GB2345695A - Stabilizer combinations for halogen-containing polymers - Google Patents

Abstract

A stabilizer combination for halogen-containing polymers, comprises A) at least one organic zinc compound with a Zn-O bond and/or a Zn-S bond or an inorganic zinc compound and B) at least one compound of the formula <EMI ID=1.1 HE=41 WI=86 LX=213 LY=549 TI=CF> <PC>in which the radicals and symbols have the following meanings:<BR> R<SB>1</SB> : H or C<SB>1</SB>-C<SB>8</SB>alkyl, C<SB>3</SB>-C<SB>8</SB>alkenyl, C<SB>7</SB>-C<SB>9</SB>phenylalkyl or C<SB>5</SB>-C<SB>8</SB>cycloalkyl;<BR> R<SB>5</SB>: H, C<SB>1</SB>-C<SB>8</SB>alkyl, C<SB>3</SB>-C<SB>8</SB>alkenyl, C<SB>5</SB>-C<SB>8</SB>cycloalkyl or G; <EMI ID=1.2 HE=25 WI=43 LX=183 LY=1209 TI=CF> <PC>m: 0 or 1; q: 1 or 2;<BR> the group L: -CH<SB>2</SB>-CHR<SB>6</SB>-, -(CH<SB>2</SB>)<SB>3</SB>-, CH=CH-, <EMI ID=1.3 HE=27 WI=40 LX=975 LY=1527 TI=CF> <EMI ID=1.4 HE=23 WI=97 LX=186 LY=1819 TI=CF> <PC>R<SB>6</SB> : H, C<SB>1</SB>-C<SB>12</SB>alkyl;<BR> and Y : -CH<SB>2</SB>-CH(OH)-CH<SB>2</SB>-.

Description

4-Acylamido-piperidine compounds in stabilizer combinations for chlorine-containing polymers The invention relates to a stabilizer combination comprising an organozinc compound with an Zn-0 and/or Zn-S bond, in particular a zinc carboxylate, and at least one compound of the formulae l, ll, ill and IV depicted below, which is suitable for stabilizing chlorine- containing polymers, especially PVC.

PVC can be stabilized by a range of additives. Compounds of lead, of barium and of cadmium are particularly suitable for this purpose, but are nowadays controversial on ecological grounds (cf."Taschenbuch der Kunststoffadditive", Eds. R. Gachter and H.

Muter, Cari Hanser Verlag, 3rd Edition, 1989, pages 303-311, and Kunststoff Handbuch PVC, Volume 2/1, G. W. Becker, D. Braun, Carl Hanser Verlag 1985, pages 531-538). The search is therefore continuing for effective stabilizers and stabilizer combinations devoid of disadvantageous properties.

Sterically hindered amines have already been added to the PVC as light stabilizers. The thermal stability may also be favourably affecte (cf. e. g. EP-A-366271 and EP-A-488951).

It has now been found that organozinc compounds, such as zinc carboxylates, can be combined advantageously with compounds of the formulae

in order to stabilize chlorine-containing polymers. In these formulae, the meanings of the radicals and symbols are as follows : X : OorS ; a : 0 to 8; b : 2 to 12 ; c : 1 or 2 ; k : 2 to 6 ; Ri H or C1-C8 alkyl, C3-C8 alkenyl, C7-C9 phenylalkyl or Cj-C3cycloalkyl ; R :C1-C8 alkyl, -NH2, R3NG-, R4-O-, [R3-NG-CX]CE-, (C1-C4 alkl)2N(CH2)k-CX-, phenyl or OH-, C1-C4 alkoxy- or C1-C4 alkyl-substituted phenyl,

R3 :H, C1-C8 alkyl, C3-C8 alkenyl, C5-C8 cycloalkyl, R2-CX-NG-(CH2)b, (C,-C4alkyl) 2N (CH.,) k- or G ; R4 C1-C4alkyl, cyclohexyl or benzyl;

-CH=CH-, -CH (OH)-CH (OH)-, -CH2-CH(OH)- or -NH(CH2)bNH-: A:-(CH2)-m, > CO, -(CH2)d-CO- or -NH(CH2)n-CO-: m : 0or 1 ; n : 2 to 12 ; p : 0or1 ; d : 1 to 8 ; q : 1 OR 2; r : 2 to 50 ; and, if p is 0, A: > CO, -(CH2)-m, -(CH2)d-CO-, -NH(CH2)n-CO-; if p is 1, A :-(CH2)-rn ; the group L: -CH2-CHR6-, -(CH2)-3, -CH=CH-,

C : H, C1-C8 alkyl, C3-C8 alkenyl, C5-C8 cycloalkyl or G ; R6 : H, C1-C12 all#yl; R7 : H or CH3 ; Q : -O- or > NH; Y :-CH2-CH (OH)-CH2-; and s : 3 to 60.

In the above formulae : C-C4alkyl is methyl, ethyl, n-propyl, isopropyl, n-, i-, sec-or t-butyl.

C1-C8 alkyl are the same radicals and, for example, n-pentyl, isopentyl, neopentyl, n-hexyl,-n-heptyl, 2-ethylhexyl, n-octyl or isooctyl.

C5-C8 cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Cyclopentyl and, in particular, cyclohexyl are preferred.

C3-C8alkenyl substituents can be branched or unbranched alkenyl, for example allyl, crotonyl, 2-methylallyl or hexenyl.

C,-C4alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.

C7-C9 phenylalkyl is, for example, benzyl, 1-or 2-phenylethyl, 3-phenylpropyl, alpha, alpha dimethylbenzyl or 2-phenylisopropyl, preferably benzyl.

Preference is given in the stabilizer combination to compounds of the formulae I to IV, in which X :O or S ; a : 0 to 4 ; b : 2 to 6 ; c : 1 or 2 ; k : 2 or 3 : ; R : H or C,-C8alkyl ; R : C1-C8 alkyl, -NH2, R3-NG-, [R3-NG-CX]cE- OR (C1-C4 alkyl)2N(CH2)k-CX-; R3 : H, C1-C8 alkyl, R2-CX-NG-(CH2)b, (C1-C4 alkyl)2N(CH2)k- or -G ;

-NH (CH2)bNH-; R5 : H, C1-C8 alkyl or G; A :-CO--(CH2)-,-(CH2) d-CO-or-NH (CH2),-CO- m : 0 or 1, n : 2 to 6 ; p : 0 or 1 ; d : 1 to 4 ; q : 1 or 2 ; r : 2 to 50 ; and, if p is 0, A: -CO-, -(CH2)m-, -(CH2)d-CO- or -NH(CH2)n-CO-; if p is 1, A :- (CH2) m- ; the group L: -CH2-CHR6-, -(CH2)3-,

R6 : H OR C1-C12 alkyl; Y : -CH2-CH(OH)-CH2-; R7 : H or CH3 Q :-O-or > NH, and s : 3 to 60.

Particufarly preferred compounds of the formulae I to IV are those in which X : O ; a : Oto4 ; b : 2to6 ; c : 1 ; R1 : H or C1-C8 alkyl; R2 : [R3-NG-CX]cE-; R3 :H, C1-C8 alkyl, R2-CX-NG-(CH2)5 or G; E : (CH2)a or -NH-(CH2)bNH-; R5 : G ; A : -(CH2)M-; m : 0 or 1 ; n : 2 to 6 ; p : O : q : 1 OR 2 ; r : 2 to 50 ; the group L: -CH2-CHR6-, -(CH2)C-, OR -CH=CH-; R6 : H; Y :-CH,-CH (OH)-CH,-.

