PL102953B1 - COLOR-STABILIZED POLYCARBONATE POLYCARBONATE COMPOSITION OF CHLORINE-BISPHENOLETHYLENE - Google Patents

Description

The subject of the invention is a thermostable composition of a halogen bis-phenol ethylene polycarbonate material stabilized in terms of color. So far, limited studies have been carried out on the properties of chlorobisphenol ethylene polycarbonates, e.g. infrared spectroscopy studies described by Z. Wielgosz, Z. Boranowska and K Janicka in Piaste und Kautschuk 19/12/902/1972 /. Z. Gobiczewski, Z. Wielgosz and K. Janicka in Piaste und Kautschuk 16/2/99/1969 / have described the research on the attempts to stabilize polycarbonates from chlorobisphenol ethylene. They found that industrially hindered phenols, such as Parmanox, i.e. 4-methyl-2,6-di-tert-butylphenol, Topanol CA, i.e. 2.2 , 3-triii (2-methyl-4-hydroxy-5-tert-butylphenyl) - butane and Jonox 330, i.e. 1,3,5-tri (3,5-di-tert-butyl-4) -hydroxybenzyl / benzene is ineffective as stabilizers for chlorobisphenol ethylene polycarbonates at elevated temperatures, for example from 160 ° to 260 ° C. Other attempts to stabilize chlorobisphenol ethylene polycarbonates have not been known so far. Surprisingly, it has been found that certain organic phosphites immunize halo bisphenol ethylene polycarbonates against the harmful effects of heat, as evidenced by the reduction of the color loss of the organophosphite-stabilized polyphenol polysphenolates. According to the invention, the heat-stable, color-stabilized, color-stabilized polycarbonate halobisphenolethylene composition of polycarbonates contains an effective amount of stabilizing organic phosphite. wherein R x, Rg and R8 are independently of each other hydrogen, alkyl, aryl, cycloalkyl, arylalkyl, alkylaryl, and combinations thereof, with at least one of the groups Rlf, B ^ or R8 not is a hydrogen atom or a group linked directly to an oxygen atom through a phenyl ring carbon, and when R2 and R8 are phenyl groups, Rx may be a hydrogen atom. It is preferred that the radicals contain from 1 to 20 carbon atoms. The alkyl group can be a methyl, ethyl, propyl, isopropyl group, various isomeric butyl groups like a butyl group, II-butyl, tert-butyl groups, various isomeric amyl groups, various isomeric hexyl groups, various isomeric nonylomer groups, different isomeric groups eicosyl groups and others; the cycloalkyl group may be cyclobutyl, cyclopentyl, k-cyclohexyl, 2-methylcyclohexyl, 4-methylcyclohexyl, 2-ethylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl and others; the aryl group can be phenyl, 1-naphthyl, 2-naphthyl, biphenylyl, triphenylyl, and others; the aralkyl group may be any of the above-mentioned alkyl groups substituted with one or more of the above-mentioned aryl groups, for example benzyl, phenylethyl, 1-phenylpropyl and others; the alkylaryl group may be any of the above-mentioned aryl groups substituted with one or more of the above-mentioned alkyl groups, for example, o-tolyl, xylyl, cumyl, mesityl, butylphenyl, nhenylphenyl, and others. Typical examples of phosphites which can be used according to the invention are: diphenylhydrodecylphosphite, diphenylphosphite, di (tert.butylphenyl) octylphosphite, triethylphosphite, triethylphosphite, triethylphenylphosphite, diphenylphenylphosphite. phenyl and others. Preferred phosphites according to the invention are diaryl phosphites, for example diphenyl phosphite and Others, and diaryl alkyl phosphites, for example diphenyl decyl phosphite and others. In the polycarbonate chain, halogen-bisphenylethylene carbonate units of the general formula II, in which each of the substituents R is independently a boron hydrogen, - bromine * or a monovalent hydrocarbyl or hydrocarbyl xyl group containing from 1 to 30 carbon atoms of Y is hydrogen, chlorine or bromine, where at least one Y is chlorine or bromine and m is an integer of at least 2. Preferred hydrocarbyl groups are monovalent alkyl groups with 1 to 4 carbon atoms or phenyl. More preferred polycarbonates contain the metals of formula II in which each R is hydrogen and each Y is chlorine. PL

Claims (9)

