DE19711690A1 - 4-Acylamido-piperidine compounds in stabilizer combinations for chlorine-containing polymers - Google Patents

Abstract

Stabilizer combinations for halogen-containing polymers A stabilizer combination for halogen-containing polymers is described, comprising A) at least one organozinc compound with a Zn-O bond and/or a Zn-S bond B) at least one compound of the formula in which R 1 , R 2 , R 3 , R 5 , R 7 , A, m, n, p, q, r, s, L, Q, Y and X are as defined in claim 1. At least some of the organozinc compound A) may be replaced by an inorganic zinc compound.

Description

The invention relates to a stabilizer combination of an organic Zinc compound with a Zn-O and / or Zn-S bond, especially one Zinc carboxylate, and at least one compound of those shown below Formulas I, II, III and IV, which are used to stabilize chlorine-containing polymers, especially PVC.

PVC can be stabilized with a number of additives.

Lead, barium and cadmium compounds are particularly good for this suitable, but are controversial today for ecological reasons. (see. "Taschenbuch der Kunststoffadditive", edited by R. Gächter and H. Müller, Carl Hanser Verlag, 3rd edition, 1989, pages 303-31 and plastic Manual PVC, Volume 2/1, G. W. Becker, D. Braun, Carl Hanser Verlag 1985, Pages 531-538). One continues to look for effective stabilizers and Stabilizer combinations without disadvantageous properties.

Sterically hindered amines have already been used as light stabilizers in PVC added. The thermal stability can also be influenced favorably (cf. e.g. EP-A-366271 and EP-A-488951).

It has now been found that organic zinc compounds, such as. B. Zinc carboxylates, advantageously with compounds of the formulas

can combine to stabilize chlorine-containing polymers. The remnants and symbols mean:
X: O or S;
a: 0 to 8; b: 2 to 12; c: 1 or 2; k: 2 to 6;
R₁: H or C₁-C₈-alkyl, C₃-C₈-alkenyl, C₇-C₉-phenylalkyl or C₅-C₈-cycloalkyl;
R₂: C₁-C₈-alkyl, -NH₂, R₃NG-, R₄-O-, [R₃-NG-CX] _c E-, (C₁-C₄-alkyl) ₂N (CH₂) _k -CX-, phenyl or with 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 , (C₁-C₄-alkyl) ₂N (CH₂) _k - or G;
R₄: C₁-C₄ alkyl, cyclohexyl or benzyl;

A: - (CH₂) - _m , <CO, - (CH₂) _d -CO- or -NH (CH₂) _n -CO-
m: 0 or 1; n: 2 to 12; p: 0 or 1; d: 1 to 8; q: 1 or 2; r: 2 to 50;
where, when p is 0, A: <CO, - (CH₂) - _m , - (CH₂) _d -CO-, -NH (CH₂) _n -CO-
if p is 1, A: - (CH₂) - _m ,
group L:

means.
R₅: H, C₁-C₈ alkyl, C₃-C₈ alkenyl, C₅-C₈ cycloalkyl or G;
R₆: H, C₁-C₁₂ alkyl;
R₇: H or CH₃;
Q: -O- or <NH;
Y: -CH₂-CH (OH) -CH₂-;
and s: 3 to 60.

In the above formulas:
C₁-C₄-alkyl: methyl, ethyl, n-propyl, iso-propyl, n-, i-, sec- or t-butyl.

C₁-C₈-alkyl: the same radicals and z. B. n-pentyl, isopentyl, neopentyl, n-hexyl, n- Heptyl, 2-ethylhexyl, n-octyl or iso-octyl.

C₅-C₈-cycloalkyl means z. B. cyclopentyl, cyclohexyl, cycloheptyl, or Cyclooctyl. Cyclopentyl and especially cyclohexyl are preferred.

Are substituents C₃-C₈-alkenyl, it can be branched or act unbranched alkenyl, such as. B. allyl, crotonyl, 2-methylallyl or Hexenyl.

C₁-C₄ alkoxy means z. B. 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 around benzyl.

In the stabilizer combination, preference is given to compounds of the formulas 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;
R¹: H or C₁-C₈ alkyl;
R₂: C₁-C₈-alkyl, -NH₂, R₃-NG-, [R₃-NG-CX] _c E- 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;

R₅: H, C₁-C₈ alkyl or G;
A: -CO-, - (CH₂) _m -, - (CH₂) _d -CO- or -NH (CH₂) _n -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;
where, when p is 0, A: -CO-, - (CH₂) _m -, - (CH₂) _d -CO- or -NH (CH₂) _n -CO-, when n is 1, A: - (CH₂) _m - is,
group L:

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

Compounds of the formulas I to IV, in which
X: O;
a: 0 to 4; b: 2 to 6; c: 1;
R₁: H or C₁-C₈ alkyl;
R₂: [R₃-NG-CX] _c E-;
R₃: H, C₁-C₈ alkyl, R₂-CX-NG- (CH₂) _b or G;
E: (CH₂) _a or -NH- (CH₂) _b NH-;
R₅: G;
A: (CH₂) _m -,
m: 0 or 1; n: 2 to 6; p: 0; q: 1 or 2; r: 2 to 50;
the group L: -CH₂-CHR₆-, - (CH₂) -₃, or -CH = CH-,
R₆: H;
Y: -CH₂-CH (OH) -CH₂-;
R₇: H;
Q: <NH;
and s: 3 to 60.

