MXPA06004870A - Stabilizer compositions for halogen containing polymers - Google Patents

Abstract

The instant invention relates to a composition and process for the stabilization of halogen containing polymer slurries, in particular polyvinylchloride (PVC). The composition comprises a halogen containing polymer in the form of an aqueous suspension or emulsion, a partially hindered phenolic antioxidant and selected sulfur containing antioxidants, which are both solid at 20°C. A further aspect of the invention is the use of specific antioxidant mixtures for the stabilization of halogen containing polymer suspensions or emulsions, in particular PVC.

Description

STABILIZING COMPOSITIONS FOR POLYMERS CONTAINING HALOGEN DESCRIPTION OF THE INVENTION The present invention relates to a composition and process for the stabilization of mixtures of halogen-containing polymers, in particular polyvinylchloride (PVC).

The composition comprises a halogen-containing polymer in the form of an aqueous suspension or emulsion, a phenolic antioxidant partially hindered and selected from sulfide containing antioxidants, both of which are solids at 20 ° C. In addition one aspect of the invention is the use of mixtures of specific antioxidants for the stabilization of polymer suspensions or halogen-containing emulsions, in particular PVC. The thermal stability of halogen-containing polymers, such as PVC, is relatively low compared to many other polymers. Because otherwise of its good total properties, this is versatile, and the cost of effectiveness, this is nevertheless an extremely favorable material. However, this can only be used, if it is well stabilized against the degradation induced by heat, light, mechanical stress, etc. Protection against thermal degradation is especially important. The protection of PVC compounds and final products against thermal degradation can be achieved by so-called "heat stabilizers" which are mainly based on metal salts of organic molecules (eg, metal soaps), as described in breadth in the literature (eg H. Zweifel, Handbook of Plastic Additives, 5th edition, Hanser, 2001, pages 427-483). However, these heat stabilizers can only be added to the composite phase. This means that the halogen-containing polymer resin after the polymerization residues remains unprotected during the monomer recovery processes and drying processes. The damage that occurs in this phase lowers the thermal stability of the resin and the corresponding compounds and final articles. To improve the heat stability during the composite phase EP 0 849 314 suggests adding in addition to a Zn carboxylate a phenolic antioxidant and a thiodipropionic acid ester. The additional use of phenolic antioxidants and thiodipropionic acid esters with conventional PVC stabilizers during the composite phase is also described in GB 1 001 344. In the case of sterically complete PVC or in partially hindered phenolic antioxidants they can already be added to the mixture. of reaction. Sometimes small complete amounts of hindered phenolic antioxidants are added at the beginning of the polymerization and frequently complete or partial hindered phenolic antioxidants are added towards the end of the polymerization. The thermal stability of the PVC resin, and also of the resulting PVC compound is therefore improved, however, not for a satisfactory complete level. It has now been discovered that the combinations of partially hindered phenolic antioxidants with thioethers or thioether esters, was added to the halogen-containing polymer reaction mixture, which is in the form of an aqueous suspension or emulsion, preferably towards the end. of the reaction, greatly improving the thermal stability of the halogen-containing polymer and the resulting polymer compound, was compared to the current state of the art. Additional stabilizers can then also be added during the composition phase. For example, the halogen-containing polymer obtained, in particular the virgin PVC resin, experienced much less dehydrochlorination (less chloride from PVC) and discoloration in the heat treatment than the PVC stabilized conventionally. One aspect of the invention is a composition comprising a) a halogen-containing polymer or copolymer in the form of an aqueous suspension or emulsion; b) a sterically hindered phenolic antioxidant with a melting point of more than 20 ° C containing a compound of formula (Ia) or (Ib) wherein n is 2 or 3 Ri is tert-butyl, C3 to C-1β secondary alkyl or C5 to C6 cycloalkyl; R'i is tert-butyl, Ci to Cis alkyl of primary or secondary bond, phenyl, phenylalkyl of C to C9 or cycloalkyl of C5 to Ce; R3 is Ci to Cis alkyl, Cx alkoxy to Gis, C5 to C6 cycloalkyl or CH2-CH2-CH2-CO-0- (Ci to C_.8) alkyl; R'2 is a divalent or trivalent bridging group; R is a group or hydrogen; R is hydrogen, methyl or a group wherein m is a number from 1 to 10; and c) a thioether or thioether ester with a melting point of more than 20 ° C of formula (Ha), (Hb) or (He) (He) in which P-n and R-12 are independently alkyl Ci to Cie k is 2 to 4; and 10 X is 2-methyl-1,2, 3-propane-triyl- or 1, 2, 3, 4-methane-tetryl-.

The bridge group R2 'is for example in position 2 or 4 relative to the OH group, preferably in position 2. The amount of polymer, in particular PVC, in the suspension or emulsion is typical of 30 to 80%, example 40 to 70% by weight, based on the aqueous phase. Contains halogen, in particular contains chlorine, polymeric materials (component (a)) can be example: vinyl chloride polymers, vinyl resins containing vinyl chloride units in their structure, such as vinyl chloride copolymers and vinyl esters of aliphatic acids, preferably vinyl acetate, vinyl chloride copolymers with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and vinyl chloride copolymers , copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; vinylidene chloride polymers and copolymers thereof with vinyl chloride and other polymerizable compounds; polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and substituted acrylic acid; polymers of chlorinated styrenes, typically dichlorostyrene; chlorinated rubbers; chlorinated ethylene polymers; polymers and postchlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride; as well as mixtures of polymers cited with themselves or with other polymerizable compounds. Other examples are PVC grafted polymers with EVA, ABS and MBS. Preferred substrates are also mixtures of the aforesaid homo- and copolymers, preferably vinyl chloride homopolymers, with other op-lactic compounds or / and slastomeric polymers, preferably mixtures with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polyactones. Chlorine-containing polymers are particularly preferably polyvinyl chloride such as suspension polymers or emulsion polymers. In a specific embodiment of the invention the sterically hindered phenolic antioxidant containing a structural element of the formula (la) or (Ib) is of formulas (Illa), (Illb) or (lile) (neither ) n is 2 or 3 Ri is tert-butyl, C 3 to C 8 alkyl of secondary bond or cycloalkyl of C 5 to C 6; R'i is tert-butyl, Ci to Cia primary or secondary linking alkyl, phenyl, phenylalkyl of C to Cg or cycloalkyl of C5 to C6; R3 is Ci to Cis alkyl, Ci to Gis alkoxy, C5 to C6 cycloalkyl or a C-io_-CH2-CO-0- (Ci to C? _) Alkyl group; R'2 is alkylene from Ci to C? , -S-, trimethylene isocyanurate, or a group -CH 2 -CH 2 -CO- (OCH 2 CH 2) p-0 -CO-CH 2 CH 2 - in which p is a number from 1 to 3; R is hydrogen, methyl or a group wherein m is a number from 1 to 10. Alkyl radicals and alkylene radicals, such as those occurring in definitions of general substituents, may be branched or unbranched. Typical examples are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl and heneicosyl. Typical examples of alkylene groups are ethylene, propylene, 2-methylpropylene, 2,2-dimethylpropylene, 2-methyl-2-n-propyl-propylene and 2-ethyl-2-n-butyl-propylene.