reservations. Also within the scope of the present invention are halobisphenol ethylene polycarbonates containing both halobisphenylethylene carbonate units of formula II and arena carbonate units of formula III, wherein Rf is an alkylene, alkylidene, cycloalkylene, cycloalkylidene or arylene bridge. combinations thereof, an ether, carbonyl, amine bridge or a bridge containing sulfur or phosphorus atoms, Ar and Ar 'denote arene radicals, Y denotes an organic, inorganic or organometallic radical, X denotes a monovalent hydrocarbon group such as alkyl, aryl, cycloalkyl and combinations thereof, a halogen atom, an ether group of the formula —OE, where E is an alkyl, cycloalkyl or aryl radical * d is an integer of at least 1, c is an integer of 45 50 55 60 65 are at least 0 or greater! I; ; ^ c, signifies * - integers including zero, a or c but not both can be; zero and in which n is an integer of at least 2. Preferred polycarbonate copolymers according to the invention are polycarbonates containing both halobisphenylethylene carbonate units of formula II and arena carbonate units of formula IV, in which each R independently represents a hydrogen atom. , chlorine, bromine or a monovalent hydrocarbon group containing from 1 to 30 carbon atoms, Rg and Rh independently represent a hydrogen atom or a monovalent hydrocarbon group containing from 1 db 30 carbon atoms, and n is an integer of at least 2 The preferred hydrocarbon lumps are monovalent AkU groups having from 1 to 4 carbon atoms, and a phenyl group. More preferred polycarbonates contain bisphenylcarbonate units of Formula IV where each R is -hydrogen and Rg and Rh are methyl. Chloride-bisphenol ethylene polycarbonates can be obtained by known methods, for example those given by S. Porejke and co-authors in the Polish Patent No. 48 893, entitled "Method for the production of self-extinguishing thermoplastics" or described by Z. Wielgosz and co-authors 76 / Polymer 17, 1072 / S. Porejko et al. And Z. Wielgosz and co-authors describe the reactions of a mixture of chlorobisphenol ethylene, i.e. 1,1-dichloro-2,2-di (4-hydroxyphenyl) ethylene and bisphenol A, i.e. 2, 2-di (4-hydroxyphenyl) propane with a carbonate precursor i.e. phosgene and an acid acceptor i.e. sodium hydroxide in the presence of a catalyst i.e. triethylamine. The reactions were carried out under the usual phosgenation reaction conditions, i.e. typically used in the phosgenation of bisphenol A as described in the "Polycarbonate" section on pages 710-764 of the Encyclopedia of Polymer Science and Technology published in 1909 by Interscience Publishers. Examples of some halobis-phenolethylene compounds from which polycarbonates and polycarbonate copolymers can be obtained in accordance with the conditions of the phosgenation reaction described by S. Porejke and co-authors Z. Wielgosz and co-authors and in the Encyclopedia of polymer Science are, among others: 2-bis (4-hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis (5-methyl-4-hydroxyphenyl) ethylene, 1,1-dibromo-2,2-bis (3,6-) di-n-butyl-4-hydroxy-phenyl) -ethylene, 1,1-dichloro-2,2-bis (2-chloro-5-ethyl-4-hydroxyphenyl) -ethylene, 1,1-dibromo 2,2-bis (2,5-dibromo-4-hydroxyphenyl) ethylene, 1-bromo-2-bis (4-hydroxyphenyl) ethylene, 1-chloro-2,2-bis / 3,5 -diisopropyl-4-hydroxy-phenyl) -ethylene, 1-bromo-2,2-bis (2,6-di-tertiary 4) utyl-4-hydroxyphenyl) -ethylene, 102: 953 5 l-chloro -2,2-bis (2,6-di-chloro-4-hydroxyphenyl) -ethylene, 1-bromo-2,2-bis (2,3-dibromo-4-hydroxyphenyl) -ethylene, 1,1 -dWAchloro-2,2-bis / 3,5-dichloro-4-hydroxyphenyl) -ethylene, 1,1-dichloro-2'-bis / 3,5-dibromo-4-hy Droxyphenyl) -ethylene, 1,1-dibromo-2,2-bis (5-chloro-4-hydroxyphenyl) -ethylene, 1-chkro-2 ^ 2-bis ^ and 3,6-dibromo-4-hydroxy - phenic / -ethylene, 1-bromo-2T2-bis (2-chloro-4-hydroxylenyl) -ethyleni1,1-dichloro-2,2-bis (1,2,3,5-trichloro-4-hydroxyphenyl) (N-ethylene, 1,1-dibromo-2-2-bis (2,3-, 6-tetrabromo-4-hydroxyphenyl) -ethylene, 1-chloro-2-biphenyl) 3-phenyl-4-hydroxyphenyl / -etyleaip 1-bromo-2,2-bis / 3,5-diphenyl-4-hydroxyphenyl) -ethylene, 1,1-dichloro-2,2-bis (2'-diphenyl) -4-hydroxy-phenyl) -ethylene , 14-dibromo-2,2-bis (3-bromo-5-phenyl-4 (-hydroxy-phenyl) -ethylfca, 1-chloro-2,2-bis (3-methoxy-4-hydroxyphenyl) -ethylene , 1-bromo-2,2-bis (3,5-dimethoxy-4-hydroxyphenyl) ethylene, 1,1-dichloro-2; 2-bis (2-ethoxy-4-hydroxyphenyl) ethylene, 1,1-dibromo-2,2-bis (2,6-diethoxy-4-hydroxyphenyl) -ethylene, 1-chloro-2,2-bis-1-phenoxy-4-hydroxyphenyl) -ethylene, 1- bromo-2,2-bis (3,5-diphenoxy-4-hydroxy-phenyl) -ethylene, 1,1-dichloro-2,2-bis (3-chloro-5-phenoxy-4--hydroxyphenyl) ethylene , 1,1-dibromo- 2,2-bis (2-bromo-5-phenoxy-4-hydroxyphenyl) ethylene. Examples of some dihydroxy arene compounds from which it is possible to obtain chlorobisphenol ethylene polycarbonates or mixtures of halobisphenol ethylene polycarbonates with other polycarbonates containing phenylcarbonate units of formula 3 and 4, according to the conditions of the phosgenation reaction described by Z. Porejke et al. And in the Encyclopedia of Polymer Science include: resorcinol, 4,4'-dihydroxy-diphenyl, 1; 6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 4,4'-dihydroxy-diphenylmethane, 1,1- di (4-hydroxyphenyl) ethane, 1,1-di (4-hydroxyphenyl) butane, 1,1-di (4-hydroxyphenyl) isobutane, 1,1-di (4-hydroxyphenyl) cyclopentane, 1,1-di) 4-hydroxyphenyl / cyclohexane, di (4-hydroxyphenyl) phenylmethane, di (4-hydroxyphenyl) - (2-chlorophenyl) methane, di (4-hydroxyphenyl) - (2,4-dichlorophenyl) - methane, di (4-hydroxyphenyl) (-) p-isopropylphenyl) methane, 6 di (4-hydroxyphenyl) naphthylmethane, 2,2-di (4-hydroxyphenyl) propane, 2- (3-methyl-4-hydroxy) nyl (-2- (4-hydroxyphenyl) propane, 2- (3-cyclohexyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) propane, 2- (3-methoxy-4-hydroxyphenyl) -2 - (4-hydroxyphenyl) propane, 2- (3-isopropyl-4-hydroxyphenyl) -2- (4-hydroxyphenyl) propane, 2,2-di (3-methyl-4-hydroxyphenyl) pTorane, 2 , 2-di (3-chloro-4-hydroxyphenyl) propane, 2,2-di (4-hydroxyphenyl) butane, 2,2-di (4-hydroxyphenyl) pentane, 2-di (4-hydroxyphenyl) - 4-methylpentane, 2,2-di (4-hydroxyphenyl) -n-hexane, 2,2-di (4-hydroxyphenyl) nonane, 4,4-di (4-hydroxyphenyl) heptane, di (4-hydroxyphenyl) - phenylmethyl / methane, di (4-hydroxyphenylmethyl) - / 4-chlorphenylmethyl methane, di (4-hydroxyphenylmethyl) - / 2,5-dichlorophenylmethyl / methane, di (4-hydroxyphenyl) - / 3,4-dichlorophenylmethyl / methane, di (4-hydroxyphenyl) - (4-fluorophenylmethyl) methane, di (4-hydroxyphenyl) - (2-naphthylmethyl) methane, di (4-hydroxyphenyl) diphenylmethane, di (4-hydroxyphenyl) phenyl cyanomethane, 1- di (4-hydroxyphenyl) ethane, MO-di [beta] -hydroxyphenyl, Z-n-decane, 1,6-biceto-1,6-di- [4-hydroxyphenyl] k) -n-hexant 1,10-biceto-1,10-di (4-hydroxyphenyl) -n-decane # 4,4'-bis (-p-hydroxyphenoxy) diphenyl, a, a, a ^ a ' zteromethyl OH *, α-n-xylene (p-hydroxyphenyl) - -β-xylene, α-α-tetromethyl-α-α-α ^ (p-hydroxyphenyl) - -n-xylene, di (2-hydroxy-3 - dimethylphenyl / methane, di (3-methyl-4-hydroxyphenyl) methane, di (2-methyl-4-hydroxyphenyl) methane, di [beta] -hydroxy ^^ - dimethylphenyl) methane, di (3-chloro-4-hydroxyphenyl) methane , di (8-methoxy-4-hydroxyphenyl) methane, di (4-hydroxy-2'-dimethylphenyl) methane, di (4-hydroxy-2,3,5,6-tetramethylphenyl) methane, di (2-methyl-) 4-hydroxy-5-isopropylphenyl) methane, di (2-methyl-4-hydroxy-5-propylphenyl) methane, di (2-methyc-4-hydroxy-5-tert-butylphenyl) methane, 5,5- di (4-hydroxyphenyl) nonane, 6,6-di (4-hydroxyphenyl) undecane, 3,3-di (4-hydroxyphenyl) butanone-2,3,3-di (3-methyl-4-hydroxyphenyl) butanone- 2,4,4-di (4-hydroxyphenyl) hexanone-3, di (4-hydroxyphenylmethyl) t (4-methoxyphenyl) methane, di (4-hydroxyphenyl) ether, di (4-hydroxyphenyl sulfide), sulfide di (3-methyl-4-hydroxyphenyl), di (4-hydroxyphenyl sulfoxide), di (4-hydroxyphenyl) sulfone, di (3-methyl-4-hydroxyphenyl) sulfone, 10 15 30 Si 30 35 40 45 50 55 80102953 7 l, l-di (4-hydroxy-3-5-dichlorophenyl) -cyclohexane, 2-di (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-di (4-hydroxy-3,5-dimethyl) -2,6-dibromofettyio (propane) and 2,2-di (4-hydroxy), 5-dibromophthyl (propane) and others. The intrinsic viscosity of the preferred bicarbonate polyethylene chlorides is at least 30 cm / g, more preferably 50 cm / g, when