Examples of the piperidine compounds of forms I to IV are:

The compounds of the formulas I to IV can be found in the chlorine-containing polymer 0.005 to 5%, preferably 0.01 to 2% and in particular 0.01 to 1% be.

Zinc compounds

The organic zinc compounds with a Zn-O bond are zinc enolates, zinc phenolates and / or zinc carboxylates. The latter are compounds from the series of the aliphatic saturated and unsaturated C _1-22 carboxylates, the aliphatic saturated or unsaturated C _2-22 carboxylates, which are substituted with at least one OH group or their chain at least by one or more O atoms interrupted (oxa acids), the cyclic and bicyclic carboxylates with 5-22 C atoms, the unsubstituted phenyl carboxylates substituted with at least one OH group and / or C _1-16 alkyl, the phenyl C _1-16 alkyl carboxylates, or the phenolates optionally substituted with C _1-12 alkyl, or the abietic acid. Zn-S compounds are, for example, Zn-mercaptide, Zn-mercaptocarboxylate and Zn-mercaptocarboxylic acid ester.

The zinc salts of the monovalent ones should be mentioned as examples Carboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, Hexanoic acid, enanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, Pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, Myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic 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, tolylic acid, dimethylbenzoic acid, ethylbenzoic acid, n- Propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid, Cinnamic acid, mandelic acid, glycolic acid; Zinc salts of divalent carboxylic acids or their monoesters, such as 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-trioxadecan-1,10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, Tartaric acid, malic acid, salicylic acid, polyglycol dicarboxylic acid (n = 10-12), Phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di- or triester of tri- or tetravalent carboxylic acids, such as Hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid and further so-called overbased zinc carboxylates or zinc lauryl mercaptide, Zinc thioglycolate, zinc hiosalicylate, zinc bis-i-octylthloglycolate, Zinc mercaptopropionate, zinc thiolactate, zinc thiomalate, zinc bis-octylmercapto propionate, zinc bis-isooctylthiolactate and zinc bis-laurylthiomalate.

The zinc enolates are preferably enolates of Acetylacetone, benzoylacetone, dibenzoylmethane and enolates the acetoacetic and benzoylacetic acid as well as the dehydroacetic acid. Furthermore inorganic zinc compounds such as zinc oxide, zinc hydroxide, Zinc carbonate, basic zinc carbonate or zinc sulfide can be used.

Neutral or basic zinc carboxylates of a carboxylic acid are preferred 2 to 22 carbon atoms (zinc soaps), such as benzoates or alkanoates, preferably C₈-alkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, Hydroxystearate and oleates, dihydroxystearates, p-tert-butylbenzoate, or (Iso) octanoate. Stearate, oleate, versatate, benzoate, p-tert-butyl benzoate and 2-ethyl hexanoate.

In addition to the zinc compounds mentioned, there are also organic compounds Aluminum compounds in question, which have an Al-O bond. To the usable and preferred aluminum compounds include u. a. preferably aluminum enolates and aluminum carboxylates. examples for Carboxylate and enolate residues are those listed above under zinc to take accordingly.  

Examples of inorganic Al compounds are aluminum hydroxide and Aluminum phosphates.

The described organic zinc compounds or their mixtures can be used in quantities from for example 0.001 to 10, advantageously 0.01 to 5, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of chlorine-containing polymer will.

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

The stabilizer combination according to the invention can be used together with other Additives are used for processing and stabilization chlorine-containing polymers are common, such as. B.

• 1. Stabilizers:
  Epoxies and epoxidized fatty acid esters; Phosphites; Thiophosphites and thiophosphates; Polyols; 1,3-dicarbonyl compounds; Mercaptocarboxylic acid esters; Dihydropyridines; Antioxidants; Light stabilizers and UV absorbers; Alkali and alkaline earth compounds; Perchlorate salts; Zeolites; Hydrotalcites; Dawsonite;
• 2. other common PVC additives such. B .:
  Lubricant; Plasticizers; Impact modifiers; Processing aids; Blowing agent; Fillers; Antistatic; Biocides; Anti-fogging agents; Pigments and dyes; Metal deactivators; Flame retardants (cf. "Handbook of PVC-Formulating" by EJ Wickson, John Wiley & Sons, New York 1993).

Examples of such additives are known to the person skilled in the art and can be found in the specialist literature. Some of the known additives and processing aids are mentioned as non-restrictive:
Phosphites: Organic phosphites are known co-stabilizers for chlorine-containing polymers. Examples are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl, triphenyl, tricresyl, tris-nonylphenyl-tris-2,4-t-butylphenyl or tricyclohexyl phosphite.

Other suitable phosphites are differently mixed aryl dialkyl. respectively. Alkyl-diarylphosphites such as phenyldioctyl, phenyldidecyl, phenyldidodecyl, Phenylditridecyl, phenylditetradecyl, phenyldipentadecyl, octyldiphenyl, Decyldiphenyl, undecyldiphenyl, dodecyldiphenyl, tridecyldiphenyl,  Tetradecyldiphenyl, pentadecyldiphenyl, oleyldiphenyl, stearyldiphenyl and dodecyl-bis-2,4-di-t-butylphenyl phosphite.