R 7 H R7'H ; Q: > NH; and s : 3 to 60.

Examples of the piperidine compounds of the formulae to IV are : 01) N, N'-bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) ethylene-1 2-diacetamide 02) N, N'-bis (2, 2, 6, 6-tetramethylpiperidin-4-yl)ethylene-1,2-formamide 03) N, N'-bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) adipamide 04) N, N'-bis (2. 2, 6,6-tetramethylpiperidin-4-yl) oxamide 05) 4-hydroxybenzamido-2, 2, 6, 6-tetramethylpiperidine

The compounds of the formulae I to IV can be present in the chlorine-containing polymer in proportions of from 0. 005 to 5%, preferably from 0. 01 to 2% and, in particular, from 0. 01 to 1 %.

Zinc compounds The organozinc compounds with a Zn-O bond comprise zinc enolates, zinc phenolates and/or zinc carboxylates. The latter are compounds from the series of the aliphatic saturated and unsatured C,-C22carboxylates, the aliphatic saturated or unsaturated C2-C22carboxylates, which are substituted with at least one OH group or whose chain is interrupted by one or more O atoms (oxa acids), the cyclic and bicyclic carboxylates of 5-22 carbon atoms, the unsubstituted, mono-or poly-OH-substituted and/or C,., 6alkyl-substituted phenylcarboxylates, the phenyl-C1 l6alkylcarboxylates, or the unsubstituted or C,, 2alkyl-substituted phenoiates, or of abietic acid. Examples of Zn-S compounds are Zn mercaptides, Zn mercaptocarboxylates and Zn mercaptocarboxylic esters.

Mention may be made by name, as examples, of the zinc salts of monovalent carboxylic acids, such as acetic acid, propionic acic, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristylic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxysteanc acid, 9, 10-dihydroxystearic acid, oleic acid, ricinoleic acid, 3, 6-dioxaheptanoic acid, 3, 6, 9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3, 5-di-tert-butyl- 4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propyibenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid, cinnamic acid, mandelic acid, glycoiic acid ; zinc salts of divalent carboxylic acids and their monoesters, such as oxalic acid, malonic acid, succininic acid, giutaric acid, adipic acid, fumaric acid, pentane1, 5-dicarboxylic acid, hexane-1, 6-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, octane1, 8-dicarboxylic acid, 3, 6, 9-trioxadecane-1,10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, malic acid, salicylic acid. polyglycoldicarboxylic acid (n=10-12), phthalic acid, isophthaiic acid. terephlha ! ic acid and hydroxyphthalic acid ; and the di-or : esters of tri-or tetravalent carboxylic acids, such as hemimellitic acid, trimelsitic acZd, pyromellitic acid, citric acid and also so-called overbased zinc carboxylates, or zinc lauryl mercaptide, sinc thioglycolate, zinc thiosalicylate, zinc bis-i-octylthioglycolate, zinc mercaptopropionate, zinc thiolactate, zinc thiomalate, zinc bis-octylmercaptopropionate, zinc bix-isooctylthiolactate and zinc bis-laurylthiomalate.

The zinc enolates preferably compnse enolates of acetylacetone, of benzoylacetone, and of dibenzoylmethane and enolates of acetcacetic and benzoylacetic esters, and of dehydroacetic acid. It is also possible to employ inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate or zinc sulfide.

Preference is given to neutral or basic zinc carboxylates of a carboxylic acid having 2 to 22 carbon atoms (zinc soaps), for example benzoates or alkanoates, preferably Csalkanoates, stearate, oleate, laurate, palmitate, behenate, Versatate, hydroxystearates and-oleates, dihydroxystearates, p-tert-butylbenzoate, or (iso) oct2noate. Particular preference is given to stearate, oleate, Versatate, benzoate, p-tert-butylbenzoaie and 2-ethylhexanoate.

In addition to the abovementioned zinc compounds, (in) organic aluminium compounds having an Al-O bond are also suitable. The preferred aluminium compounds which can be used inclue, preferably, aluminium enolates and aluminium carboxylates. Examples or carboxylate and enolate radicals can be found correspondingly in the comments made regarding zinc above.

Examples of inorganic Al compounds are aluminium hydroxide and aluminium phosphates.

The described organozinc compounds and their mixtures can be employed in amounts of, for example, from 0. 001 to 10 parts by weight, expediendy from 0. 01 to 5 parts by weight, preferably from 0. 01 to 3 parcs by weight, based on 100 parts by weight of chlorine-containing polymer.

They may also be present as mixed salts (coprecipitates).

The novel stabilizer combination can be used together with further additives which are customary for the processing and stabilization of chlorine-containing polymers, examples being 1. Stabilizers : i~pcxides and epoxidized fatty acid esters ; phosphites ; thiophosphites and thiophosphates ; polyols ; 1, 3-dicarbonyl compounds ; mercaptocarboxylic esters ; dihydropyridines ; antioxidants ; light stabilizers and UV absorbers ; alkali metaf and alkaine earth metal compounds ; perchlorate sa ! ts ; zeolites ; hydrotatcites ; dawsonites ; 2. Further common PVC additives, for exa, plue lubricants ; plasticizers ; impact modifiers ; processing aids ; blowing agents ; risers ; antistats; biocides ; antifogging agents : pigments and dyes; metal deactivators; flameproofing agents (cf in this respect"Handbook of PVC Formulating".'. J. Wickson, John Wiley & Sons, Ne,,./ York 1993).

Examples of such additives are known to the skilled worker and can be found in the technicai literature. Without limitation, mention may be made here of some of the known additives and processing aids : Phosphites : Organic phosphites are known co-stabiiizers for chlorine-containing polymers.

Examples are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl, triphenyl, tricresyl, trisnonylphenyi, tris-2, 4-t-butylphenyl or tricyclohexyl phosphite.

Further suitable phosphites are variously mixed aryl dialkyl and alky diarylphosphites, such as phenyl dioctyl, phenyl didecyl, phenyl didodecyl, phenyl ditridecyl, phenylditetradecyl, phenyt dipentadecyl, octyl diphenyl, decyl diphenyi, undecyl diphenyl, dodecyidiphenyl, tridecyl diphenyl, tetradecyi diphenyl, pentadecyl diphenyl, oleyl diphenyl, stearyl diohenyl and dodecyl bis-2, 4-di-t-butylphenyl phosphite.

Furthermore, phosphites of various diols and polyols can also be used advantageously ; examples are tetraphenyidipropylene glycol diphosphite, polydipropylene glycol phenyl phosphite, tetramethylolcyclohexanol decyi diphosphite, tetramethyloicyclohexano ! butoxyethoxyethyl diphosphite, tetramethylolcyciohexanol nonylphenyl diphosphite, bisnonyiphenyl di-trimethylotpropane diphosphite, bis-2-butoxyethyl di-trimethylolpropane diphosphite, trishydroxyethyl isocyanurate hexadecyl triphosphite, didecylpentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis-2, 4-di-t-butylphenyl pentaerythritol diphosphite, and also mixtures of these phospites and aryi/alkyl phosphite mixtures of the statistical composition (H19C9-C6H4)O1.5P(OC12,13H25,27)1.5 OR [C8H17-C6H4-O-]2P[i-C8H17O] or (H19C9-C6H4)O1.5P(OC9,11H19,23)1.5.