Ci alkoxy to _8 is for example methoxy, ethoxy, propoxy, dodecyloxy and octadecyloxy. The alkoxy residues may contain straight alkyl chains or branched alkyl groups. For example, in component c) both u are C alquilo_alkyl or C? 8alkyl and the R ?2 are C alquilo 2alkyl. The partially hindered phenolic antioxidant must have a melting point above 20 ° C in order to be a solid at room temperature. Preferably the melting point is above 25 ° C and in particular above 30 ° C. Likewise the thioether or thioether ester has a melting point of more than 20 ° C in order to be a solid at room temperature . Preferably the melting point is above 25 ° C and in particular above 30 ° C. In particular the preferred sterically hindered phenolic antioxidants are: 2-tert-butyl-4,6-dimethylphenol; 2,4-dimethyl-6- (1 '-methylundecyl-1'-yl) phenol, 2,4-dimethyl-6- (1-methylheptadecyl-l'-yl) phenol, 2,4-dimethyl-6- (1 ' - methyltridecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltetradecyl-1'-yl) phenol and mixtures thereof; 2,2'-ethylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2'-methylenebis (4,6-di-ter) -butylphenol), 2, 2'-ethylidenebis (4,6-di-tert-butylphenol); 2,2'-ethylidenebis (ß-tert-butyl-4-isobutylphenol) or (ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] .The specific compositions are example in which in component b) the sterically hindered phenolic antioxidant is 2-tert-butyl-4,6-dimethylphenol, 2, -dimethyl-6- (1'-methyltetradecyl-1'-yl) phenol or a mixture of these and component c) is di-lauryl-thio-di-propionate, di-stearyl-thio-di-propionate or a mixture thereof. More preferably it is a composition in which in component b) the sterically hindered phenolic antioxidant is 2,4-dimethyl-6- (1'-methyltetradecyl-1'-yl) phenol and component c) is di-lauryl- thio-di-propionate. The compounds of formulas Ia, Ib, Ha, Hb, He, Illa, IHb and HIc are known and largely trade articles. Typically the sterically hindered phenolic antioxidant, component b) is present in an amount from 50 ppm to 2000 ppm, preferably from 100 ppm to 1000 ppm, based on the weight of the halogen-containing monomer. Component c) is, for example, present in an amount from 50 ppm to 2000 ppm, preferably from 100 ppm to 1000 ppm, based on the weight of the halogen-containing monomer. The ratio of component b) to component c) is, for example, from 1:10 to 10: 1. In a specific embodiment of the invention the composition additionally contains a sterically hindered phenolic antioxidant different from that of component b), a phosphorus containing stabilizer, a 2-benzofuranone stabilizer, a sterically hindered amine light stabilizer or a UV absorber. More additives may be present, such as fillers, pigments, optical brighteners etc. Examples of stabilizers and additional additives are given below. 1. Antioxidants 1. 1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol , 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,6-dioctadecyl-4- methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-ethoxymethylphenol, nonylphenols which are metal or branched on the side of the chains, for example 2,6-di-nonyl-4- methylphenol. 1.2. Alkyltiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol. 1.3. Hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol , 2,6-di-tert-butylhydroquinone, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3, 5-di-ter- butyl-4-hydroxyphenyl) adipate. 1.4. Tocopherols, for example α-tocopherol, β-tocopherol, β-tocopherol, d-tocopherol and mixtures thereof (vitamin E). 1.5. Compounds 0-, N- and S-benzyl, for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl -4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate. 1. 6. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy) 5-methylbenzyl) malonate, di-dodecylmercaptoethyl-2, 2- bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] - 2, 2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate. 1.7. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di) -tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol. 1.8. Triazine compounds, for example 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis ( 3, 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 3, 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1, 3, 5-tris (3, 5-di) -tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5- tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine. 1.9. Benzylphosphonates, for example dimethyl-2, 5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4- hi- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the onoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.10. Acylaminophenols, for example 4-hydroxylauranyl, 4-hydroxysteatenyl, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate. 1.11. Esters of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, e. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, '-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane. 1.12. Esters of ß- (3,5-dicyclohexyl-4-hydroxy-nyl) propionic acid with mono- or polyhydric alcohols, eg. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane. 1.13. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, by e j. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane. 1.14. Amides of β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, eg. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) trimethylenediamide, N, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hi-drazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] pyrionyloxy) ethyl] oxamide (Naugard XL-1, supplied by Uniroyal). 1.15. Ascorbic acid (vitamin C) 1.16. Antioxidants to ínicos, for example N, N'-di-isopropil-p-phenylenediamine, N, N '-di-sec-butyl-p-phenylenediamine, N, N' -bis (1,4-dimethylpentyl) -p- phenylenediamine, N, N'-bis (l-ethyl-3-methylpentyl) -p-phenylenediane, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N '-dicyclohexyl-p-phenylenediamine, N, N '-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N' -phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) - N '-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N' -phenyl-p-phenylenediamine, N-cyclohexyl-N '-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N , N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1 -naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylamino-methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N' -tetramethyl-4 , 4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) mino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl ) phenyl] ami na, N-phenyl-1-naphthylamine tert-octylated, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonildiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of isopropyl / mono- and dialkylated isohexyl diphenylamines, a mixture of mono- and dialkylated ter-butyldiphenylamines, 2,3-dihydro-3, 3- dimethyl-4H-l, 4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated ter-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N '-tetraphenyl-1, 4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-) il) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. 2. UV absorbers and light stabilizers 2.1. 2- (2'-HydroxypheniDbenzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- ( 5 '-ter-butyl-2' -hydroxyphenyl-nil) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5 ' -di-tert-butyl-2 '-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec- butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) ) benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) ) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyl-oxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3' - tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5- chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-ethoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2- octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy) 5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3, 3- tetramethylbutyl) -6-benzotriazole-2-ylphenol]; transesterification of the product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH2CH-COO-CH2CH2-3-, in which R = 3 '-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3' - (a, α-dimethylbenzyl) -5 '- (1,1,3,3-tetramethylbutyl) phenyl] -benzotriazole; 2- [2'-hydroxy-3' - (1,1,3,3-tetramethylbutyl) -5 '- (a, a-dimethylbenzyl) phenyl] benzotriazole 2.2. 2-Hydroxybenzophenones, for example or the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4' -trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives. 2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3 , 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl ? 3, 5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate. 2.4. Acrylates, for example ethyl a-cyano-β, β-diphenylacrylate, isooctyl a-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β -methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline. 2.5. Nickel compounds, for example 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol] nickel complexes, such as the 1: 1 or 1: 2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanole, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. methyl or ethyl ester, 4-hydroxy-3, 5-di-tert-butylbenzylphosphonic acid, nickel ketoxy ace complexes, e.g. 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands. 2.6. Sterically hindered amines, for example bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2, 6, 6-pentamethyl-4-piperidyl) sebacate, bis (l-octyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-) piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, Condensate of 1- (2-hydroxyethyl) -2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N, N'-bis (2, 2, 6,6-tetramethyl-4) -piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2, 2, 6, 6-tetramethyl-4-piperidyl) nitrilotriacetate, tetracis (2.2 , 6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '- (1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4- Benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,6,6,6-tetramethylpiperidine, bis (1, 2, 2,6,6-pentamethylpiperidyl) -2-n-butyl-2- ( 2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (l-octyloxy-2, 2,6,6-tetramethylpiperidyl) sebacate, bis (l-octyloxy-2, 2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensates of N, N '-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the 2-chloro condensate ro-4,6-bis (4-n-butylamino-2, 2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, the condensate of 2- chloro-4,6-di- (4-n-butylamino-l, 2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8- acetyl-3-dodecyl-7, 7,9, 9-tetramethyl-l, 3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-l- (2,2,6,6-tetramethyl) -4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine- 2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N, N'-bis (2, 2, 6, 6-tetramethyl-4-) piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of 1,2-bis (3-aminopropylamino) tano and 2,4,6-trichloro-1,3,5 - triazine as well as 4-butylamino-2, 2, 6, 6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine as well as N, N-dibutylamine and 4-butylamino-2, 2,6,6-tetramethylpiperidine (CAS Reg. No . [192268-64-7]); N- (2, 2, 6, 6-tetramethyl-4-piperidyl) -n-dodecyl succinimide, N- (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) -n-dodecyl succinimide, 2-undecyl- 7, 7,9,9-tetramethyl-l-oxa-3,8-di-aza-4-oxo-spiro [4.5] decane, a reaction product of 7, 7, 9, 9-tetramethyl-2 -Cycloundecyl-l-oxa-3, 8-diaza-4-oxospiro- [4, 5] decane and epichlorohydrin, 1, 1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2 - (4-methoxyphenyl) ethene, N, N '-bis-formyl-N, N' -bis (2,6,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, a diester of 4-methoxymethylene-malonic acid with 1, 2, 2, 6, 6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2, 2, 6, 6-tetramethyl-4-piperidyl)] siloxane, a reaction product of maleic acid copolymer anhydride-α-olefin with 2, 2,6,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine. 2. 7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxyanilide, 2,2'-didodecyloxy-5, 5'- di-tert-butoxyanilide, 2-ethoxy-2'-ethyloxanilide, N, N! bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and their mixtures with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxyanilide, mixtures of oxanilides o and p-methoxy-disubstituted and mixtures of o- and p-ethoxy-disubstituted oxanilides. 2.8. 2- (2-Hydroxyphenyl) -1,3,5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy) 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3, 5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) ) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy -3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] - 4, 6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4) -dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl-phenyl) -1, 3, 5-triazine, 2- (2 -hydroxy-4-hexyloxy) phenyl-4,6- diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4-] (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- . { 2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine. 3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N1-salicyloyl hydrazine, N, N'-bis (salicyloylhydrazine, N, N'-bis (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-l, 2, 4- triazole, bis (benzylidene) oxalyl dihydrazide, oxanililida, isopftaloil dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladipoyl dihydrazide, N, N '-bis (salicyloyl) oxalyl dihydrazide , N, N'-bis (salicyloyl) thiopropionyl dihydrazide. 4. Phosphites and phosphonites, for triphenyl phosphite eg E, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis ( 2, 4-di-tert-butylphenyl) entaeritritol diphosphite, bis (2, 4-di-cumylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodeciloxipentaeritritol diphosphite, bis ( 2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6- tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetracis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl -12H-dibenz [d, g] -1,3, -dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-) methylphenyl) ethyl phosphite, 6-fluoro-2, 4, 8, 10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1, 3, 2-dioxaphosphocin, 2, 2 ', 2" -nitrile [triethyltris (3, 3 ', 5, 5' -tetra-tert-butyl-1,1 '-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3, 3', 5, 5 '-tetra-tert-butyl-1,1'-biphenyl-2, 2'-diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1, 3, 2-dioxaphosphine. The following phosphites are especially preferred: Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy), tris (nonylphenyl) phosphite, (B) . Hidroxi1aminas, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N- hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated sebaceous amine. 6. Nitrones, for example N-benzyl-alpha-phenylnitrona, N-ethyl-alpha-methylnitrona, N-octyl-alpha-heptylnitrona, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha- pentadecylnitrone, N-octadecyl-alpha-heptadecyl nitrone, N-hexadecyl alpha-heptadecyl nitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N, N -dialkylhydroxylamine derived from hydrogenated sebaceous amine. 7. reagents peroxides, for example esters of beta-thiodipropionic acid, for example esters of lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutilditiocarba ato, dioctadecyl disulfide, pentaerythritol tetrakis (ß dodecyl mercapto) propionate. 8. Stabilizing polyamides, for example copper salts in combination with iodides and / or phosphorous compounds and salts of divalent manganese. 9. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of high fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatechol or zinc pyrocatechol. 10. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium dioxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. , 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferably are 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyl dibenzylidene) sorbitol, and 1,3: 2, 4-di. (benzylidene) sorbitol. 11. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, bulbs glass, asbestos, talcum, kaolin, mica, barium sulfate, metal oxides and hydroxides, black carbon, graphite, wood flour and flours of fibers of other natural products, synthetic fibers. 12. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, fire retardant agents, antistatic agents and blowing agents. 13. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; U.S.4, 338, 244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3 - [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3 '-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2- ona], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran- 2-one, 3- (3, 5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzo-furan-2-one, 3- (3,4-dimethylphenyl) -5,7-di- ter-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one.

