixing rolls, kneaders, screw extruders or injection molding machines. Although the mixing ratio may vary depending on the desired physical properties of the polymer blend formed, the polyphenylene sulfide component is preferably present in an amount of about 5 to 95 parts by weight of the mixed polymer; Most preferably it is present in an amount of about 5 to about 30 parts by weight. The novel polymer compositions of the present invention may also contain various additives such as organic or inorganic fillers, stabilizers, antistatic agents and flame retardants. According to a particular embodiment of the invention, the novel polymer composition of the invention comprises a halogen-containing Dales
Contains effective flame retardant percentage of alder adduct.
This Dales Alder adduct is (A) carbon-
Cyclopentadiene in which all of the hydrogen atoms of the carbon atoms bonded to carbon double bonds are replaced with halogens such as fluorine, chlorine or bromine; and (B) ethylenic non-carbon compounds containing one or two carbon-carbon double bonds. The molar ratio of cyclopentadienyl residue to unsaturated compound residue in the adduct is 1:1 when the unsaturated compound contains one carbon-carbon double bond; 2:1 when the saturated compound contains two carbon-carbon double bonds
It is. The Diels-Alder adduct used as a flame retardant according to the invention is preferably derived from a cyclic compound having two endocyclic carbon-carbon double bonds and has the following structural formula: In the formula, X is selected from chlorine, bromine and fluorine, and V
is selected from chlorine, bromine, fluorine, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group in which the alkyl group has 1 to 10 carbon atoms, a haloalkyl group and haloalkyloxy group in which the alkyl group has 1 to 10 carbon atoms. , Q is a tetravalent saturated cyclic group having at least 4 carbon atoms;
Optionally substituted with ~6 alkyl groups, chlorine, bromine or fluorine. Preferably, the alkyl and alkoxy groups have 1 to 6 carbon atoms. Q
is preferably a tetravalent isocyclic group having 5 to 18 carbon atoms or a tetravalent heterocyclic group having 4 to 18 carbon atoms, and preferably has 1 to 5 cyclic structures.
When Q has multiple ring structures, they have shared carbon atoms. In particularly preferred halogen-containing flame retardants of the invention, Q is an allocyclic group, more preferably an allocyclic monocyclic group, especially an allotropic monocyclic group containing only hydrogen substituents. . Particularly preferred adducts of the invention are those in which Q does not have more than 10 carbon atoms. The flame retardant additives of the present invention include halogenated cyclopentadiene and open chain unsaturated compounds (e.g. altetrabromostyrene), diunsaturated homocycloaliphatic compounds (e.g. 1,5-cyclooctadiene,
cyclopentadiene, 1,4-cyclohexadiene, bicyclo(2,2,1)heptadiene and 1,2,3-trichloro-1,4-cyclohexadiene) or containing divalent sulfur or oxygen as a heterocyclic atom constituent It is a known compound made by the Diels-Alder reaction of diunsaturated heterocycloaliphatic compounds (eg furan or thiophene). Also suitable as heterocyclic reactants are monoalkyl or dialkyl derivatives of furan or thiophene in which one or both of the carbon atoms attached to the heterocyclic atoms contain an alkyl substituent of 1 to 6 carbon atoms, such as 1-methylfuran, 1-hexylfuran, 1,4-dipropylfuran, 1-methylthiophene, 1,4-dihexylthiophene, etc. can be used. Examples of halogenated cyclopentadiene compounds suitable for making flame retardant additives include hexachlorocyclopentadiene, 5,5-dimethoxytetrachlorocyclopentadiene, hexabromocyclopentadiene, 5,5-difluorotetrachlorocyclopentadiene, These include 5,5-dibromotetrachlorocyclopentadiene and 5,5-diethoxytetrachlorocyclopentadiene. Representative examples of the above-described Dales-Alder adducts that may be used in the practice of the present invention include the following. 1, 2, 2, 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; 1, 2, 3, 4, 6, 7, 8, 9, 13, 13,
14,14-dodecachloro-1,4:5,10:6,9
-Trimethano 11H-benzo[b]-fluorene; 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 11
-Dodecachloro-1,4:5,8-dimethanofluorene; 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-dodecachloro-1,4,4a,5,8,
8a, 9, 9a, 10, 10a-Decahydro 1, 4,
5,8-dimethanoanthracene; 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-dimethanodibenzothiophene; 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 adatato may also be used. The production of the above-mentioned known halogen-containing Dales-Alder adduct is described in particular in US Pat. No. 3,711,563.