The organic phosphites can be employed in an amount of, for example, from 0. 01 to 10 parts by weight, expediently from 0. 05 to 5 parts by weight and, in particular, from 0. 1 to 3 parts by weight, based on 100 parts by weight of PVC Polyols : Examples of suitable compounds of tnis type are : pentaerythriotal, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasine, mannitol, lactose, leucose, tris (hydroxyethyl) Isocyanurate, palatinite, tetramethylofcyclohexanol (TMCH), tetramethylolcyclopentanol, tetramethyloicyclopyranol, glycerol, diglycerol, pofyglycerol, thiodiglycerc. or 1-0-a-D-glycopyranosyl-D-mannitol dihydrate, and also polyvinyl alcohol and cyclodextrins. Among these, TMCH and the disaccharide a ! cohols are preferred.

The polyols can be employed in an amount of, for example, from 0. 01 to 20 parts by weight, expediently from 0. 1 to 20 parts by weight, and, in particular, from 0. 1 to 10 parts by weight, based on 100 parts by weight of PVC.

1, 3-Dicarbonyl compounds : Examples of 1, 3-dicarbonyl compounds are acetylacetone, butanoylacetone, heptanoyiacetone, stearoylacetone, palmitoylacetone, lauroyiacetone, 7-tert-nonylthioheptane-2, 4-dione, benzoylacetone, dibenzoyl methane, lauroylbenzoyl- methane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, S-hydroxycapronylbenzoylmethane, tribenzoyl methane, bis (4-methyl benzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoyl benzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetyinonane, benzoyl- acetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformyl methane, benzoyl phenylacetyl methane, bis (cyclohexanoyl) methane. di (pivaloyl) methane, acetoacetic methyl, ethyl, hexyl, octyl, dodecyl or octadecyl ester, benzoylacetic ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl ester, stearoylacetic ethyl, propyl, butyl, hexyl or octyl ester and dehydroacetic acid, and the zinc, alkali metal, alkaline earth metal or aluminium salts thereof.

The 1, 3-dicarbonyl compounds can be employed in an amount of, for example, from 0. 01 to 10 parts by weight, expediently from 0. 01 to 3 parts by weight and, in particular, from 0. 01 to 2 parts by weight, based on 100 parts by weight of PVC.

Thiophosphites and thiophosphates : Thiophosphites and thiophosphates are compounds of the general type (RS) 3P, (RS) 3P=O and (RS) 3P=S, as described in the patent documents DE 2809492, EP 090770 and EP 573394. Examples are : trithiohexyl phosphite, trithiooctyl phosphite, trithiolauryl phosphite, trithiobenzyl phosphite, tris [carboxy-i-octyloxy1 ; mevhyl trithiophosphate, S, S, S-tris [carbo-i-octyloxy] methyl trithiophosphate, S, S, S-tris [carbo-2 ethylhexyloxy] methyl trithiophosphate, S, S, S,-tris-1- (carbohexyloxy] ethyl trithiophosphate, S, S, S-tris-1-(carbo-2-ethylhexyloxy] ethyl trithiophosphate, S, S, S-tris-2- [carbo-2-ethylhexyl- oxySethy trithiophosphate.

The thiophosphites and thiophosphates can be present in the chlorine-ccntaining polymer expediently in proportions of from 0. 01 to 20%, preferably from 0. 1 to 5% and, in particular, from 0. 1 to 1%.

Mercaptocarboxylic esters : Examples of these compounds are : esters of thioglycolic acid, thiomalic acid, mercaptopropionic acids, of mercaptobenzoic acids and of thiolactic acid, as are described in FR 2459816, EP 90748, FR 2552440 and EP 365483. The mercaptocarboxylic esters also embrace corresponding polyol esters and their partial esters.

They can be present in the chlorine-containing polymer expediently in proportions of from 0. 01 to 10%, preferably from 0. 1 to 5% and, in particular, from 0. 1 to 1%.

Epoxides and epoxidized fatty acid esters : The novel stabilizer combination may addition comprise at least one epoxidized fatty acid ester. Particularly suitable for this are esters of fatty acids from natural sources, such as soya oil or rapeseed oil.

The epoxy compounds are employed in amounts of, for example, upwards of 0. 1 part per 100 parts by weight of composition, expediently from 0. 1 to 30 parts, preferably from 0. 5 up to 25 parts by weight. Further examples are epoxidized polybutadiene, epoxidized hnseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl or 2-ethylhexyl epoxystearate, tris (epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3-phenoxy-1, 2epoxypropane, bisphenol A digiycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate.

Also suitable as epoxides are derivatives of bisphenol A and of bisphenol F, as described, for example, in South African patent document ZA-2600/94.

Dihydropyridines and polydihydropyridines : Suitable monomeric dihvdropvridines are compounds as described, for example, in FR 2039496, EP 2007. EP 362012 and EP 24754. Preference is given to those of the formula

in which, Z Is C02CH3 CO2C2Hs CO2 Cl2H2s or-C02C2H,-S-CU2H2s Particularly suitable polvdihydropyridines are compounds of the following formula

in which T is unsubstituted C, 12alkyl, L is as defined for T, m and n are numbers from 0 to 20, kis0or 1, R and R'independently of one another are ethylene, propylene, butylene or an alkylene-or cycloalkylenebismethylene group of the type-(-CpH2p-X-) tCpH2p-, p is from 2 to 8, t is from 0 to 10, and X is oxygen or sulfur.

Compounds of this kind are described in more detail in EP 0286887.

The (poly) dihydropyridines can be employed in the chlorine-containing polymer expediently in proportions of from 0. 001 to 5 parts by weight and, in particular, from 0. 005 to 1 part by weight, based on the polymer.

Particular preference is given to thiodiethylenebis [5-methoxycarbonyl-2, 6-dimethyl-1, 4dihydropyridine-3-carboxylate].

Alkali metal and alkaline earth metal compounds : By these terms are meant principal the carboxylates of the above-described acids, or also corresponding oxides and hydroxides, carbonates or basic carbonates. Also suitable are mixtures thereof with organic acids. Examples are NaOH, KOH, CaO, Ca (OH2), MgO, Mg (OH) 2, CaC03, MgCO, dolomite, huntite, and also Na, K, Ca or Mg salts of fatty acids.

In the case of carboxylates of alkaline earth metals and of Zn, it is also possible to employ adducts thereof with MO or M (OH) z (M = Ca, Mg, Sr or Zn), so-called overbased compounds.

Preference is given to the use, in addition to the novel stabilizer combination, of alkali metal, alkaline earth metal and/or aluminium carboxylates, for example Na, K, Ca or aluminium stearates.

Perchlorate salts : Examples are those of the formula M (ClO4)n where M is Li, Na, K, Mg, Ca, Ba, Zn, Al, Ce or La. The index n is, in accordance with the valency o, M, 1, 2 or 3. The perchlorate salts can be present as complexes with alcools or ether alcools. In this context, the respective perchlorate can be employed in various common forms in which it is supplie ; for example as a salt or aqueous solution applied to a carrier material such as PVC, Ca silicate, zeolites or hydrotalcites, or obtained by chemical reaction of hydrotalcite with perchloric acid.

The perchlorates can be employed in an amount of, for example, from 0. 001 to 5 parts by weight, expediently from 0. 01 to 3 parts by weight and, with particular preference, from 0. 01 to 2 parts by weight, based on 100 parts by weight of PVC.