The additives are in convenience added in an amount from 0.01 parts to 10 pairs, preferably from 0.05 parts to 5 parts and in particular from 0.1 to 3 parts based on 100 parts of the halogen-containing polymer. With the exception of the antioxidants described under article 1, these additives are in common added during the mixing phase of the halogen-containing polymer. In a preferred embodiment of the invention a conventional antioxidant, such as for example the one mentioned above under article 1, is additionally present in the composition. Still further additives, which may optionally be added, are for example classic PVC stabilizers, lubricants, pigments, fillers and plasticizers. Examples are given below. a) Zinc Compounds and Other Metal Compounds Organic zinc compounds, which preferably contain a Zn-O bond, are in common zinc enolates, zinc phenolates and / or zinc carboxylates. These latter compounds are from the series of saturated aliphatics and carboxylates of Cx to C22 unsaturated, of the saturated aliphatics and unsaturated C2 to C22 carboxylates, which are substituted by at least one OH group and that whose chain is interrupted by at least one or more than atom 0 (oxa acids), of the cyclic and bicyclic carboxylates containing carbon atoms from 5 to 22, of the phenylcarboxylates which are substituted or unsubstituted by less an OH group and / or alkyl substituted or unsubstituted C1_12 alkyl phenolates, or abietic acid. Zn-S compounds are typically zinc mercaptides, zinc mercaptocarboxylates and zinc ercaptocarboxylates. Examples to be mentioned are the zinc salts of monovalent carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanic acid, 2-ethylhexanoic acid, pelargonic acid, acid decanoic, undecanoic acid, dodecanoic acid, tridecanoic acid, myristyl acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, ricinolic acid, acid 3, 6 -radioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, tolylic acid, dimethylbenzoic acid, ethylbenzoic acid, n-proylbenzoic acid, salicylic acid, p-ter- octylsalicylic, and sorbic acid, cinnamic acid, mandelic acid, glycolic acid; zinc salts of divalent carboxylic acids or monoesters, typically oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, octane-1, 8-dicarboxylic acid, 3, 6, 9-trioxadecane-1, 10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, malic acid, salicylic acid , polyglycol dicarboxylic acid (n = 10-12), italic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and of the di- or triesters of tri-or tetravalent carboxylic acids, typically hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid and also so-called zinc carboxylates or zinc laurylmercaptide, zinc thioglycolate, zinc thiosalicylate, zinc- bis-i-octylthioglycolate, zinc mercaptopropionate, zinc thiolactate, zinc thiomalate, zinc-bis-octylmercaptopropionate, zinc-bis-isooctylthiolactate and zinc-bis-laurylthiomalate. The zinc enolates are preferably acetone acetone, benzoylacetone, dibenzoylmethane as well as acetoacetic acid and benzoyl acetate enolates and also dehydrazetic acid. This is also possible from using inorganic zinc compounds, such as zinc oxide, zinc hydroxide, zinc carbonate, zinc basic carbonate or zinc sulfide. It is preferred to use neutral or basic zinc carboxylates of a carboxylic acid having from 1 to 22 carbon atoms (zinc soaps), typically benzoates or alkanoates, preferably C8 alkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearates and hydroxyoleates, ricinoleate, dihydroxystearates, p-tert-butylbenzoate, or (iso) octanoate. Stearate, oleate, versatate, benzoate, p-tert-butylbenzoate and 2-ethylhexanoate are particularly preferred. In addition to the zinc compounds mentioned, it is also possible to use organic aluminum compounds, magnesium compounds, calcium compounds, barium compounds, potassium compounds or sodium compounds, the anionic radicals corresponding to the groups listed for the compounds of zinc. Preferred compounds of this type include aluminum carboxylate, calcium carboxylate, barium carboxylate, potassium carboxylate or magnesium carboxylate, such as basic aluminum onostate, aluminum basic diestarate, aluminum tristearate, calcium stearate, aluminum octoate. , aluminum-2-ethylhexanoate, calcium-2-ethylhexanoate, barium-2-ethylhexanoate,. potassium-2-ethylhexanoate, laurate aluminum, calcium oleate, barium oleate, calcium-t-butylbenzoate, basic aluminum acetates as well as aluminum enolates or magnesium enolates, such as aluminum acetylacetonate, magnesium acetylacetonate and also aluminum alcoholates or magnesium alcoholates as well as the corresponding barium compounds. Also to be mentioned here are basic oxides, hydroxides, carbonates and carbonates of the metals mentioned above as well as their salts mixed with organic acids. Typical examples are NaOH, KOH, CaO, Ca (OH2), MgO, Mg (OH) 2, CaC03 / MgC03 dolomite, huntite, as well as Na-, K-, Ca fatty acid or Mg salts. In the case of alkaline earth metal carboxylates and zinc carboxylates it is also possible to use adducts thereof with MO or M (0H) 2 (M = Ca, Mg, Ba, Sr or Zn), so-called compounds on the background. The metal compounds described or mixtures thereof can be used in amounts of e.g. 0.0001 to 10, conveniently 0.001 to 5, preferably 0.01 to 3, e.g. , from 0.01 to 1, parts by weight, based on 100 parts of halogen-containing polymer. They can also be obtained as mixtures of salts (coprecipitates). b) Polyols Convenient compounds of this type are for example: pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trimethylolpropane, bis-trimethylolpropane, sorbitol, maltite, isomaltite, lactite, lysine, mannitol, xylitol, inositol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinite, tetramethylolcyclohexanol (TMCH) , tetra-ethylolcyclopentanol, tetramethylolcycloparanol, glycerol, diglycerol, polyglycerol, thiodiglycerol, or 1-0-aD-glucopyranosyl-D-mannitol dihydrate as well as polyvinyl alcohol and cyclodextrins; and also condensates of such polyols, typical dipentaerythritol adipate, glycerol oleate, glycerol trioleate, and the same. Preferred are TMCH, pentaerythritol, dipentaerythritol, sorbitol and disaccharide alcohols. The polyols can be used in an amount of per e. 0.01 to 20, conveniently from 0.1 to 20 and, preferably, from 0.1 to 10, parts by weight, based on 100 parts by weight of component (i). c) 1,3-Dicarbonyl compounds Illustrative examples of 1,3-dicarbonyl compounds are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-heptane-2, 4-dione, benzoylacetone, dibenzoylmethyl, lauroylbenzoylmethane. , palmitoil- benzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoyl ethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl -1-acetylnonano, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoyl-formylmethane, benzoylphenylacetylmethane, bis (cyclohexanoyl) methane, di (pivaloyl) methane, methyl acetoacetate, ethyl acetoacetate, hexyl acetoacetate, octyl acetoacetate, dodecyl acetoacetate or octadecyl acetoacetate, ethyl benzoylacetate, butyl benzoylacetate, 2-ethylhexyl benzoylacetate, dodecyl benzoylacetate or octadecyl benzoylacetate, ethyl stearoylacetate, propyl stearoylacetate, butyl stearoylacetate, hexyl stearoylacetate octyl stearoylacetate and dehydracetoacetic acid as well as zinc, alkali metal, alkaline earth metal or aluminum salts thereof. The 1,3-dicarbonyl compounds can be used in an amount eg. 0.01 to 10, conveniently 0.01 to 3 and, preferably, 0.01 to 2, parts by weight, based on 100 parts by weight of PVC. d) Epoxidized epoxy fatty acids esters In this connection, epoxidized esters of fatty acids from natural sources, such as soybean oil or rapeseed oil, are to be mentioned in particular. The epoxide compounds are preferably used in amounts of e.g. 0.1 parts by weight, based on 100 parts by weight of composition, conveniently from 0.1 to 30, preferably from 0.5 to 25 parts by weight, based on 100 parts by weight of component (i). Other examples are epoxidized polybutadiene, epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl- or 2-ethylhexylepoxystearate, tris (epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3-phenoxy-2, epoxypropane, diglycidyl ether of bisphenol A, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. Suitable epoxides are also derivatives of bisphenol A and bisphenol F, as described, inter alia, in US-A-5 492 949, US-A-5 519 077 and US-A-5 543 449. e) Dihydropyridines and polydihydropyridines Suitable monomeric dihydropyridines are as the compounds described, inter alia, in FR-A-2039496, EP-A-2007, EP-A-362012, EP-A-24754 and EP-A-716123. The preferred compounds are those of formula in which Z is CO, CH. , CO, C? H? , C02-n-C? 2H25 or -C09C, H4-S-n- < -'12 ^ -25 ' The polydihydropyridines are preferably compounds of the following formula wherein T is unsubstituted C1_12 alkyl. L has the same meaning as T. myn are numbers from 0 to 20, k is 0 or 1, R and R are each independently of the other ethylene, propylene, butylene or an alkylene- or cycloalkylenebismethylene group type - (-C H_2JJ -X--) tL. CJpJ H__2-p p is from 2 to 8, t is from 0 to 10, X is oxygen or sulfur.