Patent specifications (particularly in column 8), Patent specifications No. 3923728, Specification No. 4000114, Specification No. 3535253, and Specification No. 3687983 are hereby incorporated by reference. Cited as a reference. The proportion of halogen-containing flame retardant adduct compound used in accordance with the present invention is generally from about 1 to about 50% by weight, preferably from about 2 to about 30% by weight, based on the combined weight of polyester and polyphenylene sulfide.
It is. Particularly good results are obtained using from about 3 to about 15 weight percent of the halogen-containing adduct, based on the combined weight of the polyester and sulfide polymer components. According to another embodiment of the invention, the flame retardancy of the polyester-polyphenylene sulfide mixtures of the invention is determined by the fact that the bisphenol reactive component used to make the polyester has at least one carbon atom substituted with a halogen. From about 1 to about 50 mole percent of the bisphenol used is enhanced when the remainder of the bisphenol reaction components are bisphenols containing no halogen substituents. The halogen-containing bisphenol of the present invention corresponds to the above general formula defining the bisphenol used in producing the polyester of the present invention. According to a preferred embodiment of the invention, the halogen substituent is chlorine or bromine. Preferably, the halogen-substituted bisphenols contain 1 to 20, more preferably 2 to 8, especially 4 halogen substituents. Preferably, at least one of T and T' in the general formula of bisphenol mentioned above is halogen. In particularly preferred embodiments 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 present invention that does not contain a halogen substituent corresponds to the general formula described above (the bisphenol of the present invention is broadly defined and described above), in which G is an alkyl group, an aryl group,
an alkylaryl group, an arylalkyl group, or a cycloalkyl group, and E is a divalent alkylene group, a cycloalkylene group, or an arylene group;
-o-, -S-, -SO-, -SO ₂ -, -SO ₃ -,
-CO-,

[Formula] or GN<, and T and T' are each independently selected from the group consisting of G and OG (Ar, m, b and x are as described above), and a halogen-substituted bisphenol and Although the halogen-free bisphenol residues may be present in the same polyester component of the blend of the invention, the halogen-containing bisphenol residues and the halogen-free bisphenol residues may be present in different polyester-sulfide polymer mixtures. Preferably present in the polyester component, ie, the polyester component of the blend comprises (A) a polyester of the above halogen-containing bisphenols, and (B) a polyester of the above bisphenols free of halogen substituents. In accordance with the preferred embodiments described above, when a mixture of the polyesters described above is used, the halogen-containing bisphenol polyester is generally selected based on the total weight of the total polyester and polyphenylene sulfide of the polymer blend of the present invention. It is present in an amount of about 3 to about 40% by weight, especially about 5 to about 20% by weight. In the mixture of polyesters preferably used as the polyester component of the invention, either or both the halogen-containing bisphenol polyester and the halogen-free polyester may contain residues of aliphatic hydroxy compounds as modified constituents. . However, according to a particularly preferred embodiment of the invention, the halogen-containing bisphenol polyester component of the mixture contains the aliphatic modifier, while the halogen-free bisphenol polyester component does not contain the aliphatic modifier. . The halogen-substituted bisphenols in the halogen-containing Diels-Alder adducts and/or linear aromatic polyesters described above according to the present invention can be used in polyester-sulfide polymer blends without deleterious effects on other desirable properties of these compositions. greatly enhances the flame retardancy of
Cut this composition into extremely thin sections (e.g. about 16 minutes).