Hydrotalcites and zeolites : The chemical composition of these compounds is known to the skilled worker, for example from the patent documents DE 38^3581, US 4000100, EP 062813, WO 93/20135.

Compounds from the series of the hydrotalcites can be described by the general formula VI M 1+ 1-x # M3+x # (OH)2 # (An)x/n # mH2O (VI) in which M2* = one or more metals from the group consisting of Mg, Ca, Sr, Zn and Sn, M3+ = Al or B, A"is an anion having the valency n, n is a number from 1-2, 0 < xs0. 5, and m is a number from 0-20.

A'is preferably = OH-, ClO4, HCO3, CH3COO-, C5H5COO-, CO2-3, SO4,

(CHOHCOO) 2- 2, (CH2CO0) 2 2-, CH, CHOHCOO- 2-po. 2, Examples of hydrotalcites are Al2O3 6MgO.CO2.12H2O, Mg4.5Al2(OH)13.CO3.3.5H2O, 4MgO.Al2O3.CO2.9H2O.

4MgO. AI203 C02. 6H2O, ZnO.3MgO.Al2O3.CO2.8-9H2O and ZnO 3MgO.Al2O3.CO2.5-6H2O.

Compounds from the series of the zeolites (alkali metal and/or alkaline earth metal aluminosilicates) can be described by the general formula (Vit) Mx/n [(AlO2)x (SiO2)y].wH2O (VII) in which n is the charge of the cation M: M is an element from the first or second main group, such as Li, Na, K, Mg, Ca, Sr or Ba, or Zn, y : x is a number from 0. 8 to 15, preferably from 0. 8 to 1. 2 ; and w is a number from 0 to 300, preferably from* 0. 5 to 30.

Structures can be found, for example, in the"Atlas of Zeolite"by W. M. Meier and D. H. Olson, Butterworth-Heinemann, 3rd ed. 1992.

Examples of zeolites are sodium alumosilicates of the formulae Na12Al12Si12O48. 27 H20 [zeolite A], Na6AI6Si6024. 2 NaX. 7. 5 H20, X= OH, halogen, C104 [sodalite] ; Na6Al6Si30O72.24H2O ; Na8Al8Si40O96. 24 H20 ; Na, 6AI, 6Si2408o. 16 H20 ; Na16Al16Si32O96.16H2O ; Nas6AI6Si, 360384. 250 H20 (zeolite Y], Na86A186Si, 04. 264 H2O [zeolite X] ; or the zeotites which can be prepared by partial or complete exchange of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na, K)1 0Al10Si22O64. 20 H20 ; Ca4.5Na3[(AlO2)12(SiO2)12].30 H2O ; K9Na3 [(AlO2)12 (SiO2)12].

27 H2O.

Other suitable zeolites are : Na20*Al2O3* (2 to 5) SiO2 (3. 5 to 10) H20 [zeolite P] Na2O'AI2032 Si02' (3. 5-10) H20 (zeolite MAP) or the zeolites which can be prepared by partial or complete exchange of the Na atoms by Li, K or H atoms, such as (Li, Na, K, H), 0Al10Si22O64. 20 H20, K9Na3 [(AlO2)12 (SiO2)12]. 27 H20, K4Al4Si4O16.6H2O [zeolite K-F], Na8Al8Si40O96. 24 H20 zeolite D, as described in Barrer et a !., J. Chem. Soc.

1952, 1561-71, and in US 2, 950, 952 ; Also suitable are the following zeolites : K offretite, as described in EP-A-400. 961 : zeolite R, as described in GB 841, 812 : zeolite LZ-21 7, as described in US 4, 503. 023 : Ca-free zeolite LZ-218. as descnbed in US 4, 333, 859 ; zeolite T, zeolite LZ-220, as described in US 4, 503, 023 ; Na3K6Al9Si27O72.21 H2O [zeolite L] ; zeolite LZ-211, as described in US 4, 503, 023 ; zeolite'2-212 as described in US 4, 503, 023 ; zeolite O, zeolite LZ-217 as described in US 4, 503, 023 ; zeolite LZ-219, as described in US 4, 503, 023 ; zeolite rho, zeolite i 7-214, as described in US 4, 503, 023 ; zeolite ZK-19, as described in Arn. Mineral. 54 1607 (1969) ; zeolite W (K-M), as described in Barrer et al., J. Chem. Soc. 1956, 2882 ; and Na3oAI30Si660l92. 98 H20 [zeolite ZK-5, zeolite Q].

Particular preference is given to the use of zeolite P types of the formula Vil in which x is 2 to 5 and y is 3. 5 to 10, especially zeolite MAP of the formula VII in which x is 2 and y is 3. 5 to 10. The substance concerned is, in particular, zeolite Na-P, z. e. M is Na. This zeolite occurs generally in the variants Na-P-1, NaP-2 and Na-P-3, which differ in their cubic, . etragonal or orthorhombic structure (R M. Barrer, B. M. Munday, J. Chem. Soc. A 1971, 2909 14). The literature reference just mentioned also describes the preparation of zeolite P-1 and P-2. Zeolite P-3 is accordingly very rare and therefore of virtually no practical interest.

The structure of zeolite P-1 corresponds to the gismcndite structure known from the abovementioned Atlas of Zeolite Structures. In more recent literature (EP-A-384 070) a distinction is made between cubic (zeolite B or Pc) and tetragonal (zeoiite Pi) zeolite of the P type. Also mentioned therein are more recent zeolites of the P type with Si : AI ratios below 1. 07 : 1. These are zeolites bearing the designation MAP or MA-P, for Maximum Aluminium P. Depending on the preparation process, zeoiite P may include small fractions of other zeolites. Highly pure zeolite P has been described in WO 94/26662.

In the context of the invention it is also possible to use those finely divided, water-insoluble sodium alumosilicates which have been precipitated in the presence of water-soluble inorganic or organic dispersants and crystallized. These can be introduced in the reaction mixture in any desired manner, prior to or during the precipitation or crystallization.

Preference is given tc Na-zeolite A and Na-zeoli-e P The hydrota ! cites ana zeolites can be naturally occurrng minerals or synthetically prepared compounds.

The hydrotalcites and/or zeolites can be employed in amounts of, for example from 0. 1 to 50 parts by weight, expediently frorn 0. 1 to 10 parts by weight and, in n particular, from 0. 1 to 5 parts by weight, based on 100 parts by weight cf halogen-containing polymer Alkali metal alumocarbonates (dawsonites) : These compounds can be represented by the formula {(M2O)m.(Al2O3)nZo.pH2O} (V), in which M is H, Li, Na, K, Mg1/2, Ca1/2, Sr1/2 or Zn1/2; Z is CO2, SO2, (Cl2O7)1/2, B4O6, S2O2 (thiosulfate) or C202 (oxalate) ; m, if M is Mg,/2 or Cal/2, is a number between 1 and 2, in all other cases a number between 1 and 3 ; n is a number between 1 and 4 ; o is a number between 2 and 4 ; and p is a number between 0 and 30.