Such compounds are described in more detail in EP-A-286887. The (poly-) dihydropyridines can be used in the halogen-containing polymer conveniently in an amount of 0.001 to 5 and, preferably, 0.005 to 1, parts by weight, based on 100 parts of the polymer. Thioethylene-bis [5-methoxycarbonyl-2,6-dimethyl-l, 4-dihydropyridine-3-carboxylate] and 1,4-dihydro-2,6-dimethyl-3,5-dicarbododecyloxypyridine are particularly preferred. f) Perchlorates Typical examples are those of formula M (C104) n, in which M e Li, Na, K, Mg, Ca, Ba, Zn, Al, Ce or La. Depending on the valence of M, the index n is 1, 2 or 3. Perchlorates can be complexes with alcohols or ether alcohols. Each perchlorate can be used in different normal forms of presentation; for ex. As a salt or aqueous solution of the salts or free acid applied to a substrate such as PVC, calcium silicate, zeolites or hydrotalcites, or can be obtained by the chemical reaction of hydrotalcite with perchloric acid. Perchlorates can be used in an amount of eg. 0.001 to 5, conveniently 0.01 to 3, particularly preferably 0.01 to 2, parts by weight, based on 100 parts by weight of component (i). g) Hydrotalcites and zeolites The composition of these compounds is known to the skilled person, eg. , DE-A-3843581, US-A-4000100, EP-A-062813, WO-A-93/20135. The compounds of the hydrotalcite series can be described by the general formula III M 2 + lx • M 3 + x • (OH) 2 • (A n ") x / n • mH 2? (III), in which M 2+ = one or more of the metals selected from the group consisting of Mg, Ca, Sr, Zn and Sn, M3 + = Al or B, A is a valence anion n, n is a number from 1 to 2, 0 <x < 0.5, m is a number from 0 to 20.

An = OH ~, CIO4", HC03 ~", CH3COO ", C6H5COO", C032 ~, S? 4 ~ ", coo- HS04 ~ COO", (CHOHCOO) 22 ~, (CH2COO) 22 ~, CH3CHOHCOO ~, HP ? 32 ~ or HP042"is preferred It is also possible to use hydrotalcites comprising LiOH or Li2C03 ("solid solution"). Examples of hydrotalcites are A1203.6MgO.C02.12H20, Mg4 5Al2 (OH) 13.C03.3.5H20, 4MgO. Al203. C02.9H20, 4Mg0. A1203. C02.6H20, Zn0.3Mg0.Al203.C02.8-9H20 and ZnO.3Mg0. Al203.C02.5-6H20.