Flame retardancy is enhanced such that excellent flame retardant performance is achieved even when molded to thicknesses of less than 1 inch). This excellent flame retardant performance makes the compositions of the invention particularly suitable for molding electrical components such as miniature circuit boards and the like. The additive-containing resin mixture of the present invention can be made, if desired, by charging the polyester and sulfide polymer with the additives into conventional mixing equipment, such as a premix mixer or a melt extruder. The formed additive-containing composition can then be molded directly in an injection molding device or extruder. The molded articles thus formed have excellent flame retardancy, hydrolytic stability and tensile strength, and have enhanced dielectric properties. Fillers that can be used in the present invention include granular fillers such as granular glass (e.g. cut glass fibers,
glass lobing, glass globules and powder glass),
Particulate clay, talc, mica, inorganic natural fibers, alumina, graphite, silica, calcium carbonate, carbon black, magnesia and the like are preferred. Generally, such fillers are used to enhance the structural integrity of the polymer, such as to prevent sag and/or improve tensile strength and stiffness of the polymer composition, and to reduce shrinkage and prevent cracking. It is added to minimize, lower material costs, provide color or opacity, and improve the surface finish of the polymeric composition. Generally, the amount of particulate filler used in the compositions of the present invention will be from about 5% to about 70%, preferably from about 5% to about 40%, especially from about 5% to about 40% by weight, based on the weight of the polyester and polyphenylene sulfide polymer. It ranges from about 8 to about 30% by weight. The filler used is preferably inorganic. According to the invention, it has been found that the use of granular glass, preferably glass fibers, as filler is particularly preferred, since the presence of granular glass fibers further enhances the flame retardancy of the polymer mixtures according to the invention. The presence of particulate glass components in the compositions of the present invention allows the composition to be divided into extremely thin sections (e.g. about 16
Enhances the flame retardancy of polyester-sulfide polymer blends such that excellent flame retardant performance is achieved even when molded (to thicknesses of less than 1 inch). This excellent thermal flammability makes the glass-filled compositions of this invention particularly suitable for forming electrical components such as miniature circuits. The glass filler, especially the glass fiber filler, used in the present invention preferably contains the 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 increasing the strength of the filled polymer blend. The organic coupling agents used include, for example, transition metal complexes of unsaturated fatty acids such as methacrylate chromium chloride complexes, as well as various organic silane compounds such as vinyltrichlorosilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane, allyltrichlorosilane. Resorcinol, vinyltrimethoxysilane, amyltrimethoxysilane, phenyltriethoxysilane, β-cyclohexylethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-iodopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane , γ-chloroisobutyltriethoxysilane, γ-glyoxidoxypropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-bis-(β-hydroxyethyl)-γ-aminopropyltrimethoxysilane Contains ethoxysilane and β-(3,4-epoxycyclohexylethyl)trimethoxysilane. The coupling agent used with the glass filler according to the invention is preferably a silane coupling agent. Glass fillers are often made and commercially available to contain a coupling agent as a component of the surface of the glass. Coupling agents and their use in glass fibers are discussed in Reinforced Thermoplastics, D. V. Tito and B. G. Lanham, pp. 83-88, Hallsted Press, 1975, and G. A. Lanham, 1974. It is described in detail in The Roll of Additives in Plastics, by El Matusia, published by Willey & Sons, pp. 89-91 (these documents are cited herein by reference). do). In accordance with the present invention, it has been found that the presence of antimony additives (e.g. antimony metal and antimony compounds) is generally undesirable, since the presence of antimony components generally affects the flame retardancy of the polymer mixture, as shown in the Examples below. This is because it is harmful. The present invention will be explained below with reference to Examples, but the present invention is not intended to be limited thereto. Various modifications may be made without departing from the scope of the invention. Parts and percentages are by weight unless otherwise specified. Example 1 Preparation of linear aromatic polyester (A) By solution polymerization 165.7 parts of isophthaloyl chloride, 29.2 parts of terephthaloyl chloride and 223.5 parts of bisphenol A [2,2-bis-(4-hydroxyphthaloyl chloride)] 2270 parts of methylene chloride (water content
10ppm) at 25°C. 200.7 parts of triethylamine were added at a constant rate to the reaction mixture over 7.5 hours while stirring and purging with nitrogen. The reaction mixture was kept at 15°C. After the triethylamine addition was complete, the mixture was stirred at 20° C. for 2 hours. then
6.8 parts of benzoyl chloride was added to react with the end groups of the polymer. . After 1 hour, 13.7 parts of isopropanol was added to react with excess benzoyl chloride. After 30 minutes dilute hydrochloric acid (0.5% solution
570 parts) was added to react with excess triethylamine, and the mixture was further stirred for 30 minutes. The two phases were then separated by gravity and the aqueous phase was removed. The polymer solution was additionally washed with the same amount of water until the chloride ion content in the polymer solution was 0.1 ppm. The polymer was then precipitated from the solution and dried in a vacuum oven until the water concentration was below 0.1%. The high molecular weight polymer formed was 0.74 dl/dl in symmetrical tetrachloroethane (30°C).
It had an intrinsic viscosity of g. (B) By melt (ester exchange) polymerization Bisphenol-A (1319.1 g), diphenyl terephthalate (275.9 g) and diphenyl isophthalate (1562.9 g) were dried in a vacuum oven at 75°C for several hours to yield 0.07 g. of anhydrous lithium hydroxide transesterification catalyst under a nitrogen atmosphere. The vessel was equipped with a thermometer, a nitrogen inlet on a Y-tube, a mechanical stirrer, a short Vigreux column, a distillation head and a three-necked flask receiver. Heat the container to 210°C to melt the reaction components,
Vacuum pressure was gradually applied to the stirred melt. The temperature of the reaction mixture was gradually increased to allow phenol to flood into the receiver. After 1.4 hours, the temperature of the reaction mixture reached 228℃, and the pressure of the reaction mixture was about 0.5mm.