measured at 25 ° C. in methylene chloride or chloroform or a similar solvent system. The upper limit of the intrinsic viscosity is not critical, although it should be about 15.0 cm / g. Particularly useful are halobisphenol ethylene polycarbonates having an intrinsic viscosity ranging from about 38 to about 70 cm8 / g. It is preferred that the polycarbonates of halobisphenolethylene contain such an amount of the above-described repeating units of formula 2 or 13 or 4 such that the average molecular weight of the homopolycarbonates or copolycarbonates, including their mixtures with other polycarbonates, is at least about 5000, and more preferably from about 10 0 0 to about 50,000. Polycarbonates having such an average molecular weight are readily processable at temperatures ranging from about 230 ° to 343.3 ° C. Mixtures of halobisphenolethylene polycarbonates with any other polycarbonate containing arenocarbonate units of formula III or 4S described above are also an object of the present invention. Such mixtures can be obtained by any of the known methods. Preferred mixtures are obtained by heating a mixture of halobisphenploethylene polycarbonates and any other polycarbonate to a temperature above their softening point (s). It is preferable, when preparing the mixture without the use of a solvent, to heat the mixture to the above-mentioned elevated temperature, that is to say above the melting point, while mechanically treating the mixture. Thus, mixing can be carried out in single or multi-screw extruders, in Banbury mixers, on rolling mills or by other mechanical devices in which the mixture is subjected to shear stresses at elevated temperatures. Particularly useful in the invention are the halobisphenol ethylene monocarbonates containing an epoxy compound in addition to the organic phosphite, that is, a compound containing at least one epoxy group of formula 5. Any saturated or unsaturated epoxy compounds may be used, including aliphatic compounds, including aliphatic compounds. , aromatics and heterocyclic compounds which are referred to herein as epoxides. Epoxies may be, if desired, substituted with non-interfering substituents, e.g., halogen atoms, phosphorus atoms, ether type radicals and the like. Epoxies can also be monomeric and polymeric compounds, derived from natural sources or obtained synthetically. Examples of some preferred aliphatic epoxides which can be used in the present invention are the compounds of formula 6 in which Ri and Rj are independently of each other an alkyl group of 1 to 24 carbon atoms and p is an integer ranging from 1 to 10. Examples of usable cycloaliphatic epoxides are epoxidized cycloaliphatic compounds having 1-2 cycloaliphatic rings having 6 carbon atoms in each ring, in which in at least one cycloaliphatic ring at least one oxygen bridge connects with one oxygen bridge. we carbon. Examples of usable aromatic epoxides are aromatic glycide ethers, aromatic diglycide ethers containing 1 to 3 rings or aromatic polyglycide ethers containing 1 to 3 aromatic rings. Examples of compounds belonging to the abovementioned groups of epoxides which can be used according to the invention are: butadiene dipoxide, epoxidized polybutadiene, diglycide ether, bisphenol A diglycide ether, phthalic acid diglycidic ester, soybean dihydroxide ester soybean oil. Tetraphenylethylene epoxide, octyl epoxytalate, 3,4-epoxycyclohexylmethyl ester 3,4-epoxycyclohexanecarboxylic acid, 3,4-epoxy-6-methylcyclohexylmethyl ester 3,4-epoxy-6-methylcyclohexylcarboxylate methyl ester, 40 2,3-epoxy methyl ester 3,4-epoxycyclohexanecarboxylic acid, 3,4-epoxycyclohexanecarboxylic acid 4- / 3,4-epoxy-5-methylcyclohexyl / butyl ester, 3,4-epoxycyclohexylethylene oxide, 45 di (3,4-epoxy-6-methylcyclohexylmethylene) adipate tyl), 3,4-epoxycyclohexanecarboxylic acid cyclohexylmethyl ester and 6-methylcyclohexanecar acid 3,4-epoxy-6-methylcyclohexylmethyl ester boxing. In general, epoxides with preferred properties contain from about 3 to about 30 carbon atoms. Preferred epoxides according to the invention are bisphenol-A diglycide ether and 3,4-epoxy-cyclohexylmethyl ester of 