Compounds of the zeolite series (alkali metal aluminosilicates or alkaline earth metal aluminosilicates) can be described by the general formula (IV) Mx / n [(Al? 2)? (Si? 2) y]. H20 (IV), in which n is the charge of the cation M; M is an element of the first or second main group of the Periodic Table, such as Li, Na, K, Mg, Ca, Sr or Ba, or Zn, and: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; And it is a number from 0 to 300, preferably from 0.5 to 30. Structures can be found, for example, in "Atlas of Zeolite" by .M. Meier and D.H.Olson, Butter orth-Heinemann, 3. Ed. 1992. Examples of zeolites are sodium aluminosilicates of formulas Na12Al12Si12048. 27 H20 [zeolite A], Na6 l6Sig? 24.2 NaX.7. 5 H20, X = OH, halogen, C104 [sodalite]; Na6Al6Si30O72. 24 H20; Na8Al8Si40O96 .24 H20; Na1gAl1gSi24O80. 16H20; Na16Al16Si32096. 16H2O; Na56Al56Si136O384 .250H2? [zeolite Y], Na86Al86Si106O384.264H2O [zeolite X]; as well as zeolite X- and Y- in a A1 / Si ratio of 1/1; or the zeolites which are represented by the partial or complete exchange of the sodium atoms by Li atoms, K atoms, Mg atoms, Ca atoms, Sr atoms or Zn atoms such as (Na, K) 10Al10Si22? 64.20H2O; Ca4-5Na3 [(A102) 12 (S02) 12] .30 H20; K9Na3 [(Al02) 12 (SiO2) 12] .27 H20. Other suitable zeolites are: Na2? "Al2? 3 * (2 to 5) Si? 2" (3.5 to 10) H2O [zeolite P] Na2? "Al2? 3 * 2 SIO2 '(3.5-10) H2? (Zeolite) MAP) or the zeolites which can be represented by the partial or complete exchange of Na atoms by Li atoms, K atoms or H atoms, typical (Li, Na, K, H) i0Al? 0Si22? 64.20H2? , KgNa3 [(AIO2) 12 (Si? 2) 12] -27 H2O, K4Al4SÍ4? I6 * 6H2? [Zeolite KF], a8AlsSÍ40? 96 -24H20 zeolite D, as described in Barrer et al., J. Chem Soc. 1952, 1561-71, and in US 2 950 952. The following zeolites are also convenient: K-offerite, as described in EP-A-400 961; R zeolite, as described in GB-A- 841 812, zeolite LZ-217, as described in US-A-4 503 023, calcium free zeolite LZ-218, as described in US-A-4 333 859, zeolite T, zeolite LZ-220, as described in US Pat. described in US-A-4 503 023; a3K6AlgSÍ27? 72.21 H2O [zeolite L]; zeolite LZ-211, as described in US-A-4 503 023; zeolite LZ-212, as described in U S-A-4 503 023, zeolite O, zeolite LZ-217, as described in US-A-4 503 023; zeolite LZ-219, as described in US-A-4 503 023; Rho zeolite, LZ-14 zeolite, as described in US-A-4 503 023; ZK-19 zeolite, as described in Am. Mineral. 54 1607 (1969); zeolite W (K-M), as described in Barrer et al. J. Chem. Soc. 1956, 2882; Na3? l3? YES66? l92-98 H2O [zeolite ZK-5, zeolite Q]; as well as A1P0 compounds with zeolite structure. It is preferred to use zeolite types P of formula M20 * Al203"xSi0_" and H_0 (IVa), wherein x is from 2 to 5, y, and is from 3.5 to 10, and M is an alkaline earth metal atom and, very particular preferably, zeolite MAP of formula IVa, wherein x is 2 y, and is 3.5 to 10. Preferably it is Na-P zeolite, for ex. M is Na. This zeolite is usually obtained in the variants Na-P-1, NaP-2 and Na-P-3, which differ from each other in their cubic, tetragonal or ortho-morphic structure (RMBarrer, BMMunday, J.Chem Soc. A 1971, 2909-14). The literature mentioned above also describes the preparation of zeolite P-1 and P-2. According to this literature, zeolite P-3 is very rare and is therefore of strong radical interest. The structure of zeolite P-l corresponds to the wave-like structure known from Atlas of Zeolite Structures. The most recent literature (EP-A-384 070) elaborates a difference between cubic (zeolite B or Pc) and tetragonal (zeolitea P] _) zeolite of type P. It is also the newest mention of zeolites of type P which has Yes ratio: l of less than 1.07: 1. These zeolites are called MAP or MA-P for "maximum aluminum P". It depends on the method of In the preparation, zeolite P may contain minor amounts of other zeolites. A very pure zeolite P was described in WO-A-94/26662. Within the scope of this invention, it is also possible to use those water insoluble sodium algiminosilicate fine particles which can be precipitated and crystallized in the presence of water soluble organic and inorganic dispersants. These can be added to the reaction mixture in any way before or during the precipitation or crystallization of sodium zeolite A, sodium zeolite P, sodium zeolite X and sodium zeolite Y are particularly preferred. Hydrotalcites and zeolites can be also obtained compounds that occur in natural minerals or compounds that occur synthetically. The hydrotalcites and / or zeolites can be used in amounts of e.g. 0.1 to 50, conveniently from 0.1 to 10, and preferably from 0.1 to 5, parts by weight, based on 100 parts by weight of halogen-containing polymer. h) Alkyl alumocarbonates (dausonites), These compounds can be represented by the formula. { (M2?) M. (Al203) n-Zo-pH20} (V), wherein M is H, Li, Na, K, Mg? / 2, Ca? / 2, Sr? / 2 or Zn? / 2; Z is C02, SO2, (Cl2? 7)? / 2, B4O6, S2O2 (thiosulfate) or C2O2 (oxalate); m, if M = Mg? / 2 or Ca? / 2, it is a number from 1 to 2, and in all other cases a number from 1 to 3; n is a number from 1 to 4; or is a number from 2 to 4; and p is a number from 0 to 30. The compounds of alumo salts of formula (V) which may be used, may be prepared mineral compounds that occur naturally or in a synthetic manner. The metals can be partially exchanged one from the other. The aforementioned alumo salt compounds are crystalline, partially crystalline or amorphous or can be in the form of a dried gel. The compounds of alumous salts can also be obtained in rare crystalline modifications. EP 394670 describes a method for the preparation of such compounds. Typical examples of alumo salt salt compounds occur naturally are indigirite, tunisite, alumohydrocalcite, para-alumohydrocalcite, strontiodreserite and hydroestrontiodreserite. Other examples of alumo salt compounds are: potassium alumocarbonate. { (K2O). (AI2O3). (CO2) 2.2H20} , alu sodium otiosulfate. { (Na2?). (AI2O3). (S2O2) 2 -2H20} , potassium alumosulfite. { (K2O). (AI2O3). (SO2) 2 • 2H20} , calcium alumooxalate. { (CaO) (AI2O3). (C2O2) 2 • 5H20} , magnesium alumotetraborate. { (MgO). (AI2O3). (B4O6) 2 • 5H20} , í ([Mgo.2Nao.6] 2?). (AI2O3). (CO2) 2 • 4. IH2O} ,. { ([Mgo.2Nao.6l20). (AI2O3). (CO2) 2 • 4.3H 0.}. Y . { ([Mgo.3Nao.4J20). (AI2O3). (CO2) 2.2 • .9H20} . The mixed alumosal compounds can be obtained by methods known per se by cation exchange, preferably from alkali metal salt compound or by combination of precipitation (see, for example, US 5 055 284). Preferred alumo salt compounds are those of the formula above, in which M is Na or K; Z is CO2, SO2 or (Cl2? 7)? / 2; m is 1-3; n 1-4; or is 2-4, and p is 0-20. Z is preferably CO2 in particular. Other preferred compounds are those which may be represented by the following formulas: M2O.AI2O3. (C02) 2-PH20 (la), (M2O) 2 • (AI2O3) 2 • (CO2) 2 -pH2? (Ib), M20. (Al2? 3) 2- (C? 2) 2-PH2? (le), in which M is an etal, such as Na, K, Mg? / 2, Ca? / 2, Sr? / 2 or Zn? / 2, and p is a number from 0 to 12. Sodium aluminohydroxycarbonate (DASC) and the potassium homolog compound (DAPC) are particularly preferred.