It became Hg. The reaction mixture was then flushed with dry nitrogen, the vacuum was released, and the viscous reaction mixture was poured into a foil-lined glass dish and allowed to cool to room temperature. The bisphenol-A-isophthalate-terephthalate prepolymer thus obtained was crushed and dried overnight at 70°C in a vacuum oven. The dried prepolymer (1070 g) was placed in a 2 gallon oil-heated stainless steel reactor equipped with an agitator under a nitrogen atmosphere and heated to 210° C. with agitation. Stirring of the melt was started after 1 hour. 1.3 from the start of heating
After a period of time, reduced pressure (approximately 0.6 mmHg) was applied. The reaction temperature was gradually increased to 305°C over about 2 hours. The stirred reaction mixture was then kept at 305°C under vacuum for 6.7 hours. The reactor was opened and the obtained polyester was taken out from the reactor and allowed to cool to room temperature. 30℃
A clear yellow bisphenol-A-isophthalate-terephthalate polyester was obtained having a relative viscosity of 1.36 measured in tetrachloroethane. The above procedure was repeated using 1100 g of prepolymer in the polymerization reaction. A similar polymer was obtained with a relative viscosity of 1.35, measured in tetrachloroethane at 30°C. Example 2 Manufacture of molding composition A linear aromatic polyester was prepared by the method of Example 1(A) and dried at 120° C. for 4 hours. 100 parts of polyphenylene sulfide (marketed under the trade name Ryton V-1 by Philips Petroleum Company) having a melt flow index of 6000 when measured at 600° with a 5 kg weight using a standard orifice was added to 900 parts of polyester and mixed by rolling for 0.5 to 1 hour. Blend in a two-roll Farrel mill (front roll is 480
The mixture was kneaded for 1.5 to 3.0 minutes at 45 rpm on the 425° (back roll heated to 425°). The blend was then sheeted and ground to 4 mm particles in a pulverizer.
The particles were dried for 1-2 hours at 120°C and injection molded to make tensile and flexural specimens. The injection molding conditions were as follows. Barrel temperature (〓) 600 Nozzle temperature (〓) 580 Molder temperature (〓) 250 Screw speed (rpm) 120 Back pressure (psi) 625 Injection pressure (psi) 11200 Plasticizing time (sec) 8 Filling time (sec) 3 Total injection time (seconds) 10 The tensile specimens thus prepared were tested and found to have the following physical properties: For comparison, a control example that does not contain polyphenylene sulfide is also shown.

【table】

[Table] Examples 3 to 6 Production of molding compositions Linear aromatic polyesters were prepared by the method of Example 1(A) and dried at 120°C for 4 hours. Example 2
Particles of 4 mm were made according to the method described in . The particles were dried at 120°C for 4 hours and then made into polyphenylene sulfide pellets (Philips) with a melt flow index of 50 when measured at 600° using a standard orifice and a 5Kg weight.
Ryton 6 from Petroleum Corporation
(commercially available under the trade name) in various proportions. Tensile test specimens were prepared and tested, and the results are shown in Table 1 below. The aromatic polyesters of the invention generally have an intrinsic viscosity of at least 0.5 dl/g, preferably at least 0.6 dl/g, measured in symmetrical tetrachloroethane at 30°C.

【table】

TABLE These examples demonstrate the significant improvement in hydrolytic stability achieved by mixing polyphenylene sulfide with linear aromatic polyester compositions. Example 7 About 450 parts of a bisphenol-A-isophthalate polyester resin having an isophthalate:terephthalate ratio of 5.67 made as described in Example 1(A) was dried at 120° C. for about 4 hours and Gradually feed it into the Farrell mill described in 2, operate the front roll at 450〓 and the rear roll at 410〓,
The melting of the resin was completed and a band of transparent resin was formed on the front roll. Approximately 50 parts of the polyphenylene sulfide resin of Example 2 was then added until a homogeneous resin band was formed on the front roll. The resin mixture was kneaded for about 1.5-3 minutes and then milled into sheets. Example 2 of kneaded resin band
Grind into particles of approximately 4 mm as shown in Figure 2, and leave for approximately 4 hours.