The alumo salt compounds of the formula (V) which can be used can be naturally occurring mineras or synthetically prepared compounds. The metals can be partially substituted by one another. The abovementioned alumo salt compounds are crystalline, partially crystalline or amorphous or can be present in the form of a dried gel. The alumo salt compounds can also be present in rarer, crystalline modifications. A process for preparing such compounds is specified in EP 394670. Examples of naturally occurring alumo salt compounds are indigirite, tunisite, alumohydrocalcite, para-alumohydrocalcite, strontiodresserite and hydrostrontiodresserite. Further examples of alumo salt compounds are potassium alumocarbonate {(K20). (Ai203). (C02) 2. 2H20}, sodium alumothiosulfate { (Na20). (AI203). (S202) 2. 2H20}, potassium alumosulfite { (K20). (AI203). (S0 2. 2H20}, calcium alumooxalate {(CaO).(Al2O3). (C202) 2. 5H20}, magnesium alumotetraborate {(MgO).(Al2O3).(B4O6)2.5H2O}, {([Mg0.2Na0.6]2O).(Al2O3)(CO2)2. 4. 1H2O}, {([Mg0.2Na0.6]2 O). (AI203). (CO2)2. 2. 4. 3H20} and f ( [MgO. 3Nao. 4120). (AI203)- (CO2) 2. 2. 4. 9H20}.

The mixed alumo salt compounds can be obtained in accordance with methods known per se by cationic exchange, preferably from the alkali metal alumo salt compounds, or by combined precipitation (see for example US 5, 055, 284).

Preferred alumo salt compounds are those of the above formula in which M is Na or K ; Z is CO2, SO2 or (Cl2O7)1/2; m is 1-3 ; n is 1-4 ; o is 2-4 and p is 0-20. Z is particularly preferably co2.

Also preferred are compounds which can be represented by the following formulae : M20. AI203. (CO2) 2. pH20 (la), (M20) 2. (AI203) 2. (CO2) 2 pH20 (Ib), M20. (Al2O3)2.(CO2)2.pH2O (lc) in which M is a metal such as Na, K, Mg,, 2, Ca"2, Sri/2 or Znl/2 and p is a number from 0 to 12.

Particular preference is given to sodium alumodihydroxycarbonate (DASC) and the homologous potassium compound (DAPC).

The dawsonites can be employed in an amount of, for example, from 0. 01 to 50 parts by weight, expediently from 0. 1 to 10 parts by weight, particularly preferably from 0. 1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.

The novel stabilizer combination can be used together with further additives which are customary for the processing and stabilizing of chlorine-containing polymers, examples being : Antioxidants : Suitable examples are : 1. Alkvlated monophenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2-butyl4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-ethyiphenoi, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di tert-butyl-4-isobutylphenoi, 2, 6-dicyclopentyf-4-methyl phenol, 2- (a-methylcyclohexyl)- 4, 6-dimethylphenol, 2, 6-dioctadecyl-4-methylphenol, 2, 4, 6-tricyclohexylphenol, 2, 6-di-tert butyf-4-methoxymethylphenoi, 2, 6-dinonyl-4-methyfphenol, 2, 4-dimethyl-6- (1'-methylundec- 1'-yi)-phenol, 2, 4-dimethyl-6-(1'-methyiheptadec-1'-yl) phenol, 2, 4-dimethyl-6-(1'-methyl tridec-1'-yi) phenol and mixtures thereof.

2. Atkvtthiomethytphenots. for example 2, 4-dioctylthiomethyl-6-tert-butylphenol, 2, 4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2, 6-didodecyl- thiomethyl-4-nonylphenol.

3. Hydroquinones and alkylated hydrouinones. for example 2, 6-di-tert-butyl- 4-methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2, 5-ci-te,--amylhydroquinone, 2, 6-diphenyl 4-octadecyloxyphenol, 2, 6-di-tert-butylhydroqu ! none, 2, 5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl sterate. bis (3. 5-di-tert butyl-4-hydroxyphenyl) adipate 4. Tocopherols, for example a-tocopherol, b-tccopherol, g-tocopherol, d-tocopherol and mixtures thereof (vitamin E).

5. Hvdroxvlated thiodiphenyl ethers, for example 2, 2'-thiobis (6-tert-butyl-4-methyl-phenol), 2, 2'-thiobis (4-octyiphenol), 4, 4'-thiobis(6-tert-butyl-3-methylphenol), 4, 4'-thiobis-(6-tert-butyl2-methylphenol), 4, 4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis (2, 6-dimethyl-4-hydroxyphenyl) disulfide.

6. Alkylidenebisphenols, for example 2, 2'-methylenebis (6-tert-butyl-4-methyiphenol), 2, 2'-methylenebis (6-tert-butyl-4-ethylphenol), 2, 2'-methylenebis[4-methyl-6-(a-methyl cyclohexyl) phenol], 2, 2'-methyienebis (4-methyl-6-cyciohexylphenol), 2, 2'-methylenebis (6-nonyl-4-methylphenol), 2, 2'-methylenebis (4, 6-di-tert-butylphenol), 2, 2'-ethylidenebis (4, 6-di-tert-butylphenol), 2, 2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2, 2'-methylene- bis (6- (a-methylbenzyl)-4-nonylphenol], 2, 2'-methyfenebis [6- (a, a-dimethylbenzyl)-4-nonyl- phenol], 4, 4'-methylenebis (2, 6-di-tert-butylphenol), 4, 4'-methylenebis (6-tert-butyl-2-methyl- phenol), 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-tert-butyl-5-methyl 2-hydroxybenzyl)-4-methyl phenol, 1, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis [3, 3-bis (3'-tert-butyl-4'-h ydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl- phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl- 4-methyiphenyi] terephthalate, 1, 1-bis (3, 5-dimethyl-2-hydroxyphenyl) butane, 2, 2-bis (3, 5-ditert-butyl-4-hydroxyphenyl) propane, 2, 2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n dodecylmercaptobutane, 1, 1, 5, 5-tetra- (5-tert-butyl-4-hydroxy-2-methyfphenyl) pentane.

7. O-, N-and S-benzol compounds, for example 3, 5, 3', 5'-tetra-tert-butyl-4, 4'-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3, 5-dimethylbenzylmercaptoacetate, tris (3, 5-ditert-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-hydroxybenzyimercaptoacetate.

8. Hydroxybenzylated malonates, for example dioctadecyl 2, 2-bis (3, 5-di-tert-butyl 2-hydroxybenzyl) malonate, dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2, 2-bis (3, 5-di-tert-butyl-4-hyd. oxybenzyl) malonate, di (4-(1, 1, 3, 3-tetramethylbutyl) phenyl] 2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate.

9. Aromatic hydroxybenzyt compounds, for example 1, 3, 5-tris (3, 5-di-tert-butyl4-hydroxybenzyf)-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.

10. Triazine compounds, for example 2, 4-bisoctylmercapto-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, 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1, 3, 5-tris (3, 5di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1, 3, 5-triazine, 1, 3, 5-tris (3, 5-dicyclohexyl= 4-hydroxybenzyl) isocyanurate.

11. 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-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzyi- phosphonate, the calcium salt of the monoethyl ester of 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate.

13. Esters of b- 3, 5-di-tert-butyl-4-hydroxvphenv ) oropionic acid with mono-or polyhydric alcools, e. g. with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyi) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyiolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane.

14. Esters of b- (5-tert-butyl-4-hvdroxv-3-methylohenyl) orooionic acid with mono-or polyhydric alcools, e. g. with methanol, ethanol, octanol, octadecanol, 1, 6-hexanedioi, 1, 9 nonane-diol, ethylene glycol, 1, 2-propanediol, neoenryl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, ; ris (hydroxyethyl) isocyanurate, N, N'- bis (hydroxyethyl) oxalamide, 3-thiaundecanoi, 3-thiapentadecanol, tnmetnylhexaneciol, trimethylol-propane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane.