In place of the dausonites, it is also possible to use silicates having cation exchange properties, such as bentonites, magadiite, haremite, and the like. The Dausonites can be used in an amount of eg. 0.01 to 50, conveniently from 0.1 to 10, particularly preferably from 0.1 to 5, parts by weight, based on 100 parts by weight of halogen-containing polymer. i) Plasticizers Suitable organic plasticizers are, for example, those of the following groups: A) Phthalates: Typical examples of such plasticizers are dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-iso- octyl phthalate, di-iso-nonyl phthalate, di-iso-decyl phthalate, di-iso-tridecyl phthalate, dicyclohexyl phthalate, di-methylcyclohexyl phthalate, dimethyl glycol phthalate, dibutyl glycol phthalate, benzylbutyl phthalate and diphenyl phthalate as well as mixtures of phthalates , such as C7_9 alkyl and C9_ 1X linear predominant alcohols, n-C6_ alkyl phthalates and n-C8_10 alkyl phthalates. Of these, dibutyl phthalate, dihexyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-iso-octyl phthalate, di-iso-nonyl phthalate, di-iso-decyl phthalate, di-iso-tridecyl phthalate and benzylbutyl phthalate as well as the aforementioned alkyl phthalate mixtures. Particular preference is given to di-2-ethylhexyl phthalate, di-iso-nonyl phthalate and di-iso-decyl phthalate, which are also known by their normal abbreviations DOP (di-octyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate). B) Esters of aliphatic dicarboxylic acids, in particular esters of adipic acid, azelaic acid and sebacic acid Typical examples of such plasticizers are di-2-ethylhexylladipate, di-isooctyladipate (mixture), di-isononyl adipate (mixture), di-isodecyl adipate (mixture), benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and di-isodecyl sebacate (mixture). Di-2-ethylhexyl adipate and di-isooctyl adipate are preferred. C) TrimelitATES, typical tri-2-ethylhexyl tri elite, tri-isodecyltrimellitate (mixture), tri-isotridecyl trimellitate, tri-isooctyltrimellitate (mixture) as well as trialkyl-C6_8 trimellitate, trialkyl-C5_10 trimellitate, trialkyl-C.7_9 trimellitate and trialkyl-C9_11 trimellitate. The last mentioned trimellitates are obtained by esterifying the trimellitic acid with the corresponding alkanol mixtures. Preferably they are tri-2-ethylhexyl trimellitate and the mentioned trimellitates of alkanol mixtures. Normal abbreviations used are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimellitate) and TITD ™ (triisotridecyl trimellitate). D) Epoxid plasticizers These are in principle the unsaturated epoxidized fatty acids, such as epoxidized soybean oil. E) Polymeric plasticizers The most customary initial materials used for the preparation of polyester plasticizers are: dicarboxylic acid, such as adipic acid, phthalic acid, azelaic acid and sebacic acid; diols, such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol. F) Phosphoric acid esters Typical examples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyldi-phenyl phosphate, cresylphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixileneyl phosphate. Tri-2-ethylhexyl () phosphate and Rephos 50 and 95 (ex. FMC) are preferred. G) Chlorinated hydrocarbons (paraffins) H) Hydrocarbons I) Monoesters, by e. , butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkyl sulfonate. J) Glycol esters, eg. , diglycol benzoate. The definitions and examples of plasticizers from groups A) to J) are found in the following reference books: "Taschenbuch der Kunststoffadditive", edited by R. Gachter and H. Müller, Cari Hanser Verlag, 1989, chapter 5 S 341-442 . "PVC Technology", editor .V. Titow, 4th Ed., Elsevier Publishers, 1984, chapter 6, pages 147-180. It is also possible to use mixtures of different plasticizers. The plasticizers can be used in an amount of eg. 5 to 120, from 10 to 100, parts by weight, based on 100 parts by weight of PVC. j) Suitable lubricants are for example: Montan wax, fatty acid ester, PE waxes, amide waxes, chloroparaffin, glycerol ester, solid or liquid paraffin or alkaline earth metal soaps, or silicone-based lubricants, as described in EP -A-225261. Lubricants which can be used are also described in "Taschenbuch der Kunststoffadditive", edited by R. Gachter and H. Müller, Carl Hanser Verlag, 3rd Ed. 1989, pages 478-488. Prior to being added to the polymeric materials, the lubricants can also be mixed with the stabilizers. k) Convenient fillers ("Handbook of PVC-Formulating", by EJ Wickson, John Wiley &Sons, New York 1993, p.393-449) are reinforcing agents ("Taschenbuch der Kunststoffadditive", editors R. Gáchter and H Müller, Cari Hanser Verlag, 3rd Ed. 1989, pages 549-615) can be for example: calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibers, talc, kaolin, chalk, mica, metal oxides and metal hydroxides, black carbon or graphite. Chalk is preferred. 1) Pigments Suitable materials are known by a person esperta. Typical examples of inorganic pigments are Ti? 2, black carbon, Fe2? 3, Sb2? 3, (Ti, Ba, Sb)? 2, Cr2? 3, spinels, such as cobalt blue and green cobalt, Cd (S, Se ), blue ultramarine. Ti 2, also in micronized form, is preferred. Organic pigments are, for example, azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, pyrrolopyrrilidone pigments and anthraquinone pigments. Plus Details are found in "Handbook of PVC For ulating", E.J. Wickson, John Wiley & Sons, New York 1993, p. 449-474. m) Organotin Compounds Organotin compounds are, for example, organotin oxides, organotin sulfides, organotin carboxylates, organotin mercaptocarboxylates, mercaptide organotin and / or organotin mercaptocarboxylates, such as dibutyltin oxide, dioctyltin maleinate, dibutyltin semiester maleic acid, bis-dibutyltin-2-ethylhexanoate oxide and other SnO compounds, as described, among others, in EP-A-573394. Suitable organotin mercatides are, for example, compounds of general structure RnSn (SA) _n, in which R is, among others, a methyl, butyl, octyl, lauryl or carbobutoxyethyl group, n is 1 or 2, and A is typically a decyl, dodecyl or carboalkoxymethyl or carboalkyloxyethyl radical, and the alkoxy molecule is a C6 alkoxy a. Cis straight chain or branched or a cycloalkoxy radical of C5 to C8. Illustrative examples of such tin compounds are dimethyltin bis-carboisooctyloxymethyl mercaptide, dibutyltin dilauryl mercaptide, dioctyltin bis-carbo-2-ethylhexoxymethyl mercaptide, dimethyl tin bis ercaptoethyl stearate, octyltin tris-carbo-2-ethylhexoxymethyl mercaptide, monomethyltin mercaptoethyl oleate sulphide and bis-dimethyltin mercaptoethyl stearate sulfide. n) Organic Nitrogen Compounds Suitable organic nitrogen compounds are, for example, ureas and thioureas, aminobenzenesulfonates, aminobenzoates, aminobenzamides, cyanamides, dicyandes, guanidines, guanamines, melamines, indoles, aminocrotonates, tetrazoles, triazoles, substituted aminotriazoles, -aminophenols, inouracils, pyrroles, aminopyrroles, and others, as described, among others, in DE-A-746 081, US-A-2 557 474, DD-A-652, DE-A-871 834, EP-A-174 412, DE-A-1 162 073, US-A-2 367 483, GB-A-923 319, DE-A-862 512, DE-A-2 524 659, DE-A-1 544 768, DE-A-1 134 197, EP-A-2 756, DE-A-3 048 659, DE-A-3 602 367, EP-A-48 222, EP-A-41 479, EP- A-65 934, EP-A-22 087, EP-A-465 405 and EP-A-390 739. The optional additives mentioned above can be added to the polymers for example during the composition phase in known manner, by mixing of the compounds and also optional additives with the halogen-containing polymer using known apparatus two such as mixers, calenders, mixers, extruders, mills and Similar. In this process they can be added alone or as a mixture, or also in the form of so-called batch mixtures. The novel polymer compositions can be brought to the desired shape by known methods, such as calendering, extrusion, injection molding, sintering or spinning, and also by extrusion by melt molding or processing by the plastisol process. The polymer compositions can also be processed to foam. The final polymer compositions are convenient eg. , for semi-rigid formulations or flexible formulations, for example for flexible formulations for wire linings, insulation cable, floors, tubes and closing profiles. In the form of semi-rigid formulations, said polymer compositions are suitable for decorative films, foams, agricultural covers, pipes, closure configurations, office films, extruded configurations and plates, floor and panel films, coating materials and coating materials. leather and artificial leather as well as anti-scratch films (for use in cars). In the form of rigid formulations, the compositions are suitable for articles for hollow articles (bottles), packaging films, thermoformable films, blow films, films anti-slamming (automobiles), pipes, foams, heavy configurations (window frames), wall light configurations, construction configurations, capes, hardware, and domestic appliances (computers and domestic applications) as well as other injection molded articles. Examples of the use of the compositions stabilized according to the invention as plastisols are artificial leather, coating materials, floors, textile coating, wall coverings, reel coatings, antiscratching films and automotive anticorrosives. Examples of sintered applications of the polymer compositions stabilized according to this invention are lubricants, mold lubricant and spool coatings. Another aspect of the invention is a process for the stabilization of halogen-containing polymers against thermal degradation, which process comprises adding to the halogen-containing polymer during the polymerization process b) a sterically hindered phenolic antioxidant with a melting point of more than 20 ° C containing a structural element of formula (la) or (Ib) wherein n is 2 or 3 Ri is tert-butyl, secondary alkyl bond of C3 to C.8 or cycloalkyl of C5 to C6; R'i is terbutyl, primary or secondary alkyl bond of Ci to C? 8, phenyl, phenylalkyl of C7 to Cg or cycloalkyl of C5 to Cs; R3 is Ci to Cis alkyl, Ci to C8 alkoxy or C5 to C6 cycloalkyl; R'2 is divalent or trivalent bridging group; * denotes a direct link or is hydrogen; R2 is hydrogen, methyl or a group wherein m is a number from 1 to 10; and c) a thioether or thioether ester with a melting point of more than 20 ° C of formula (Ha), (Hb) or (He) (He) in which Rn and Ri2 are independently alkyl from Ci to C? 8 k is 2 to 4; and X is 2-methyl-l, 2,3-propane-triyl- or 1, 2, 3, 4-methano-tetryl-.