3,4-epoxy cyckhexane carboxylic acid. According to another variant of the invention, in addition to the phosphites, which can be used alone or together with epoxy compounds to improve the thermal and color stability of halobisphenol ethylene polycarbonates, it is also possible to use cadmium, barium and / or cerium aliphatic, cycloaliphatic and aromatic salts. carboxylic acids or carbonic acids. Such salts are herein referred to as metal salts. It is preferable to use cadmium, barium and / or cerium carboxylic acids with 2 to 20 carbon atoms, aromatic acids with 7 to 20 carbon atoms and carbonic acids as stabilizers for polycarbonates, whether used alone or in combination. in combination with phosphite or phosphites and epoxides. Examples of cadmium, barium and cerium salts of aliphatic acids with 2 to 20 carbon atoms, aromatic acids with 7 to 20 carbon atoms and carbon acids are, among others, such metal salts as acetate, butylate, adipate, capricate, stearate, arachidate, cyclohexane carboxylate, benzoate, phthalate, isophthalate, terephthalate, methylbenzoate, cadmium, barium or cerium naphthoate or carbonate. The use of cadmium, barium or cerium 2-ethyl adipate is preferred. In general, it is preferable to use the cadmium, barium or cerium salts of the abovementioned organic acids by using a stabilizing amount of an organic acid corresponding to the type of the abovementioned acids in addition to these salts. The stabilizing organic phosphite compositions described herein include hydrocarbon-substituted phosphite, hydrocarbon-substituted phosphite or hydrocarbon-substituted phosphite or epoxide or epoxide or epoxide or hydrocarbon-substituted phosphite or hydrocarbon-substituted phosphite compositions. compounds, epoxides or epoxides and one or more cadmium, barium or cerium salts of aliphatic, cycloaliphatic, aromatic or carbonic acid or carboxylic acids or mixtures containing constituents of the group (3) and an organic acid corresponding to the cadmium salt-forming acid , barium and cerium mentioned above. Typically, the amount of the stabilizing organic phosphite or other stabilizer corresponds to the effective amount, that is, the amount that increases the thermal or color stability of halobisphenol ethylene polycarbonates. In general, the effective amount of stabilizer or stabilizer composition in the context of the present invention may be as low as 0.010 parts by weight or less to as high as 0.5 parts by weight or even more per 100 parts by weight of halobisphenol ethylene polycarbonate. For utility and economy reasons, the amount of stabilizer or stabilizing composition is generally from about 0.025 to about 1.0 parts by weight per 100 parts by weight of cobisphenol ethylene chlorinated polycarbonate. According to a preferred embodiment of the invention, the stabilizing composition comprises from about 0.05 to about 0.25 parts by weight of organic phosphite, from about 0.05 to about 0.25 parts by weight of epoxy, and from about 0.5 to about 0.25 parts by weight. parts by weight of the cadmium, barium or cerium salt of a 2 to 20 carbon alkanecarboxylic acid, an aromatic carboxylic acid of 7 to 20 carbon atoms or of carbonic acid per 100 parts by weight of a halobisphenol ethylene polycarbonate composition. The following examples illustrate the method of the invention without, however, limiting the invention in any way. These examples used the basic method of making and testing stabilizers for halobisphenol ethylene polycarbonates, unless otherwise stated. In some examples there are deviations from the basic method. The basic way. A series of chlorobisphenol ethylene polycarbonates were obtained by reacting an aqueous alkaline solution of 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene with phosgene in the presence of triethylamine and methylene chloride at a temperature from about 0 ° to about 40 ° C. The result of this reaction was a polychlorobis-phenol polycarbonate having a high molecular weight and the intrinsic viscosity (measured in methylene chloride at 25.30C) of 52.5 cm8 / g. Each stabilizer or stabilizer composition combines 20? chlorobisphenol polycarbonate