15. Esters of b- (3. 5-dicyclohexyl-4-hvdroxypnenyl) proDionic acid with mono-or polyhydric alcohols, e. g. with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol. ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethvl-i-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane.

16. Esters of 3, 5-di-tert-butyl-4-hvdroxvphenvl acetic acid with mono-or polyhydric alcohols, e. g. with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycoi, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane.

17. Amides of b-(3. 5-di-tert-butvl-4-hvdroxvPhenvl) ProDionic acid, for example N, N'-bis (3, 5di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis (3, 5-di-tert-butyl- 4-hydroxyphenylpropionyl)trimethylenediamine, N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenyl propionyl) hydrazine.

If desired it is also possible to employ a mixture of antioxidants differing in structure.

The antioxidants can be employed in an amount of, for example, from 0. 01 to 10 parts by weight, expediently from 0. 05 to 10 parts by weight and, in particular, from 0. 05 to 5 parts by weight, based on 100 parts by weight of PVC.

UV absorbers and light stabilizers : examples of these are : 1. 2-(2'-HydroxvDhenvl) benzotriazolesl for example 2- (2'-hydroxy-5'-methylphenyl)- benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'- hydroxy-phenyl)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'-octoxyphenyl) benzotriazole, 2- (3', 5'-di-te^- amyl-2'-hydroxy-phenyl) benzotriazole, 2- (3', 5'-bis (a, a-dimethylbenzyl)-2'-hydroxyphenyl)- benzotriazole, a mixture of 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl)-5- chlorobenzo-triazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyloxy) carbonylethylj-2'-hydroxyphenyl)- 5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5chlorobenzo-triazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2- methoxycarbonylethyl) 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, and 2- (3'-tert-butyl-2'-hydroxy-5'- (2-isooctyloxy- carbonylethyl) phenylbenzotriazole, 2, 2'-methylenebis [4- (1, 1, 3, 3-tetramethylbutyl)-6-benzo- triazol-2-ylphenol] ; the transesterification product of 2- [3'-tert-butyl-5'- (2-methoxycarbonyt- ethyl)-2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300 ; [RCH2CH2COO(CH2)3]2 where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2', 4'-trihydroxy and 2'-hydroxy-4, 4'-dimethoxy derivative.

3. Esters of substituted or unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert butylbenzoyl) resorcinol, benzoyiresorcinol, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyi 3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3, 5-di-tert-butyl4-hydroxybenzoate, 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert-butyi-4-hydroxybenzoate.

4. Acryiates, for example ethyl a-cyano-b, b-diphenylacrylate or isooctyl a-cyano P, -diphenylacryiate, methyl a-carbomethoxycinnamate, methyl a-cyano-b-methylp-methoxycinnamate or butyl a-cyano- -methyl-p-methoxycinnamate, methyzi a-carbo methoxy-p-methoxycinnamate and N- (b-carbomethoxy-b-cyanovinyl)-2-methylindoline.

5. Nicket compounds, for example nickel complexes of 2, 2'-thio-bis [4- (1, 1, 3, 3-tetramethylbutyl) phenol], such as the 1 : 1 or 1 : 2 complex, with or without additionai ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiccarbamate, nickel salts of monoalkyl esters, such as of the methy ! or ethyl ester, of 4-hydroxy-3, 5-di-tert-butylbenzylphosphomc acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecyl ketoxime, ncckel complexes of 1-phenyl-o-lauroyl- 5-hydroxypyrazole, with or without addition ligands.

6. Stericallv hindered amines, for example bis (2, 2, 6, 6-tetramethylpiperidyl) sebacate, bis (2, 2, 6, 6-tetramethylpipendyl) succinate, bis (1, 2, 2, 6, 6-pentamethylpioeridyl) sebacate, bis (1, 2, 2, 6, 6-pentamethylpipendyl) n-butyl 3, 5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-hydroxyethyl-2. 2. 6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,N'-bis(2,2,6,6-tetramethy.-4-piperidyl)hexamethylenediamine and 4-tertoctylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate. tetrakis (2, 2, 6, 6-tetramethyl-4-piperidyl) 1, 2, 3, 4-butanetetraoate, 1, 1'- (1, 2-ethanediyl)- bis (3, 3, 5, 5-tetra-nethylpiperazinone), 4-benzoyl-2, 2, 6, 6-tetramethylpiperidine, 4-stearyloxy2, 2, 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] decan2, 4-dione, bis (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2, 2, 6, 6-tetra methylpiperidyl) succinate, the condensate of N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexa methylenediamine and 4-morpholino-2, 6-dichioro-1, 3, 5-triazine, the condensate of 2-chloro- 4, 6-di (4-n-butylamino-2, 2, 6, 6-tetramethyipiperidyl)-1, 3, 5-tnazineandl, 2-bis (3-aminopropylamino) ethane, the condensate of 2 chloro-4, 6-di-(4-n-butylamino-1, 2, 2, 6, 6-pentamethyl- piperidyl)-1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl- 7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [4. 5] decane-2, 4-dione, 3-dodecyl-1- (2, 2, 6, 6-tetramethyl 4-piperidyl) pyrrolidine-2, 5-dione, 3-dodecyl-1-(1, 2, 2, 6, 6-pentamethyl-4-piperidyl) pyrrolidine2, 5-dione.

7. Oxalamides, for example 4, 4'-dioctyloxyoxanilide, 2, 2'-diethoxyoxanilide, 2, 2'-dioctyloxy- 5, 5'-di-tert-butyloxanilide, 2, 2'-didodecyloxy-5, 5'-di-tert-butyloxanilide, 2-ethoxy-2'ethyioxanilide, N, N'-bis (3-dimethyZaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'- ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5, 4'-di-tert-butyloxanilide and mixtures of o-and p-methoxy and of o-and p-ethoxy-disubstituted oxanilides.

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-hydroxy4-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- (2-hydroxy-3-buyoxypropyloxy)-phenyl]- 4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4, 6-bis (2, 4-dimethylphenyl)-1, 3, 5-triazine.

The novel stabilizer mixture is preferred with alkali metal or alkaline earth metal carboxylates, especially calcium carboxylates, with aluminium carboxylates, with 1, 3-dicarbonyl compounds, with dihydropyridines, with phosphites or with combinations of these substances.

Plasticizers : Examples of suitable organic plasticlzers are those from the followina groups : A) Phthalic esters : Examples of such piasticizers are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyi, di-noctyl, di-isooctyl, di-isononyl, di-isodecyl, di-isotridecyl, dicyclohexyl, di-methylcyclohexyl, dimethylglycol, dibutylglycol, benzyl butyl and diphenyl phthalate, and also mixtures of phthalates, such as C7-9- and C9-11 alkyl phthalates from predominantly linear alcools, C6-1 0n-alkyl phthalates and C8-10-n-alkyl phthalates, Among these, preference is given to dibutyl, dihexyl, di-2-ethyihexyl, di-n-octyl, di-isooctyl, di-isononyl, di-isodecyl, di-isotridecyl and benzyl butyl phthalate and to the abovementioned mixtures of alkyl phthalates. Particular preference is given to di-2-ethylhexyl, di-isononyl and di-isodecyl phthalate, which are also known under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (dilsononyl phthalate), and DIDP (diisodecyl phthalate).