In a specific embodiment the process for the stabilization of the halogen-containing polymers against thermal degradation comprises adding to the halogen-containing polymer, which is in an aqueous suspension or emulsion during or after the polymerization process b) a sterically hindered phenolic antioxidant with a melting point of more than 20 ° C containing a compound of formula (la) or (Ib) in which n is 2 or 3 Ri is tert butyl, secondary alkyl bond of C3 to C? 8 or cycloalkyl of C5 to e; R'i is terbutyl, primary or secondary linking alkyl of Ci to C_8, phenyl, phenylalkyl of C to Cg or cycloalkyl of C5 to C5; R3 is C1 to C8 alkyl, Ci to C8 alkoxy, C5 to C6 cycloalkyl or CH2-CH2-CH2-CO-0- (Ci to C_8) alkyl; R'2 is a divalent or trivalent bridging group; R is a group R is hydrogen, met wherein m is a number from 1 to 10; and c) a thioether or thioether ester with a melting point of more than 20 ° C of formula (Ha), (Hb) or (He) (He) in which Rn and R? they are independently Ci to C alkyl? 8 k is 2 to 4; and X is 2-methyl-l, 2,3-propane-triyl- or 1, 2, 3, 4-methano-tetryl-.

The definitions, preferences and optional additives given above, also applied to the polymerization process. For example, PVC can be produced from vinyl chloride monomer (VCM) by three different processes. The most widely used is the type of polymerization suspension, with approximate amounts of 80 to 85%. Drops of liquid vinyl chloride are dispersed in water using a protective coliode in a stirred pressurized reactor. Polymerization occurs within the droplets as a result of the use of an oil-soluble initiator. The product is in the form of 100-150 μm porous diameter grains. Another process is the emulsion route, in which the monomer is dispersed in water, using agitation and powerful surfactants and the polymerization is carried out in the aqueous phase, using a water soluble initiator. The polymerization product is in the form of an aqueous latex dispersion dispersion of PVC particles in diameter 0.1-2.0 μm. These are dry-drilled to form large agglomerates, which are ground before be dispersed in solvents and plasticizers to give plastisols, used in a variety of applications of dispersive applications and immersion applications. The third route is volume or mass polymerization. As the name implies the polymerization is carried out in vinyl chloride (VCM) in the absence of water. A review of PVC making is for example described in Encyclopedia of Polymer Science and Engineering, second edition, vol. 17, pages 295-376. The compounds b) and e) can be added during the polymerization reaction or after the reaction is completed. With respect to the polymerization of vinyl chloride, the blunt amount of polyvinyl chloride is prepared by suspension polymerization. In this process, the vinyl chloride monomer and the initiator are dispersed by stirring in a water phase at its own temperature and pressure. Suspended agents such as methyl or ethyl cellulose, gelatin, polyvinyl alcohol or other water-soluble polymers are used to stabilize the suspension during the polymerization reaction. Unreacted VCM is removed by a vacuum stripping process. The fine polymer granules in the form of a mixture are discharged from the reactor and centrifuged or filtered to remove the water. TO through washing and drying the polymer to remove traces of the stabilizing suspension and the reaction medium concludes the process. At the end of the polymerization cycle the pressure in the system begins to drip, followed very closely by a peak in the polymerization rate. Beyond the peak, the velocity begins to drip clearly and the globular polymer becomes less porous as the free monomer is absorbed in the polymer and polymerizes. Such a change in character in the particle, both in terms of porosity and particle size distribution, is disadvantageous for elaboration in terms of reducing the development and economy of production. Therefore, the porous structure of the granulate is desired to increase trapped plasticizers to form dry mixtures for various extrudates or calendering operations. In order to avoid such adverse effects, the manufacturing will terminate the polymerization reaction prior to completing the monomer conversion. The elaboration experience will better determine the point at which the polymerization is finished to give high quality polymer, although 70 to 90% the conversion reflects a general point of termination. Components b) and c) are preferably added to this phase of PVC processing.

Particularly preferred is a process in which the polymerization is a polymerization suspension and the components b) and e) are added as an emulsion to the mixture towards the end of the polymerization reaction. A further aspect of the invention is the use of a sterically hindered phenolic antioxidant with a melting point of more than 20 ° C together with a thioether or thioether ester with a melting point of more than 20 ° C in accordance with claim 1 for the thermal stabilization of aqueous suspensions or emulsions of halogen-containing polymers. The following examples illustrate the invention.

General polymerization procedure: A standard PVC polymerization reaction is carried out in accordance with the suspension process in batch operation. A double jacketed pressure reactor of a volume of 5000 ml is operated at a temperature of 57 ° C, and a stirring speed of 1000 rpm. The pressure and temperature in the reactor during the reaction are recorded. The following recipe is added to the reactor: 1000 ml demineralized water, degassed 375 g vinyl chloride monomer 1500 mg polyvinyl alcohol, suspending agent 0.1 mol-% (based on vinyl chloride monomer) of initiator di-2-ethylhexylperoxodicarbonate, 75% in isodecane (Luperox 233M®, supplier: Atofine) 300 ppm (based on the weight of vinyl chloride monomer) of the additives given in table 1 are added at the beginning of the drop pressure (after approximately 3h reaction time). After an additional reaction time of 1 hour, the reactor is degassed, and the polymer obtained is separated by filtration. The crude polymer obtained is washed with water, filtered, washed with ethanol, and dried under vacuum at 40 ° C, until constant remaining weight. Yield: 88%.