as follows: by coating the chlorobisphenol polycarbonate in powder form with a solution containing the stabilizer or stabilizing composition to be tested, by evaporating a solvent which in most cases is not a chlorobisphenol ethylene solvent, and by squeezing 750 milligrams at room temperature. of this chlorobisphenol ethylene polycarbonate to obtain a tablet, / 4 / by squeezing the tablet at a temperature of 240 ° C and a pressure of 55.16-10 µl niuton / m2 to obtain a transparent disc with a diameter of 25.4 mm and a thickness of 93.08-10 - * mm, / € / subjecting the formed disc to a temperature of 300 ° C and a pressure of 55.16-10 * newton / m2 for an additional 5 minutes and / 7 / measuring the color of the disc by the method of measuring the absorbance of light with a wavelength of 425 nanometers by dissolving 100 milligrams of the disc in 5 milliliters of chloroform, contained in a 1 cm cuvette. A low absorbance number, for example, 0.022, is the most stable, while a high absorption value of, for example, 0.060, is the least durable. Examples I to V. Table 1 shows the absorption values of the 1,1-dichloro-2,2-bis (4-hydroxyphenyl) polycarbonate control sample - Table 1 55 00 Example No. X II III IV V Ingredient (s) stabilizing 1 control sample diphenyl phosphite diphenyl phosphite cadmium heptane carboxylate * / diphenyl phosphite total cadmium heptane carboxylate * / triphenyl phosphite value (per 100 parts) - 0.15 0.150 0.087 0.063 0.300 0.15 0.15 0.040 0.048 0.048 0.048 (4) is * / 50% by weight of heptane carboxylic acid 102 953 l and 12 ethylene no stabilizing component, and by l, l-dichloro-2,2-bis (4-hydroxyphenyl) ethylene polycarbonate containing phosphite, salt of alkanecarboxylic acid and compositions of the phosphate phosphites from the salt of an alkanoic acid. The amount of each stabilizer is also listed. The above data indicate that not all phosphites are effective stabilizers for halobisphenolethylene polycarbonates and organic phosphites, metal salts, and organic phosphite compositions and metal salts within the meaning of the present invention as effective stabilizers for halobisphenolethylene carbonates. Examples VI to IX. Table 2 shows the data analogous to the data in Table 1. In these examples, the samples were post-treated by subjecting them to a temperature of 315 ° C and a pressure of 55.16-10 Newton per m2 for 15 minutes. The light absorption of 425 nanometers wavelength by the solution obtained by dissolving 53 milligrams of the disc in 1 milliliter of methylene chloride was measured by placing this solution in a 1 cm cuvette. Table 2 Example 1 No. VI VII VIII XI 1 Stabilizing component, control sample (a) diphenyl decyl phosphite / b) 3,4-epoxy-cyclohexylmethyl 3,4-epoxycyclohexanecarboxylic acid ester together / a) diphenyl decyl phosphite / g / cadmium heptane carboxylate * / total 3,4-epoxycyclohexylmethyl ester 1 of 3,4-epoxycyclo- acid | | hexane carboxylic acid | Amount per 100 (parts) .— 0.036 0.114 0.150 0.063 0.087 0.150 0.15 Absorbance 1 (425 \ nm 1 0.335 0.245 0.175 0.940 | * / 50 * / w / w heptanecarboxylic acid The above data shows that the phosphite compositions organic with metal salts and compositions of organic phosphites with epoxides are effective stabilizers for halogenated bisphenol ethylene carbonates. 4-hydroxy-phenyl) -ethylene and 10 parts by weight of bisphenol A polycarbonate, having a significant density (measured in methylene chloride) of 52 cm / g and obtained in the process of 2,2-bis reaction carried out under usual industrial conditions (4-hydroxyphenyl) propane with phosgene in the presence of triethylamine and methylene chloride, extruded and injection molded to obtain a polymeric mixture of intrinsic viscosity (measured at 25 ° C in methylene chloride) of 47 cm / g. The polycarbonate compounds were injected into the mold, the injection temperature being approximately 263.9 ° C and the mold temperature approximately 93.3 ° C. The obtained polycarbonate mixtures were tested to calculate the color intensity and the color code according to the General Electric method. In this method, the color intensity index (CI) is calculated, indicating the brightness of the color, and the color code index (CC), indicating the dominant color / shade / hue, e.g. purple, blue, green, yellow, orange or red. The color intensity and the color code of the mixture containing 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene polycarbonate were determined by measuring light absorption with wavelengths of 436, 490, 546, 570 , 620 and 660 nanometers by placing in a 10 cm cuvette the solution obtained after dissolving 2.5 g of the injection product in 50 milliliters of methylene chloride. The numerical values of the color intensity were calculated from the equation: CI = 10 /! P + N / where P = A4M + A4W + A64I; N = A670 + A620 + Afli0. The color code was calculated from the equation: CC =. / P + IN [/ 10 where P and N have the meaning given above. A small value of the color intensity, eg, 15.0, means that the composition has better thermal and color stability, in contrast to the control sample, for which the color intensity is higher, eg, 23.0. The test results are given in Table 3, Table 3 No. IX X Stabilizing component, control sample (a) diphenyl decyl phosphite / b) 3,4-epoxy-cyclohexylmethyl ester of 3,4-epoxycyclohexanecarboxylic acid in total Amount (per 100 parts) - 0.036 0.144 0.150 CC 5.5 5.5 CI 23.0 15.0 Examples XI-XII. The color of a mixture of 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene polycarbonate and bisphenol polycarbonate A was measured using the method described in Examples IX and X, except that the amount of polycarbonate 1 1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene was 96 parts by weight and the amount of bisphenol polycarbonate A 4 parts by weight 102953 l * Table 4 14 Example [¦ 'No. ¦' XI XII r .. Ingredient stabilizing control sample / a / diphenyl decyl phosphite / b / 3,4-epoxy-cyclohexylmethyl ester 3,4-epoxycyclohexanecarboxylic acid total (per 100 parts) '¦ -. : 0.036 0.114 0.150 cc 5.4 5.5 CI 29.0 1 *, 0.01 However, the examples given above give the values for absorption, color intensity and color code for 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethylene polycarbonates and mixtures thereof, when other halobisphenol ethylene polycarbonates are used. and mixtures of these polycarbonates gave similar results. In general, the compositions of the halogen-bisphenolethylene polycarbonates according to the invention may contain, in addition to the stabilizing ingredients described herein, other additional substances, e.g. , anti-drip, surfactants, etc. Stabilized halobisphenol polycarbonates can be formed and shaped by conventional molding methods into films, sheets, fibers, laminates and other articles, including reinforced articles. ! It will be obvious to those skilled in the art that the particular embodiments of the present invention described herein may be varied and modified without exceeding the scope of the invention and resulting from the appended claims. Claims 15 1. The thermostable co-composition of a polycarbonate material of halobisphenol ethylene, stabilized in terms of color, characterized in that it contains about 1 to 100 parts by weight of mers; halobisphenylethylene carbonates of formula II, in which each of the R substituents independently is hydrogen, chlorine, bromine or a monovalent hydrocarbyl or hydrocarboxylic group containing from 1 to 3Q carbon atoms, each of the Y substituents is a chlorine or bromine hydrogen atom, wherein at least one Y is chlorine or bromine, and m is an integer of at least 2 and about 99-0 parts by weight of arene-carbonate units of formula III, wherein Rf is an alkylene, alkylidene, cycloalkylene, cycloalkylidene moiety or an arylene bridge or any other combination, an ether, carbonyl, amine bridge or a bridge containing sulfur or phosphorus atoms, Ar and Ar 'denote arene radicals, each of the Y substituents is an organic, inorganic or organometallic radical, X denotes one - a novel hydrocarbyl group such as an alkyl, aryl or cycloalkyl group or combinations thereof, a halogen atom, an ether group of the formula —OE, in where E is an alkyl, cycloalkyl or aryl radical, d is an integer of at least 1, c is an integer of at least zero or greater, and, b, c are integers including zero, a or c but not both can be zero simultaneously, where n is an integer of at least 2, and the effective amount of the phosphite-containing stabilizer. organic. 