Furthermore, phosphites of different diols or polyols can also be used advantageously: e.g. B. tetraphenyl dipropylene glycol diphosphite, Polydipropylenglykolphenylphosphit, tetramethylolcyclohexanol decyldiphosphit, tetramethylolcyclohexanol-butoxyethoxy-ethyldiphosphit, tetramethylolcyclohexanol-nonylphenyldiphosphit, bis-nonylphenyl-di trimethylolpropandiphosphit, bis-2-butoxyethyl-di trimethylolpropandiphosphit, trishydroxyethyl hexadecyltriphosphit, Didecylpentaerythritdiphosphit, distearyl pentaerythritol diphosphite, bis-2,4-di -t-butylphenylpentaerythritol diphosphite, and mixtures of these phosphites and aryl / alkylphosphite mixtures of the statistical composition (H₁₉C₉-C₆H₄) O _1.5 P (OC _12.13 H _25.27 ) _1.5 or [C₈H₁₇-C₆H₄-O-] ₂P [i-C₈H₁₇O] or (H₁₉C₉-C₆H₄) O _1.5 P (OC _9.11 H _19.23 ) _1.5 .

The organic phosphites can be used in an amount of, for example, 0.01 to 10, advantageously 0.05 to 5 and in particular 0.1 to 3 parts by weight, based on 100 parts by weight of PVC.
Polyols: Examples of compounds of this type are:
Pentaerythritol, Dipentaerythritol, Tripentaerythritol, Bistrimethylolpropane, Trimethylolethane, Bistrimethylolethane, Trimethylolpropane, Sorbitol, Maltitol, Isomaltitol, Lactitol, Lycasin, Mannitol, Lactose, Leucrose, Tris- (hydroxyethyl) isocyanurolamethyltrolamethyltrolamethyltrolamethyltrolamethyltolamethyltrolamethyltrolamethyltrolamethyltrolamethyltrolamethyltrolamethyltrolamethyltrolamethyltrolamethyltrolamethyltrolamethyltrolamylolamylolamylolamethyltrolamethyltrolamylolamylolamyltolamethyloltrylolamethyloltrylolamethyloltrylolamyl-tol-methylol-tetramethanol-tetramethyl-tetramethylamine Diglycerin, polyglycerin, thiodiglycerin, or 1-0-alpha-D-glycopyranosyl-D-mannitol dihydrate as well as polyvinyl alcohol and cyclodextrins. Of these, TMCH and the disaccharide alcohols are preferred.

The polyols can be used in an amount of, for example, 0.01 to 20, advantageously 0.1 to 20 and in particular 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, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert.nonylthio-heptanedione-2,4, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, benzylmethane, palmitoylmethane, palmitoylmethane, palmitoylmethane , Isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoyl) Benzoyl-1-acetylnonane, benzoyl-acetyl-phenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoyl-phenylacetylmethane, bis (cyclohexanoyl) methane, di (pivaletylacetic acid) methane, methane , ethyl ester, hexyl ester, octyl ester, dodecyl ester or octadecyl ester, benzoylacetic acid ethyl ester, butyl ester, -2-ethylhexyl ester, dodecyl ester or octadecyl ester, stearoylacetic acid ethyl, propyl, butyl, h exyl or octyl esters and dehydroacetic acid and their zinc, alkali, alkaline earth or aluminum salts. The 1,3-dicarbonyl compounds can be used in an amount of, for example, 0.01 to 10, advantageously 0.01 to 3 and in particular 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 = 0 and (RS) ₃P = S, as understood in the patents DE 28 09 492, EP 090770 and EP 573394 are described. Examples are: trithiohexylphosphite, trithiooctylphosphite, trithiolaurylphosphite, trithiobenzylphosphite, trithiophosphoric acid-tris- [carboxy-i-octyloxy] -methyl ester, trithiophosphoric acid-S, S, S- tris- [carbo-i-octyloxyith-methylphosphate, S, S-tris [carbo-2-ethylhexyloxy] methyl ester, trithiophosphoric acid-S, S, S, -tris-1- [carbo-hexyloxy] ethyl ester, trithiophosphoric acid-S, S, S-tris-1- [ carbo-2-ethylhexyloxy] ethyl ester, trithiophosphoric acid S, S, S tris-2- [carbo-2-ethylhexyloxy] ethyl ester.

The thiophosphites or thiophosphates can expediently be present in the chlorine-containing polymer in an amount of 0.01 to 20, preferably 0.1 to 5, in particular 0.1 to 1%.
Mercaptocarboxylic acid esters: Examples of these compounds are: esters of thioglycolic acid, thio malic acid, mercaptopropionic acid, mercaptobenzoic acids or thiolactic acid, as described in FR 2459816, EP 90748, FR 2552440 and EP 365483. The mercaptocarboxylic acid esters also include corresponding polyol esters or their partial esters.

They can suitably be present in the chlorine-containing polymer in an amount of 0.01 to 10, preferably 0.1 to 5, in particular 0.1 to 1%.
Epoxides and epoxidized fatty acid esters: The stabilizer combination according to the invention can additionally contain at least one epoxidized fatty acid ester. For this purpose, esters of fatty acids from natural sources such as soybean oil or rapeseed oil are particularly suitable.

The epoxy compounds are used in amounts of, for example, from 0.1 part, based on 100 parts by weight of composition, advantageously from 0.1 to 30, preferably from 0.5 to 25 parts by weight. Other examples are epoxidized polybutadiene, epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methyl butyl or 2-ethylhexylepoxystearate, tris (epoxy propyl) isocyanurate, epoxidized castor oil, epoxidized sunflower oil, 3- Phenoxy-1,2-epoxypropane, bisphenol A diglycidyl ether, vinylcyclohexene di epoxy, dicyclopentadiene diepoxide and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate.