Dry at 120°C. 58.3 parts of dried resin mixture particles shredded glass fibers (3/16 in. long; trade name 419AA, made by Owens Corning Fiberglass Corporation, which contains a silane coupling agent) mixed with. The formed mixture was heated to a barrel temperature of 600〓, a molding machine temperature of 215~225〓,
It was added to an Arberg Alrounder 200 injection molder operated at an injection pressure of approximately 14,000 psi. The mixture was formed into bar samples and subsequently reground and dried as described above to obtain a homogeneous blend. The dried, reground glass fiber-resin mixture was then charged to an Arberg 221E/150 injection molding machine operated at a barrel temperature of 550°, a molder temperature of approximately 290-295°, and an injection pressure of approximately 16,760 psi.
The resin-fiberglass blend was injection molded into specimens approximately 5 inches long, 0.5 inches wide, and 1/16 inch thick. Some of the 1/16 inch thick samples were subjected to the flame retardancy test described below. The remaining 1/16 inch thick sample piece was dried at 120°C for approximately 2 hours and subjected to pressures of 30,000 to 35,000 psi and 400 to 430 psi.
Test specimens 5 inches long, 0.5 inches wide and 1/32 inch thick were obtained by compression molding between aluminum sheets lined with steel plates in a compressor operated at . Test specimens with a thickness of 1/16 inch and 1/32 inch were tested according to the UL-94 Standard for Safety, published by Underwriters Laboratories, Inc., May 2, 1975, 2nd revised edition, pages 6 to 8. Flame retardancy was evaluated using the vertical combustion test described in ``. V-0, V-1, or V-
It was rated 2. V-0 indicates the highest degree of flame retardancy;
-2 indicates the lowest flame retardance. The oxygen index of samples of injected resin products obtained from the latter Arberg molding machine was also measured. The results of the above flame retardancy test for the excellent glass fiber filled resin blend obtained in this example are shown in Table 2 below. Example 8 To provide a basis for comparing the flame retardance of the unfilled resin blends of the present invention with the flame retardance of the glass fiber filled resin blends described above, a book containing the polyester of Example 1(A) was prepared. The unfilled resin blends of the invention were compounded and injection molded substantially as described above in Examples 2 and 7 to form 1/16 inch and 1/32 inch thick specimens as described in Example 7. Since no glass fiber component was used, there was no need to regrind and reshape the product as described in Example 7 to obtain a homogeneous blend. The sample pieces were evaluated for flame retardancy using the UL-94 flame test as shown in Example 7, and the oxygen index was also measured. The test data obtained are shown in Table 2 in comparison with that of the product of Example 7. Example 9 The procedure of Example 7 was repeated except that the bisphenol-A-isophthalate-terephthalate polyester used was made by melt polymerization as described in Example 1(B). Flame retardancy and oxygen index of the 1/16 inch thick samples were not measured. The results of this example are also shown in Table 2 below. Example 10 The same proportions of polyester and polyphenylene sulfide as in Example 8 were used, except that the bisphenol-A-isophthalate-terephthalate polyester used was made by melt polymerization as described in Example 1(B). The method of Example 8 was repeated. The flame retardance and oxygen index of the 1/16 inch thick samples were not measured. The results of this example are also shown in Table 2 below. Examples 11-13 (Comparative Examples) Examples 11-13, using the polyester of Example 1(A) and shown in Table 2 below, are control examples that are substantially comparable to Examples 7 and 8. The products of Examples 11-13 have compositions substantially comparable to those shown in Examples 7 and 8, except that one or more of the ingredients of the products of Examples 7 and 8 are omitted. Control examples 11-12
shows the flame retardant effect produced by adding an antimony compound (Sb ₂ O ₃ ) to the resin composition of the present invention. When using the glass fiber filler component in these control examples, the mixture was kneaded and molded to form Example 7.
Flame retardancy was tested according to the method of A control example was carried out essentially the same as the method of Example 8, in which case no glass fiber filler was used. The antimony additive used in Examples 11-12 was added to the resin mixture during compounding.

Table 2 In Example 8 of Table 2, the ratio of polyester to polyphenylene sulfide is 9:1, which corresponds to the ratio of these components in Examples 7, 10, 12 and 13. As is clear from the data in Table 2 by comparing the results of Example 7 and Example 8, the use of granular glass fibers in the resin blend of the present invention improves the UL-
94 significantly increases the flame retardancy of the resin blend by both test rating and oxygen index. The results of Examples 9 and 10 show that similar benefits from filler use can be obtained when the polyester is made by melt polymerization. By comparing the test results of the product of Example 8 with the test results of the product of Example 11, it was determined that the unfilled product of the present invention, as made in Example 8, was superior to that of its polyester component. Has flame retardant properties. The test results of Examples 7 and 8 were combined with Examples 12 and 8.