2. A thermostable composition of a halogenated bisphenol ethylene polycarbonate material, stabilized in terms of color, characterized in that it contains about 1 to 100 parts by weight of halobisphenylethylene carbonate units of the formula II, in which each of the R substituents is independently hydrogen, chlorine, bromine or mono- a value, hydrocarbyl or hydrocarbyloxy group containing from 1 to 30 carbon atoms, each of Y is hydrogen, chlorine or bromine, where at least one Y is chlorine or bromine and m is an integer of at least 2 and about 90 to 0 parts by weight of a polycarbonate containing units of formula IV, in which each of the substituents R independently has the meaning given above, and Rg and Rh independently represent a hydrogen atom or a monovalent group Hydrocarbon, containing from 1 to 30 carbon atoms, and effective stabilizer containing organic phosphite. 3. The thermostable composition according to claim 1, A compound according to claim 2, characterized in that the units of formula II are those of formula VII, in which each of the R substituents is independently hydrogen, chlorine or bromine, an alkyl group of 1 to 4 carbon atoms or a phenyl group, and m is an inch ¬ total of at least 2, and as units of formula IV contains units of formula 8, in which each of R independently has the meaning given above, Rg and Rh independently represent a hydrogen atom, an alkyl group of 1 to 4 carbon atoms or a phenyl group, and n is an integer of at least 2, and an organic phosphite in an amount from 0.025 parts by weight to 1.0 parts by weight per 100 parts by weight of polycarbonate with halobisphenol ethylene 4. The thermostable composition according to claim 1, A compound as claimed in claim 3, characterized in that it contains a phosphite of formula 1, wherein R 2, R 2 and R j are independently hydrogen, alkyl, aryl, cycloalkyl,. aralkyl and alkylaryl, and combinations thereof, where at least one of Ru R2 and R * is not a hydrogen atom or a group linked directly to the oxygen atom through the phenyl ring carbon, and that when R2 and R8 represent a phenyl group, B, x can be a hydrogen atom. 5. The thermostable composition according to claim 1, 5. The composition of claim 1, which also includes an epoxy. 35 40 60 102 953 15 6. The thermostable composition according to claim 1, The epoxide of claim 5, wherein the epoxide is aliphatic epoxides of formula VI, in which Ri and Rj independently represent an alkyl group of 1 to 24 carbon atoms and p is a total number of 1 to 10, cycloaliphatic epoxides are Containing 11H2 aliphatic rings with 6 carbon atoms in each ring, where in at least one cycloaliphatic ring at least one oxygen bridge connects adjacent carbon atoms, or aromatic epoxides being aromatic glycide ethers, aromatic glycidic ethers containing 1-3 rings and aromatic polyglycide ethers containing 1-3 aromatic rings. 7. The thermostable composition according to claim 1, 6. A method as claimed in claim 1, characterized in that it also contains a cadmium, 16 bar or cerium salt of an aliphatic, cycloaliphatic or aromatic carboxylic acid or carbonic acid. 8. The thermostable composition according to claim 1, wherein the salts are cadmium, barium or cerium salts of an aliphatic carboxylic acid with 2 to 20 carbon atoms, an aromatic carboxylic acid with 7 to 20 carbon atoms or carbonic acid. 9. The thermostable composition according to claim 1, And the remaining Y is hydrogen, and the formula 4 units in which R are hydrogen, hydrogen, and Rg and Rh are methyl. V 0R2 RiO-P "0R3 Wzbr 1 (R) <(RU C n A Y Y 0- 0 n c + J m Formula 2 -hO-h (Y) d I Ar Ja (X) e I -Rf -Ib lY) d -Ar- 0 II 0-C Jn Formula 3102 953 (R) 4 (R) * Rg O f (Mg ^ -c - ^ o-c4- Rh Formula 4 n A A ¦C C- - | -Rl-C C -Rj + - Pattern 5 Pattern 6 R R R A R a a o u o-c- -! M Pattern 7102 953 R R R g o c- ^ py-o-c-h in Pattern 8 Bltk 641/79 r. 95 copies A4 Price PLN 45 PL