Bisphenol-A and bisphenol-F derivatives are also possible as epoxides, such as, for. B. described in the South African patent specification ZA-2600/94.
Dihydropyridines and polydihydropyridines: As monomeric dihydropyridines there are compounds such as B. in FR 2039496, EP 2007, EP 362012 and EP 24754 described in question. Those of the formula are preferred

wherein Z stands for CO₂CH₃, CO₂C₂H₅, CO₂ ⁿ C₁₂H₂₅ or -CO₂C₂H₄-S- ⁿ C₁₂H₂₅.

As polydihydropyridines there are mainly compounds of the following Formula in question

where T is unsubstituted C _1-12 alkyl.

L has the same meaning as T.
m and n represent numbers from 0 to 20,
k is 0 or 1,
R and R 'independently of one another are ethylene, propylene, butylene or an alkylene or cycloalkylene bismethylene group of the type - (- C _p H _2p -X-) _t C _p H _2p -.
p is 2 to 8,
t is 0 to 10
X represents oxygen or sulfur.

Such compounds are described in more detail in EP-0286887.

The (poly) dihydropyridines can expediently in the chlorine-containing polymer 0.001 to 5 and in particular 0.005 to 1 part by weight, based on the Polymer.

Thiodiethylene bis- [5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylate] is particularly preferred.
Alkali and alkaline earth compounds: These are primarily the carboxylates of the acids described above, but also corresponding oxides or hydroxides, carbonates or basic carbonates. Their mixtures with organic acids are also suitable. Examples are NaOH, KOH, CaO, Ca (OH₂), MgO, Mg (OH) ₂, CaCO₃, MgCO₃ dolomite, huntite, and fatty acidic Na, K, Ca or Mg salts.

In the case of alkaline earth and Zn carboxylates, their adducts with MO or M (OH) ₂ (M = Ca, Mg, Sr or Zn), so-called "overbased" compounds, are used.

In addition to the stabilizer combination according to the invention, alkali metal, alkaline earth metal and / or aluminum carboxylates are preferably used, such as, for. B. Na, K, Ca or aluminum 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 corresponds to the value of M 1, 2 or 3. The perchlorate salts can be complexed with alcohols or ether alcohols. The respective perchlorate can be used in various common dosage forms; e.g. B. as a salt or aqueous solution drawn on a support material such as PVC, calcium silicate, zeolites or hydrotalcites, or by chemical reaction of hydrotalcite with perchloric acid.

The perchlorates can be used in an amount of, for example, 0.001 to 5, advantageously 0.01 to 3, particularly preferably 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 person skilled in the art, e.g. B. from the patents DE 38 43 581, US 4000100, EP 062813, WO 93/20135. Compounds from the series of hydrotalcites can be represented by the general formula VI,

M ²⁺ _1- xM ³⁺ _x · (OH) ₂ · (A ^n- ) _{x / n} · mH₂O (VI)

to be discribed,
in which
M ²⁺ = one or more of the metals from the group Mg, Ca, Sr, Zn or Sn,
M ³⁺ = Al or B,
A ^{n represents} an anion with valence n,
n is a number from 1-2,
0 <x 0.5,
m is a number from 0-20.

Is preferred

represents;
Examples of hydrotalcites are
Al₂O₃ · 6MgO · CO₂ · 12H₂O, Mg _4.5 Al₂ (OH) ₁₃ · CO₃ · 3.5H₂O, 4MgO · Al₂O₃ · CO₂] H₂O,
4MgO · Al₂O₃ · CO₂ · 6H₂O, ZnO · 3MgO · Al₂O₃ · CO₂ · 8-9H₂O and
ZnO3MgOAl₂O₃CO₂5-6H₂O.

Compounds from the series of zeolites (alkali or alkaline earth alumosilicates) can by the general formula (VII)

M _{x / n} [(AlO₂) _x (SiO₂) _y ] · wH₂O (VII)

to be discribed,
where n is the charge of the cation M;
M is an element of 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 WM Meier and DH Olson, Butterworth-Heinemann, 3rd edition 1992.
Examples of zeolites are sodium aluminosilicates of the formulas
Na₁₂Al₁₂Si₁₂O₄₈ · 27H₂O [zeolite A], Na₆Al₆Si₆O₂₄ · 2 NaX · 7.5 H₂O, X = OH, halogen, ClO₄ [sodalite]; Na₆Al₆Si₃₀O₇₂ · 24H₂O; Na₈Al₈Si₄₀O₉₆ · 24H₂O;
Na₁₆Al₁₆Si₂₄0₈₀ · 16H₂O; Na₁₆Al₁₆Si₃₂O₉₆ · 16H₂O; Na₅₆Al₅₆Si₁₃₆O₃₈₄ · 25OH₂O [zeolite Y], Na₈₆Al₈₆Si₁₀₆O₃₈₄ · 264H₂O [zeolite X];
or the zeolites which can be represented by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as
(Na, K) ₁₀Al₁₀i₂₂O₆₄ · 20H₂O; Ca _4.5 Na₃ [(AlO₂) ₁₂ (SiO₂) ₁₂] · 30 H₂O;
K₉Na₃ [(AlO₂) ₁₂ (SiO₂) ₁₂] · 27H₂O.