Evaluation of the thermal stability of PVC resin: The heat stability of PVC resins is evaluated by measuring the dehydrochlorination reaction using a "763 PVC Thermomat®" (supplier Metrohm AG, CH 9101 Herisau, Switzerland). The amount of hydrochloric acid released from the resin PVC resin is measured by its thermal instability. The amount of hydrochloric acid is quantified by dissolving it in the water, and measuring the conductivity of the solution (see Table 1). The length is taken to reach a certain level of conductivity, the most stable is the resin. Table 1: * Test: dehydrochlorination at 180 ° C, air (minutes to reach a conductivity of 60 microsiemens / cm) Preparation of PVC compounds and evaluation of their thermal stability: The heat stability of PVC compounds is measured by ground preparation of mixtures based on the following recipe: PVC resin (S-PVC K-60) 300 g Commercial processing medium 9 g Wax 2 g Calcium stearate 2 g Methyl tin mercatur stabilizer 1 g The mixture is placed in a roll mill heater 2 about 195 ° C for up to 15 minutes. Every 3 minutes the material is removed from the mill and pressed into plates. The color (yellowish index, YI according to DIN 6174) of the plates is measured. The lowest YI, the best of the thermal stability compounds of the PVC compound (Table 2). The results in Table 2 clearly indicate that the stabilization according to the present invention increases the stability during the composition step.

Table 2 Thermal stability (color) of the PVC compound Irganox 245® Compound 1 Irganox 1076® Irganox 1141® mixture of compound 1 and Irganox 1076, 4: 1; DLTDP is di-lauryl-thio-di-propionate All compounds are supplied by Ciba Specialty Chemicals.

Claims (15)

1. CLAIMS 1. A composition characterized by comprising c) a halogen-containing polymer or copolymer in the form of an aqueous suspension or emulsion; d) a sterically hindered phenolic antioxidant with a melting point of more than 20 ° C containing a compound of formula (Ia) or (Ib) wherein n is 2 or 3 Ri is tert-butyl, C3 to C8 alkyl of secondary bond or cycloalkyl of C5 to C6; R'i is tert-butyl, C 1 -C 8 alkyl of primary or secondary bond, phenyl, phenylalkyl of C to Cg or cycloalkyl of C 5 to C 6; R 3 is C 1 to C 8 alkyl, C 1 to C 8 alkoxy, C 5 to C 6 cycloalkyl or CH 1 -CH 2 -CO-0- (Ci to C 8) alkyl; R'2 is a divalent or trivalent bridging group; R is a or hydrogen; R2 is hydrogen, methyl or a group wherein m is a number from 1 to 10; and c) a thioether or thioether ester with a melting point of more than 20 ° C of formula (Ha), (Hb) or (He) wherein 10 n and Ri are independently C 1 to C 8 alkyl is 2 to 4; and X is 2-methyl-1,2, 3-propane-triyl- or 1, 2, 3, 4-methano-tetryl-.
2. 2. A composition according to claim 1 characterized in that the sterically hindered phenolic antioxidant contains a structural element of formula (la) or (Ib) is of formulas (Illa), (IHb) or (HIc) n is 2 or 3 Ri is tert-butyl, C 3 to C 8 alkyl of secondary bond or cycloalkyl of C 5 to C 6; R'i is tert-butyl, Ci to C 8 alkyl of primary or secondary bond, phenyl, phenylalkyl of C7 to Cg or cycloalkyl of C5 to C6; R3 is C1 to C8 alkyl, Ci to C8 alkoxy, C5 to C6 cycloalkyl or an alkyl group -CH2-CH2-CO-0- (Ci to C8); R'2 is alkylene of Ci to C? 2, -S-, trimethylene isocyanurate, or a group -CH2-CH2-CO- (OCH2CH2) p-0-CO-CH2CH2- in which p is a number from 1 to 3; R2 is hydrogen, methyl or a group wherein m is a number from 1 to 10.
3. 3. A composition according to claim 1 characterized in that the halogen-containing polymer is VC.
4. 4. A composition according to claim 1 characterized in that in compound c) both Rn are C? 2 alkyl or C? 8 alkyl and R_2 are C? 2 alkyl.
5. A composition according to claim 1 characterized in that in compound b) the sterically hindered phenolic antioxidant is 2-tert-butyl-4,6-dimethylphenol; 2,4-dimethyl-6- (1 '-methylundec-1' -yl) phenol, 2,4-dimethyl-6- (1-methylheptadec-1-yl) phenol, 2, 4-dimethyl-6- (1 '-methyltridec-1' -yl) phenol, 2,4-dimethyl-6- (1'-methyltetradec-1-yl) phenol and mixtures thereof; 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-ethylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis (4,6-di-ter) -butylphenol), 2, 2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol) or (ethylenebis (oxyethylene) bis [3- ( 5-tert-butyl-4-hydroxy-m-tolyl) ropionate].
6. 6. A composition according to claim 1 characterized in that in compound b) the sterically hindered phenolic antioxidant is 2-tert-butyl-4,6-dimethylphenol, 2,4-dimethyl-6- (1'-methyltetradec-1 '- il) phenol or a mixture of these and component c) is di-lauryl-thio-di-propionate, di-stearylthio-di-propionate or a mixture thereof.
7. 7. A composition according to claim 1 characterized in that in compound b) the sterically hindered phenolic antioxidant is 2, -dimethyl-6- (1'-methyltetradec-1'-yl) phenol and component c) is di- lauryl-thio-di-propionate.
8. 8. A composition according to claim 1 characterized in that the sterically hindered phenolic antioxidant, component b) is present in an amount from 50 ppm to 2000 ppm based on the weight of the halogen-containing polymer.
9. 9. A composition according to claim 1 characterized in that component c) is present in an amount from 50 ppm to 2000 ppm based on the weight of the halogen-containing monomer.
10. 10. A composition according to claim 1 characterized in that the ratio of component b) to component c) is from 1:10 to 10: 1.
11. 11. A composition according to claim 1 characterized in that it additionally contains a sterically hindered phenolic antioxidant different from that of component b), a phosphorus-containing stabilizer, a 2-benzofuranone stabilizer, a sterically hindered amine light stabilizer or a UV-absorber. .
12. 12. A process for the stabilization of halogen-containing polymers against thermal degradation, characterized in that the process comprises adding to the halogen-containing polymer, which is an aqueous suspension or emulsion during or after the polymerization process b) a phenolic antioxidant sterically hindered with a melting point of more than 20 ° C containing a compound of formula (la) or (Ib) wherein n is 2 or 3 Ri is tert-butyl, C3 to 8 alkyl of secondary bond or cycloalkyl of C5 to e; R'i is tert-butyl, C 1 -C 8 alkyl of primary or secondary bond, phenyl, phenylalkyl of C 7 to Cg or cycloalkyl of C 5 to C 6; R3 is C1 to C4 alkyl, Ci to C8 alkoxy, C5 to C6 cycloalkyl or CH2-CH2-CH2-CO-0- (Ci to C? 8) alkyl; R'2 is a divalent or trivalent bridging group; R is a group R2 is hydrogen, wherein m is a number from 1 to 10; and c1) 0 a thioether or thioether ester with a melting point of more than 20 ° C of formula (Ha), (Hb) or (lie) wherein 15 Rn and R12 are independently alkyl from Ci to Cis k is 2 to 4; Y X is 2-methyl-1, 2, 3-? Ropano-triilo- or 1, 2, 3, 4-methano-tetrilo-.
13. 13-. A process according to claim 12 characterized in that components b) and c) are added at the end of the polymerization reaction.
14. 14. A process according to claim 12 characterized in that the polymerization is a suspension polymerization and the components a) and b) are added as an emulsion to the mixture at the end of the polymerization reaction.
15. 15. The use of a sterically hindered phenolic antioxidant with a melting point of more than 20 ° C together with a thioether or thioether ester with a melting point of more than 20 ° C in accordance with claim 1 for thermal stabilization of aqueous suspensions or emulsions of halogen-containing polymers.