A comparison with the test results of No. 13 shows that the presence of antimony components in the resin blends of the present invention (both filled and unfilled) is detrimental to the flame retardancy of the blends. It will be appreciated that procedural variations in the experimental methods described above may be made without departing from the scope of the invention. For example, in Example 7, the same result of providing a homogeneous glass filler-resin mixture is obtained without the need to re-grind the molded glass fiber-containing resin article. In this alternative method, after being ground into particles and dried, the Farrel Mill resin product is added to the hopper end of a screw extruder (e.g., a Hutch Polytest 45 single screw extruder or a Werner Pfaider ZDS-K28 twin screw extruder) and The glass component is added downstream of the extruder (or the granulated glass is mixed with dry ground particles and the formed mixture is added to the hopper end of the extruder). The formed extruded resin containing a homogeneous dispersion of glass components is then cut into pellets, which are then injection molded as in Examples 2 and 8. Also, instead of adding the particulate glass component separately as in Example 7, the glass component was added before adding the sulfide polymer of the resin blend to the polyester.
It can also be intimately mixed with the sulfide polymer component. Other forms of particulate glass filler such as glass strands, glass lobbing, glass pellets, powdered glass, and glass microspheres can be used in place of the chopped glass fibers used in the examples above. Example 14 Approximately 450 parts of a bisphenol-A-isophthalate-terephthalate polyester resin having an isophthalate:terephthalate ratio of 5.67 made as described in Example 1(A) was dried at 120° C. for 4 hours;
The resin was gradually charged into the Farrel mill shown in Example 2, which was operated with a front roll of 450 mm and a rear roll of 410 mm, to complete resin melting and form a transparent resin band on the front roll. Approximately 50 parts of the polyphenylene sulfide of Example 2 was then added until a homogeneous resin band was obtained on the front roll. in the same way
20 parts 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-dimethanodobenzo [a,
e] Cyclooctene (hereinafter abbreviated as COD) was added to the resin mixture in the mill. Knead the resin and COD mixture for about 1.5-3 minutes,
It was then sheeted from a mill, ground to 4 mm particles and dried at 120°C for 4 hours. The dried resin blend particles were heated to a barrel temperature of 550〓,
The mixture was placed in an Arburg 221E/150 injection molding machine operated at a molding temperature of 275-280㎓ and an injection pressure of 20,000 psi.
The COD-containing blend was injection molded into specimens 5 inches long, 0.5 inches wide, and 1/16 inch thick. Some of the 1/16 inch thick samples were subjected to the flame retardancy test described below. The remainder of the 1/16 inch thick sample was dried at 120°C for 2 hours and
Specimens 5 inches long, 0.5 inches wide, and 1/32 inch thick were compression molded between sheets of aluminum lined with stainless steel plates in a Carver-Hore Paten Laboratory Press operated at 400-430 mm at 35,000 psi pressure. Got a piece. The flame retardance of samples with thicknesses of 1/16 inch and 1/32 inch was evaluated using the UL-94 vertical combustion test. The oxygen index of samples of injection molded resin blends obtained from Arberg injection molding machines was also measured. The results of these experiments are shown in Table 3 below. Example 15 A blend of COD and polyester and polyphenylene sulfide was obtained from a Farrel mill and processed according to the method of Example 14 by milling to 4 mm particles and drying at 120° C. for 4 hours. Glass fiber (419AA) cut from dry particles
(3/16 inch long) manufactured by Owens Corning Fiberglass Corporation under the trade name of Owens Corning Fiberglass Corporation. The formed mixture is then
It was added to an Arberg Al Rounder 200 injection molding machine operated at a barrel temperature of 550㎓, a molder temperature of 215-225㎓, and an injection pressure of about 20,000 psi. The mixture was formed into specimens, which were subsequently reground as described above and dried to yield a homogeneous mixture of resin blend and glass fibers. The dry reground mixture was then transferred to an Arberg 221E/150 injection molding machine (barrel temperature 550〓, molder temperature 290-295〓 injection pressure
(operated at 20,000 psi) and formed into 5 inch x 0.5 inch x 1/16 inch specimens as described in Example 7. A portion of the latter sample was subjected to flame retardancy testing, as in Example 14, and the remainder was compression molded to obtain specimens measuring 5 in x 0.5 in x 1/32 in. 1/16 inch and 1/32 inch specimens were tested for flame retardancy as shown in Example 14. The results of this example are shown in Table 3. Example 16 (Control) The method of Example 15 was followed except that the addition of polyphenylene sulfide and COD to the Farrel mill was followed by the addition of 5 parts of granular antimony trioxide and the measurement of the oxygen index. repeated. The moldings formed had an unsatisfactory degree of embrittlement, ie the specimens could be broken by hand with slight bending pressure. The flame retardant test results for this product are shown in Table 3. Examples 17-27 (Comparative Examples) In these Examples, the flame retardants of Examples 14, 15, and 16 were used except that one or more of the constituents of the compositions shown in Examples 14, 15, and 16 were removed. Flame retardant compositions were made and tested that were comparable to the anti-oxidant compositions. The method of Example 15 was used when glass fibers were present as a component in these compositions. The method of Example 14 was used in the absence of glass fibers. The flame retardant results of these comparative examples are shown in Table 3 below in comparison with the results of Examples 14-16.