B) Esters of aliphatic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid Examples of such plasticizers are di-2-ethylhexyl adipate, di-isooctyl adipate (mixture), di isononyl adipate (mixture), di-isodecyl adipate (mixture), benzyi butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di-2-ethylhexyl sebacate and di-isodecyl sebacate (mixture). Preference is given to di-2-ethylhexyl adipate and di-isooctyl adipate.

C) Trimeilitic esters, for example tri-2-ethyihexyl trimellitate, tri-isodecyl trimellitate (mixture), tri-isotridecyl trimellitate, tri-iscoctyl trimellitate (mixture) and also tri-C6-aalkyl, tri-C6., oalkyl, tri-Cr9alkyl and tri-C9-11alkyl trimellitates. The latter trimellitates are formed by esterification of trimeliitic acid with the corresponding mixtures of alkanols. Preferred trimellitates are tri-2-ethylhexyi trimeilitate and the abovementioned trimellitates from alkanol mixtures. Common abbreviations are TOTM (trioctyl trimelkitate, tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimeilitate) and TITDTM (triisotridecyl trimellitate).

D) Epoxy plasticizers These are pnncipally epoxidized unsa : urated fatty acids such as epoxidized soybean oil, E) Polymer plasticizers The most common starting materials for the preparation of the polyester plasticizers are : dicarboxylic acids such as adipic, phthalic, azelaic and sebacic acid ; and diols such as 1, 2-prcpanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanedioi, neopentylglycol and diethylene glycol F) Phosphoric esters Examples of such phosphoric esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2ethylhexyl phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate.

Preference is given to tri-2-ethyfhexyl phosphate and to Reofos 50 and 95 (from FMC).

G) Chlorinated hydrocarbons (paraffin) H) Hydrocarbons I) Monoesters, for example butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkylsuifonic esters.

J) Glycol esters, for example diglycol benzoates.

Definitions and examples of plasticizers from groups A) to J) can be found in the following handbooks : "Taschenbuch der Kunststoffadditive", eds. R. Gachter and H. Mufler, Carl Hanser Verlag, 1989, Chapter 5, pp. 341-442.

"PVC Technology", ed. W. V. Titow, 4th. Ed., Eisevier Publishers, 1984, Chapter 6, pages 147-180.

It is also possible to employ mixtures of different plasticizers.

The plasticizers can be employed in an amount of, for example, from 5 to 120 parts by weight, expediently from 10 to 100 parts by weight, based on 100 parts by weight of PVC.

Examples of suitable lubricants are : montan wax, fatty acid esters, PE waxes, amide waxes, chlorinated paraffins, glycerol esters or alkaline earth metals soaps, and silicone- based lubricants as described in EP 225261. Lubricants which can be used are a ! so described in"Taschenbuch der Kunststoffadditive", eds. R. Gachter and H. Muller, Carl Hanser Verlag, 3rd edition, 1989, pages 478-488.

Fillers : Examples of possible fillers ("Handbook of PVC-Formulating"by E. J. Wickson, John Wiley & Sons, New York 1993, pp. 393-449) and reinforcing agents ("Taschenbuch der Kunststoffadditive", eds. R. Gachter and H. Mller, Carl Hanser Verlag, 3rd edition, 1989, pages 549-615) are : calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibres, talc, kaolin, chalk, mica, metal oxides and metal hydroxides, carbon black or graphite), preference being given to chalk.

Pigments : Suitabte substances are known to the skilled worker. Examples of inorganic pigments are TiOz, carbon black, Fe20, Sb203, (Ti, Ba, Sb) 02, Cr203, spinels such as cobalt blue and cobalt green, Cd (S, Se), ultramarine blue Preference is given to TiO2, including its micronized form. Examples of organic pigments are azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, pyrrolopyrrote pigments and anthraquinone pigments. Further details are to be found in"Handbook of PVC Formulating", E. J. Wickson, John Wiley & Sons, New York 1993, pp. 449-474.

Examples of the chlorine-containing polymers to be stabilized or their recyclates are : polymers of vinyl chloride, vinyl resins containing vinyi chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacryiic acid and with acrylonitrile, copolymers of vinyi 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 copolymers of vinyl chloride, 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 ; polymers of vinylidene chloride 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 of alpha-substituted acrylic acid ; polymers of chlorinated styrenes, for example dichlorostyrene ; chlorinated rubbers ; chlorinated polymers of ethylene ; polymers and post-chlorinated polymers of chlorobutadiene and copoiymers thereof with vinyl chloride, chlorinated natural and synthetic rubbers ; and mixtures of the abovementioned polymers with each other or with other polymerizable compounds.

In the context of this invention the term PVC also mcludes copolymers witn polymerizable compounds such as acrylonitrile, vinyl acetate or A3S, whlch can be suspension, bulk or emulsion polymers. Preference is giver, to PVC homopolymer, alone or in combination with polyacrylates.

Also included are the graft polymers of PVC with EVA. ABS and MBS. Other preferred substrates are mixtures of the abovement ! oned homo-and copotymers. especially, viny ; chloride homopolymers, with other thermoplastic and/or elastomeric polymers, especially blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Preference is given to suspension polymers and buik polymers, and to mulsion polymers.

A particuiarly preferred chlorine-containing polymer is polyvinyi chloride, especially as suspension polymer and bulk polymer.

For stabilization in the context of this invention, further suitable polymers are, in particular, recyclates of chlorine-containing polymers, these polymers being the polymers described in more detail above that have undergone damage through processing, use or storage. PVC recyclate is particularly preferred. The recyclates may also include small amounts of extraneous substances, for example paper, pigments, adhesives, which are often difficult to remove. These extraneous substances may also arise from contact with various materials in the course of use or of reprocessing, examples being residues of fuel, fractions of coating material, traces of metal and residues of initiator.

The stabilizer mixture is employed in a manner familiar to the skilled worker.

It is also possible, for instance, for the stabilizer mixture to be processed together with conventional additives, prior to the actual use, by shaping it into, for example, granules or extrudate or a paste.

The present invention addition provides for the use of the above-described stabilizer mixture-as granules, extrudate or paste and/or in conjunction with lubricants (so-called one-packformulations)-for stabilizing a halogen-containing polymer or polymer recyclate.

For the individual stabilizers and for the halogen-containing polymer itself, the preferences expressed above apply ; similarly, one of the above-described addition constituents can be employed.

The stabilizer mixture can be added to the polymer in a known manner, the abovementioned stabilizers and, if desired, further additives being mixed with the halogencontaining polymer using known devices such as mixers, compounders, extruders, mills and the like. In this context the stabilizers can be added individually or as a mixture or else ! the form of so-called masterbatches. The invention consequently also provides a process for stabilizing halogen-containing polymer, which comprises mixing the stabilizer components and, if desired further additives with the PVC using devices such as calenders, mixers. compounders, extruders and the like.

The invention also relates to the polymer compositions stabilized in this way comprising the novel stabilizer mixture. They can be brought into the desired form by known methods.

Examples of such methods are calendering, extrusion, injection moulding, sintering or spinning, and aiso extrusion blow moulding or processing by the plastisol process. The polymer compositions can also be processed to foams.

The invention also relates to the use of the stabilized polymer compositions for preparing mouldings which can be prepared from halogen-containing polymer. The novel polymer compositions are suitable for semirigid and flexible formulations, for example for flexible formulations for wire sheathing and cable insulation. In the form of semirigid formulations, the novel polymer compositions are suitabte for decorative films, foams, agricultural films, hoses, sealing profiles, office films, extruded profiles and sheets, flooring films and sheets, coated products and synthetic leathers, and also crashpad sheets (for use in the automotive sector).