Other suitable zeolites are:
Na₂O · Al₂O₃ · (2 to 5) SiO₂ · (3.5 to 10) H₂O [zeolite P]
Na₂O · Al₂O₃ · 2 SiO₂ · (3.5-10) H₂O (zeolite MAP)
or the zeolites which can be represented by partial or complete replacement of the Na atoms by Li, K or H atoms, such as
(Li, Na, K, H) ₁₀Al₁₀Si₂₂O₆₄ · 20H₂O, K₉Na₃ [(AlO₂) ₁₂ (SiO₂) ₁₂] · 27H₂O, K₄Al₄Si₄O₁₆ · 6H₂O [Zeolite KF], Na₈Al₈Si₄₀O₉₆ · 24 H₂O Barrel zeolite D, as in J Chem. Soc. 1952, 1561-71, and in US 2,950,952;

The following zeolites are also suitable:
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 described 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 LZ-21 2 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 LZ-214 as described in US 4,503,023; Zeolite ZK-19, as in Am. Mineral. 54 1607 (1969); Zeolite W (KM) as described in Barrer et al. J. Chem. Soc. 1956, 2882; Na₃₀Al₃₀Si₆₆O₁₉₂ · 98H₂O [zeolite ZK-5, zeolite Q].

Zeolite P types of the formula IV are particularly preferably used, in which x 2 to 5 and y 3.5 to 10 are, very particularly preferably, zeolite MAP of the formula IV, where x is 2 and y are 3.5 to 10. In particular, it is zeolite Na- P, d. H. M stands for Na. This zeolite generally occurs in the variants Na P-1, NaP-2 and Na-P-3, which are characterized by their cubic, tetragonal or distinguish orthorhombic structure (R.M. Barrer, B.M. Munday, J. Chem. Soc. A 1971, 2909-14). In the literature just mentioned there is also Preparation of zeolite P-1 and P-2 described. Zeolite P-3 is very good after that rare and therefore hardly of practical interest. The structure of the zeolite P-1 corresponds to that known from the Atlas of Zeolite Structures mentioned above Gismondite structure. In more recent literature (EP-A-384 070) between cubic (Zeolite B or Pc) and tetragonal (Zeolite P₁) P-type zeolite distinguished. Newer P-type zeolites with Si: Al are also produced there Ratios below 1.07: 1 called. These are zeolites with the Designation MAP or MA-P for "Maximum Aluminum P". Depending on Manufacturing process, zeolite P can contain small amounts of other zeolites contain. Very pure zeolite P has been described in WO 94/26662.

In the context of the invention, such finely divided, water-insoluble can also be Use sodium aluminosilicates in the presence of water-soluble inorganic or organic dispersants and have been crystallized. These can be done in any way before or during the precipitation or crystallization are introduced into the reaction mixture.

Na zeolite A and Na zeolite P are preferred.

The hydrotalcites and zeolites can be naturally occurring minerals or be synthetically produced compounds.

The hydrotalcites and / or zeolites can be used in amounts of, for example, 0.1 to 50, advantageously 0.1 to 10 and in particular 0.1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer.
Alkaline alumocarbonates (Dawsonite): These compounds can be represented by the formula

{M₂O) _m · (Al₂O₃) _n · Z _o · pH₂O} (V),

represent
wherein MH, Li, Na, K, Mg _1/2 , Ca _1/2 , Sr _1/2 or Zn _1/2 ; ZCO₂, SO₂, (Cl₂O₇) _1/2 , B₄O₆, S₂O₂ (thiosulfate) or C₂O₂ (oxalate); in if M is Mg _1/2 or Ca _1/2 , 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 a number between 2 and 4; and p is a number between 0 and 30.

The aluminum salt compounds of formula (V) that can be used can be naturally occurring minerals or synthetically produced compounds. The metals can be partially interchanged. The aluminum salt compounds mentioned are crystalline, partially crystalline or amorphous or can be present as a dried gel. The aluminum salt compounds can also be present in rarer, crystalline modifications. A process for the preparation of such compounds is given in EP 394670. Examples of naturally occurring aluminum salt compounds are indigirite, tunisite, alumohydrocalcite, para-alumohydrocalcite, strontiodresserite and hydro-strontiodresserite. Other examples of aluminum salt compounds are potassium alumocarbonate {(K₂O) · (Al₂O₃) · (CO₂) ₂.2H₂O}, sodium alumothiosulfate {(Na₂O) · (Al₂O₃) · (S₂O₂) ₂ · 2H₂O} potassium alumosulfite {(K₂O) · (Al₂O₃ ) · (SO₂) ₂ · 2H₂O}, calcium alumoxalate {(CaO) · (Al₂O₃) · (C₂O₂) ₂ · 5H₂O}, magnesium alumotetraborate {(MgO) · (Al₂O₃) · (B₄O₆) ₂ · 5H₂O}, {([Mg _0.2 Na _0.6 ] ₂O) · (Al₂O₃) · (CO₂) ₂ · 4.1H₂O}, {([Mg _0.2 Na _0.6 ] ₂O) · (Al₂O₃) · (CO₂) ₂ · 4 , 3H₂O} and {([Mg _0.3 Na₀ · ₄] ₂O) · (Al₂O₃) · (CO₂) _2.2 · 4.9H₂O}.