[Table] Note: * The product was unsatisfactory as it could not be molded due to the brittleness of this mixture.
** Not measured.
*** Average of 8 measurements ranging from 34.8 to 40.1.

1
＊＊＊＊ Pure polyphenylene sulfide is extremely brittle.

Claims (1)

[Scope of Claims] 1. In the form of a mixture, (a) a linear aromatic polyester of components comprising bisphenols and dicarboxylic acids;
and (b) 5 to 95 parts by weight of polyphenylene sulfide, and 1 to 50% by weight of halogen-containing Dales based on the total weight of the linear aromatic polyester and polyphenylene sulfide. - an alder adduct is present, and the adduct is such that (A) all of the hydrogen atoms of the carbon atoms bonded by carbon-carbon double bonds are replaced by halogens selected from the group consisting of fluorine, chlorine and bromine; and (B) a halogen-containing Diels-Alder adduct of an ethylenically unsaturated organic compound containing one or two carbon-carbon double bonds, in which the cyclopentadienyl residue in the adduct is The molar ratio of saturated compound residues is 1 when the unsaturated compound contains one carbon-carbon double bond:
1 and 2:1 when the unsaturated compound contains two carbon-carbon double bonds, and the composition is substantially free of antimony components. 2 The halogen-containing adduct has the structural formula (wherein X is selected from chlorine, bromine and fluorine,
V is chlorine, bromine, fluorine, an alkyl group having 1 to 10 carbon atoms, an alkyloxy group in which the alkyl group contains 1 to 10 carbon atoms, an alkyl group containing 1 to 10 carbon atoms, and halo is chlorine; selected from haloalkyl and haloalkyloxy groups which are bromine or fluorine, Q being at least 4 alkyl groups having 1 to 6 carbon atoms, optionally substituted with chlorine or fluorine;
The composition according to claim 1, wherein the composition is a tetravalent saturated cyclic group having 4 carbon atoms. 3. The composition according to claim 2, wherein Q is a homocyclic ring having 5 to 18 carbon atoms. 4. The composition of claim 3, wherein the halogen-containing adduct is present in an amount of 2 to 30% by weight, based on the total weight of the polyester and polyphenylene sulfide, and Q is a homocyclic ring. . 5. The composition according to claim 4, wherein Q is a ring having 5 to 10 carbon atoms, and X and V are chlorine. 6. The composition of claim 5, wherein the halogen-containing adduct is present in an amount of 3 to 15% by weight, based on the total weight of the polyester and polyphenylene sulfide. 7 Halogen-containing adducts are 1, 2, 3, 4,
7,8,9,10,13,13,14,14-dodecachloro-1,4,4a,5,6,6a,7,10,10a,11,
7. The composition according to claim 6, which is 12,12a-dodecahydro-1,4:7,10-dimethanodibenzo[a,e]cyclooctene. 8. The composition of claim 1 which also contains a reinforcing effective amount of filler material. 9 The filler material is 5% based on the total weight of polyester and polyphenylene sulfide.
9. The composition of claim 8, wherein the particulate glass is present in an amount of ~70% by weight. 10. The composition of claim 9, wherein said particulate glass filler is a glass filler present in an amount of 5 to 40% by weight based on the combined weight of polyester and polyphenylene sulfide. 11 Linear bisphenol A-isophthalate-terephthalate polyester in the form of a mixture (ratio of isophthalate groups to terephthalate groups is 75:25 ~
90:10), 5-30% by weight based on the total weight of polyester and polyphenylene sulfide
of polyphenylene sulfide, and 2 to 30% by weight of 1,2,3,4,7, based on the total weight of the polyester and polyphenylene sulfide.