In the form of rigid formulations, the novel polymer compositions are suitable for hollow articles (bottes), packaging films (thermoform films), blown films, crashpad sheets (cars), pipes, foams, heavy profiles (window frames), transparent wall profiles, construction profiles, sidings, fittings and apparatus enclosures (computers, domestic appliances) and also other injection-moulded articles.

Examples of the use of the polymer compositions stabilized in accordance with the invention as plastisoi are artificial leathers, flooring, textile coatings, wallpapers, coil coatings and underbody protection for motor vehicles.

Examples of sinter applications of the polymer compositions stabilized in accordance with the invention are slush, slush mould and coil coatings.

The preparation of the N-piperidinyltriazines is known from the literature (cf. e. g. Hcuben Weyl"Methoden der organischen Chemie"Vol. VIII, pp. 233-237, SAUERSTOFFVERBINDUNGEN ! I1, 3rd Ed., Thieme Verlag Stuttgart 1952). As starting materia'for the reaction with various N-piperidinylamines it is possible to employ cyanuric chlonde. diamino-chloro-1, 3, 5-triazine or variously substituted bisdialklyamino-chloro-1,3, 5triazines or dalkylamno-and ! or alkylamino-dichloro-1, 3, 5-triazlnes The examples which foliow ilustrat2 the invention in more detaf without restricting it. As in the remainder of the description, parts and percentages are by weight unless stated otherwise.

Example 1 : N, N'-bis [2, 2, 6. 6-te : ramethyloiperidm-4-ylloxamide 156. 3 g (0. 8 mol) of 4-amino-2, 2, 6, 6-tetramethylpiperidine are added slowly with stirring to 56. 1 g (0. 4 mol). of diethyl oxalate, aminolysis taking place with severe evolution of heat.

The temperature rises to about 100 C. Following the addition of 150 mi of xylene, ethanol is distille off at 88-137 C over the course of 18. 5 hours. The batch is subsequently taken up in 1500 mi of xylene, filtered while hot, and cooled. The precipitated crystals are fiitered off with suction and recrystallized from xylene.

Yield 120g (82% of theory) m. p. 225-231 C.

The following products (Examples 2-8) were prepared by reacting 4-amino-2, 2, 6, 6 tetramethylpiperidine with the corresponding acid chlorides or by reacting bis-2, 2, 6, 6 tetramethylpiperidinyl-1, 6-hexanediamine with acetic anhydride :

m. p. 273 C decomp., m. p. 217 C ; m. p. 145 C ; m. p. 197-199 C ; m. p 79-81 C ;

m. p. > 300 C ; m. p. 140-143 C.

Example 9 : For preparing the stabilizers I and 11, a Zn/Ca stearate mixture is mixed intensively with a commercial beta-diketone (stab. I) and also with the piperidine compound 5 in a ratio of 8 : 2 : 1. 5 (stab. II) in a tumble mixer for a period of 1. 5 hours. Of these stabilizer mixtures, portions of 1. 0 part (stab. I) or 1. 15 parts (stab. ll) are each mixed with 100 parts of S-PVC (K value 70) and 21 parts of a mixture of dioctyl phthalate/epoxidized soya oil and with a commercial liquid aryl-alkyl phosphite, and the mixture is plasticated on mixing roilers at 190 C for 5 minutes. Test specimens are cut from the resulting sheets (thickness 0. 2 mm) and are subjected to thermal stress in a Mathis Thermotakter at 180 C for the period indicated in Table 1 below. Subsequently the Yellowness index (YI) is determined in accordance with ASTM-1925-70.

The lower the YI value found, the more effective the prevention by the stabilizer system of yellowing and therefore of damage to the material. The long-ter thermal stability of the stabilized polymer is evident from the sudden onset of massive discoiouration. A stabilizer is all the more effective the longer this discolouration is delayed under thermal stress conditions. Heat test : Y of test specimens at 180 C Table 1

Stabilizer Coadditive Test duration [min] Interrupted 0 6 12 24 48 at time [min] I-5. 1 5.4 black black 17 II Compd. 5 5. 7 6. 0 6. 5 7. 9 12. 8 70

Claims (14)

1. WHAT IS CLAIMED IS : 1. A stabilizer combination for halogen-containing polymers, comprising A) at least one organic zinc compound with a Zn-O bond and/or a Zn-S bond B) at least one compound of the formula

   in which the radicals and symbols have the following meanings : R, : H or C1-C8 alkyl, C3-C8 alkenyl, C7-C9 phenylalkyl or C5-C8cycloalkyl ; Rs : H, C1-C8alkyl, C3-C8alkenyl, Cs-C8cycloalkyl or G ;

   m : 0 or 1 ; q : 1or2 : the group L :-CH2-CHR6-,-(CH2)3-,-CH=CH-,

   R6 : H, C,-C,2alkyl ; and Y:-CH2-CH(OH)-CH22. A stabilizer combination according to claim 1, in which the radicals and symbols have the following meanings : R, : H or C,-C8alkyl ; R5 : H, C,-C8alkyl or G ; m : 0 or 1 ; q : 1 or
2. 2 ; the group L :-CH2-CHR6-,- (CH2) 3-,

   R6 : H, C1-C, 2alkyl ; and Y :-CH2-CH (OH)-CH2-.
3. 3. A stabilizer combination according to claim 1, in which the radicals and symbols have the following meanings : Ri : H or C,-Cealkyl ; R5 : G ; m : 0 or 1 ; q : 1 or 2 ; the group L :-CH2-CHR6-,-(CH2) 3-or-CH=CH-; R6 : H ; and Y :-CH2-CH (OH)-CH2-.
4. 4. A stabilizer combination according to claim 1 in which the organic zinc compound has a Zn-O bond.
5. 5. A stabilizer combination according to claim 1 in which the organic zinc compound is a zinc carboxylate.
6. 6. A stabilizer combination according to any preceding claim which addition comprises alkali metal compounds and/or alkaline earth metal compounds and/or aluminium compounds.
7. 7. A stabilizer combination according to any preceding claim which addition comprises calcium carboxyíates.
8. 8. A stabilizer combination according to any preceding claim which addition comprises aluminium carboxylates.
9. 9. A stabilizer combination according to any preceding claim which additionally comprises at least one further substance from the group consisting of the epoxides and epoxidised fatty acid esters, phosphites, thiophosphites and thiophosphates, polyols, 1, 3 carbonyl compounds, mercaptocarboxylic esters, dihydropyridines, antioxidants, light stabilizers and UV absorbers, alkali metal compounds and alkaline earth metal compounds, perchlorate salts, zeolites, hydrotalcites and dawsonites.
10. 10. A stabilizer combination according to any one of the preceding claims in which the combination further comprises an inorganic zinc compound.
11. 11. A stabilizer combination for halogen-containing polymers, comprising : a) at least one inorganic zinc compound b) at least one compound B) as defined claim 1.
12. 12. A composition comprising a halogen-containing polymer and a stabilizer combination according to any one of the preceding claims.
13. 13. A process for stabilizing halogen-containing polymers, which comprises adding to them a stabilizer combination according to any one of claims 1 to 11.
14. 14. A stabilizer combination according to claim 1 comprising one or more compounds substantially as hereinbefore described.