The mixed aluminum salt compounds can be prepared according to known methods Process by cation exchange, preferably from the alkali-aluminum salt Compounds or by combination precipitation (see for example US 5,055,284) can be obtained.

Preferred are alumino salt compounds of the above formula, wherein M is Na or K; Z CO₂, SO₂ or (Cl₂O₇) _1/2 ; m 1-3; n 1-4; o 2-4 and p mean 0-20. Z is particularly preferably CO₂.

Furthermore, compounds are preferred which are represented by the following formulas display:

M₂O · Al₂O₃ · (CO₂) ₂ · pH₂O (Ia),

(M₂O) ₂ · (Al₂O₃) ₂ · (CO₂) ₂ · pH₂O (Ib),

M₂O · (Al₂O₃) ₂ · (CO₂) ₂ · pH₂O (Ic)

where M is a metal such as Na, K, Mg _1/2 , Ca _1/2 , Sr _1/2 or Zn _1/2 and p is a number from 0 to 12.

Sodium aluminodihydroxy carbonate (DASC) and die are particularly preferred homologous potassium compound (DAPC).

The dawsonites can be used in an amount of, for example, 0.01 to 50, Appropriately 0.1 to 10, particularly preferably 0.1 to 5 parts by weight, based can be applied to 100 parts by weight of halogen-containing polymer.

The stabilizer combination according to the invention can be used together with other additives which are common for the processing and stabilization of chlorine-containing polymers, such as. B .:
Antioxidants: These include, for example:

• 1. Alkylated monophenols, e.g. B. 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n- butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4- methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di- octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'- methyl-undec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl) - phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) phenol and mixtures from that.
• 2. alkylthiomethylphenols, e.g. B. 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4- Di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
• 3. hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4- methoxyphenol, 2,5-di-tert-butyl hydroquinone, 2,5-di-tert-amyl hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy anisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4- hydroxyphenyl) adipate.
• 4. tocopherols, e.g. B. alpha-tocopherol, beta-tocopherol, g-tocopherol, d- Tocopherol and mixtures thereof (vitamin E).  
• 5. Hydroxylated thiodiphenyl ether, e.g. B. 2,2'-thio-bis- (6-tert-butyl-4- methylphenol), 2,2'-thio-bis- (4-octylphenol), 4,4'-thio-bis- (6-tert-butyl-3- methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis- (3,6- di-sec.-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
• 6. alkylidene bisphenols, e.g. B. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis- [4-methyl- 6- (alpha-methylcyclohexyl) phenol], 2,2'-methylene-bis- (4-methyl-6- cyclohexylphenol), 2,2'-methylene-bis- (6-nonyl-4-methyl phenol), 2,2'- Methylene-bis- (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert- butylphenol), 2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 2,2'- Methylene-bis- [6- (alpha-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis- [6- (aipha, alpha-dimethylbenzyl) -4-nonylphenol], 4,4′-methylene-bis- (2,6-di- tert-butylphenol), 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1,1-bis- (5- tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2- hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5-tert-butyl-4-hydroxy-2- methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n- dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'- hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) - dicyclopentadiene, bis- [2- (3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl) -6-tert- butyl 4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2- hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercapto butane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
• 7. O-, N- and S-benzyl compounds, e.g. B. 3,5,3 ', 5'-tetra-tert-butyl-4,4- dihydroxy-dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, 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.
• 8. Hydroxybenzylated malonates, e.g. B. 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, di- [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.  
• 9. Hydroxybenzyl aromatics, e.g. B. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) - 2,4,6-trimethylbenzene, 1,4-bis (3,6-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, e.g. B. 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, 1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6- dlmethylbenzyl) 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-hydroxy) phenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris- (3,5-dicyciohexyl-4- hydroxybenzyl) isocyanurate.
• 11. Benzylphosphonates, e.g. B. Dimethyl-2,5-di-tert-butyl-4- hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxy benzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3- methylbenzylphosphonate, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic acid monoethyl ester.
• 12. acylaminophenols, e.g. B. 4-hydroxy lauric anilide, 4- Hydroxystearic acid aniide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) - carbamic acid octyl ester.
• 13. Esters of beta (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with one or polyhydric alcohols, such as. B. 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) - oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- trioxabicyclo- [2.2.2] octane.
• 14. Esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, such as. B. 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 (hydroxy) ethyl isocyanurate, N, N'-bis  (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- trioxabicyclo- [2.2.2] octane.
• 15. Esters of beta- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with one or polyhydric alcohols, such as. B. 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 (hydroxy) ethyl isocyanurate, N, N′-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- trioxablcyclo- [2.2.2] octane.
• 16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with one or polyhydric alcohols, such as. B. 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 (hydroxy) ethyl isocyanurate, N, N′-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- trioxabicyclo- [2.2.2] octane.
• 17. Amides of beta (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as, for. B. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N′-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

If necessary, a mixture of antioxidants different structure can be used.