8, 9, 10, 13, 13, 14, 14-Dodeka halo 1,
4, 4a, 5, 6, 6a, 7, 10, 10a, 11, 12,
12a-dodecahydro-1,4:7,10-dimethanodibenzo[a,e]cyclooctene, the halo substituent is selected from the group consisting of chlorine and bromine, and the composition is substantially free of antimony components. A flame retardant composition according to claim 1. 12. The composition of claim 11, wherein the halo substituent is chlorine. 13. The composition of claim 11 which also contains 10 to 40% by weight of glass fibers, based on the total weight of polyester and polyphenylene sulfide. 14. The composition of claim 11, wherein the halo substituent is chlorine. 15 containing, in the form of a mixture, (a) 5 to 95 parts by weight of polyphenylene sulfide and (b) 5 to 95 parts by weight of a linear aromatic polyester or a mixture of the above polyesters of the components comprising a dicarboxylic acid and a bisphenol; The phenol component contains both bisphenols in which at least one carbon atom is substituted with a halogen, and the above-mentioned halogen-free bisphenols, and the halogen-containing bisphenols are 1 to 1 based on the total bisphenol components. 50
A thermoplastic polymer composition present in an amount less than mol %. 16 A mixture of polyesters comprising (A) the halogen-free bisphenol polyester and (B) the halogen-containing bisphenol polyester, wherein the halogen-containing bisphenol polyester is based on the total weight of the polyester and polysulfide. 16. A composition according to claim 15, wherein the composition is present in an amount of -40% by weight. 17 The dicarboxylic acid is an aromatic dicarboxylic acid, and the halogen-containing bisphenol contains up to 20 halogen substituents, and 5 to 20% by weight based on the weight of the polyester and polysulfide.
17. The composition of claim 16, wherein the composition is present in an amount of . 18 The above bisphenol containing no halogen has the general formula (In the formula, Ar is an aromatic group, G is an alkyl group,
an aryl group, alkylaryl group, arylalkyl group or cycloalkyl group, E is a divalent alkylene group, cycloalkylene group or arylene group, -O-, -S-, -SO-, -SO ₂ -,
-SO ₃ -, -CO-, [Formula] or GN<, T and T' are each independently selected from the group consisting of G and OG, and m is the number of substitutable hydrogen atoms on E from 0 to b is an integer from 0 to
is an integer up to the number of substitutable hydrogen atoms on Ar, and x is 0 or 1), and the above halogen-containing bisphenol has the general formula (In the formula, G is an alkyl group, a haloalkyl group, an aryl group, a haloaryl group, an alkylaryl group,
haloalkylaryl group, arylalkyl group,
A haloarylalkyl group, a cycloalkyl group, or a halocycloalkyl group, and E is a divalent alkylene group, a haloalkylene group, a cycloalkylene group, a halocycloalkylene group, an arylene group, or a haloarylene group, -O-, -S- ,-SO-,
-SO ₂ -, -SO ₃ -, -CO-, [Formula] or GN<, T and T' are each independently selected from the group consisting of halogen, G and OG, Ar,
18. The composition of claim 17, wherein x, m and b are as defined above. 19. The composition of claim 18, wherein the halogen-containing bisphenol contains up to 8 halogen substituents on different carbon atoms of the bisphenol. 20. The composition according to claim 19, wherein the halogen is chlorine or bromine, and at least one of T and T' is a halogen. 21. The composition of claim 20, wherein said linear aromatic polyester of halogen-containing bisphenols contains an aliphatic modifier and all of the halogen substituents are present as T and T'. 22. The composition according to claim 21, wherein the aliphatic modifier is a glycol having 2 to 100 carbon atoms. 23. The composition of claim 22, wherein the glycol is neopentyl glycol, diethylene glycol, 1,6-hexanediol, ethylene glycol, and mixtures thereof. 24 Claims in which the halogen-free bisphenol is bisphenol A, the halogen of the halogen-containing bisphenol is bromine, and the aromatic dicarboxylic acid is selected from the group consisting of isophthalic acid, terephthalic acid, and mixtures thereof. Composition according to item 23. 25 The halogen-containing bisphenol is 2,2-bis-(4-hydroxy-3,5-dibromophenyl)-propane, the dicarboxylic acid is a mixture of isophthalic acid and terephthalic acid, and the polyphenylene sulfide is a polyester. and about 5 to 50% based on the weight of polyphenylene sulfide.
Claim 24 present in an amount of about 30% by weight
Compositions as described in Section. 26. The composition according to claim 15, which is substantially free of antimony components.