The antioxidants can be used in an amount of, for example, 0.01 to 10, advantageously 0.05 to 10 and in particular 0.05 to 5 parts by weight, based on 100 parts by weight of PVC.
UV absorbers and light stabilizers: Examples include:

• 1. 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-Hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl- 2′-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy- 5 ′ - (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ′, 5, -di-tert-butyl- 2-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5 '-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5, -di-tert-amyl-2'-hydroxyphenyl) - benzotriazole, 2- (3 ′, 5′-bis (aipha, alpha-dimethylbenzyl) -2′-hydroxyphenyl) benzotriazole, mixture of 2- (3′-tert-butyl-2′-hydroxy-5 ′ - ( 2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole , 2- (3'-tert-Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phen yl) -benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-tert-butyl-5' - [2- ( 2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzot riazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tert-butyl-2 '-Hydroxy-5' - (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, - 2,2'- methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol- ]; Transesterification product of 2- [3′-tert-butyl-5 ′ - (2-methoxycarbonylethyl) -2′-hydroxyphenyl] benzotriazole with polyethylene glycol 300; with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.
• 2. 2-hydroxybenzophenones, such as. B. the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy 4,4'-dimethoxy derivative.
• 3. Esters of optionally substituted benzoic acids, such as. B. 4-tert-butyl phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, Bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4- 2,4-di-tert-butylphenyl hydroxybenzoate, 3,5-di-tert-butyl-4- hexadecyl hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxy octadecyl benzoate, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2- methyl 4,6-di-tert-butylphenyl ester.
• 4. Acrylates, such as. B. alpha-cyan-beta, beta-diphenylacrylic acid ethyl ester or isooctyl ester, alpha-carbomethoxy cinnamic acid methyl ester, alpha Cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, alpha-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- (beta Carbomethoxy-beta-cyanovinyl) -2-methyl-indoline.  
• 5. Nickel compounds, such as. B. Nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3- tetra-methylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyciohexyl-diethanolamine, nickel dibutyldithiocarbamate, Nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid mono alkyl esters, such as methyl or ethyl ester, nickel complexes of Ketoximes, such as from 2-hydroxy-4-methyl-phenyl-undecylketoxime, Nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, if appropriate with additional ligands.
• 6. Sterically hindered amines, such as. B. bis- (2,2,6,6-tetramethyl-piperidyl) - sebacate, bis (2,2,6,6-tetramethyl-piperidyl) succinate, bis (1,2,2,6,6- pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, Condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy- piperidine and succinic acid, condensation product of N, N′-bis- (2,2,6,6- Tetramethyl-4-piperidyl) hexamethylene diamine and 4-tert-octylamino-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-tetramethyl-piperazinone), 4-benzoyl-2,2,6,6-tetra methylpiperidine, 4-stearyloxy-2,2,6,6-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] decane-2,4-dione, Bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6- tetramethylpiperidyl) succinate, condensation product of N, N′-bis (2,2,6,6- tetramethyl-4-piperidyl) hexamethylene diamine and 4-morpholino-2,6- dichloro-1,3,5-triazine, condensation product from 2 chloro-4,6-di- (4-n- butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3- aminopropylamino) athan, condensation product of 2-chloro-4,6-di- (4-n- butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3- aminopropylamino) -ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8- triazaspiro [4.5] decan-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) pyrrolidine-2,5-dione.
• 7. oxalic acid diamides, such as. B. 4,4-di-octyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-  butyl oxanilide, 2-ethoxy-2'-ethyl oxanilide, N, N'-bis (3-dimethylaminopropyl) - oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2- Ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy- and of o- and p-ethoxy-di-substituted oxanilides.
• 8. 2- (2-hydroxyphenyl) -1,3,5-triazines such as e.g. B. 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-bls (2,4- dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propoxyphenyl) -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-butyloxy propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-trlazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, -3.5- triazine.

The stabilizer mixture according to the invention is preferred with alkali metal or alkaline earth metal carboxylates, in particular calcium carboxylates, with aluminum carboxylates, with 1,3-dicarbonyl compounds, with dihydropyridines, with phosphites or combinations of these substances.
Plasticizers: Examples of suitable organic plasticizers are those from the following groups:

A) Phthalic acid esters

Examples of such plasticizers are dimethyl, diethyl, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-iso-octyl, di-iso-nonyl, di-iso-decyl , Di-isotridecyl, dicyclohexyl, dimethylcyclohexyl, dimethylglycol, dibutylglycol, benzylbutyl and diphenyl phthalate and mixtures of phthalates such as C _7-9 and C _9-11 alkyl phthalates from predominantly linear alcohols, C _6-10 n alkyl phthalates and C _8-10 n alkyl phthalates. Of these, dibutyl, dihexyl, di-2-ethylhexyl, di-n-octyl, di-iso-octyl, di-isononyl, di-iso-decyl, di-iso-tridecyl and benzyl butyl are preferred phthalate and the mixtures of alkyl phthalates mentioned. Particularly preferred are di-2-ethylhexyl, di-iso-nonyl and di-iso-decyl phthalate, which are also used under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate) are known.

B) esters of aliphatic dicarboxylic acids, in particular esters of adipic, Azelaic and sebacic acid

Examples of such plasticizers are di-2-ethylhexyl adipate, di- isooctyl adipate (mixture), di-iso-nonyl adipate (mixture), di-iso-decyl adipate (Mixture), benzyl butyl adipate, benzyl octyl adipate, di-2-ethylhexyl azelate, di- 2-ethylhexyl sebacate and di-iso-decyl sebacate (mixture). Are preferred Di-2-ethylhexyl adipate and di-iso-octyl adipate.

C) Trimellitic acid ester

For example, tri-2-ethylhexyl trimellithate, tri-iso-decyl trimellithate (mixture), tri-iso-tridecyl trimellithate, tri-iso-octyl trimellithate (mixture) and tri-C _6-8 alkyl, Tn-C _6-10 alkyl, Tri-C _7-9 alkyl and Tri-C _9-11 alkyl trimellithates. The latter trimellithates are formed by esterifying trimellitic acid with the corresponding alkanol mixtures. Preferred trimellithates are tri-2-ethylhexyl trimellithate and the trimellithates mentioned from alkanol mixtures. Common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimellitate) and TITDTM (triisotridecyl trimellitate).

D) epoxy plasticizer

The main are epoxidized unsaturated fatty acids such as. B. epoxidized soy.

E) polymer plasticizer

The most common raw materials for making the Polyester plasticizers are: dicarboxylic acids such as adipic, phthalic, azelaic 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

Examples of such phosphoric acid esters are tributyl phosphate, tri-2- ethyl butyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethyl-hexyl-di-phenyl phosphate, cresyl diphenyl phosphate, Triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Prefers are tri-2-ethylhexyl phosphate and ®Reofos 50 and 95 (ex. FMC).

G) Chlorinated hydrocarbons (paraffins) H) hydrocarbons I) monoesters, e.g. B. butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and Alkyl sulfonic acid esters J) glycol esters, e.g. B. Diglykolbenzoate

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

"PVC Technology", publisher W. V. Titow, 4th. Ed., Elsevier Publishers, 1984, Chapter 6. Pages 147-180.

Mixtures of different plasticizers can also be used will.

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

Examples of suitable lubricants are:
Montan waxes, fatty acid esters, PE waxes, amide waxes, chlorinated paraffins, glycerol esters or alkaline earths soaps or silicone-based lubricants as described in EP 225261. Usable lubricants are also described in "Taschenbuch der Kunststoffadditive", edited by R. Gächter and H. Müller, Carl Hanser Verlag, 3rd edition, 1989, pages 478-488.
Fillers: fillers ("Handbook of PVC-Formulating" by EJ Wickson, John Wiley & Sons, New York 1993 pp. 393-449) and reinforcing agents ("Taschenbuch der Kunststoffadditive", editors R. Gächter and H. Müller, Carl Hanser Verlag , 3rd edition, 1989, pages 549-615) can e.g. Example: calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass fibers, talc, kaolin, chalk, mica, metal oxides and hydroxides, carbon black or graphite), chalk is preferred.
Pigments: Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are TiO₂, carbon black, Fe₂O₃, Sb₂O₃, (Ti, Ba, Sb) O₂, Cr₂O₃, spinels such as cobalt blue and cobalt green, Cd (S, Se), ultramarine blue. TiO₂ is preferred, also in micronized form. Organic pigments are e.g. B. azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, pyrrolopyrrole pigments and anthraquinone pigments. Further details can be found in "Handbook of PVC Formulating", EJ 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, containing vinyl resins Vinyl chloride units in their structure, such as copolymers of vinyl chloride and Vinyl esters of aliphatic acids, especially vinyl acetate, copolymers vinyl chloride 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 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 of the same with vinyl chloride and other polymerizable Links; Polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of Acrylic acid and the alpha-substituted acrylic acid; Polymers of chlorinated Styrenes, for example dichlorostyrene; chlorinated gums; chlorinated polymers of Ethylene; Polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride, chlorinated natural and synthesis rubbers, and mixtures of the polymers mentioned among themselves or with other polymerizable compounds.

In the context of this invention, copolymers are also included under PVC polymerizable compounds such as acrylonitrile, vinyl acetate or ABS understand, which are suspension, bulk or emulsion polymers can act. PVC homopolymer is also preferred in combination with Polyacrylates.

Also included are the graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the above Homopolymers and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic and / or elastomeric polymers, in particular  Blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and Polylactones.

Suspension and bulk polymers and emulsion polymers are preferred.

Polyvinyl chloride is particularly preferred as the chlorine-containing polymer. in particular as a suspension polymer and bulk polymer.

Furthermore, stabilization also comes within the scope of this invention Recyclates of chlorine-containing polymers in particular, in which case is the polymers described in more detail above, which by Processing, use or storage have been damaged. PVC recyclate is particularly preferred. Small ones can also be found in the recyclates Amounts of foreign matter may be included, such as. B. paper, pigments, Adhesives that are often difficult to remove. These foreign substances can also from contact with various substances during use or Work up come, such. B. fuel residues, paint, traces of metal and Remaining initiator.

The stabilizer mixture is used by a person skilled in the art known way.

The stabilizer mixture can e.g. B. also together with conventional Additions before the actual use for example Granules or extrudate or a paste can be processed.

Another object of the present invention is the use of stabilizer mixture just described - also as granules, extrudate or paste also in connection with lubricant (so-called one-pack) - for Stabilization of a halogen-containing polymer or polymer recyclate. For the individual stabilizers and the halogen-containing polymer itself apply the preferences explained above, also one of the further components described above can be used.

The stabilizer mixture can the polymer in a known manner be added, using known ones Devices such as mixers, kneaders, extruders, mills and the like, the mentioned stabilizers and any other additives with the halogen-containing polymer mixed. The stabilizers can be used individually or added in a mixture or in the form of so-called  Masterbatches. The invention thus also relates to a method for Stabilization of halogen-containing polymer, characterized in that using devices such as calenders, mixers, Kneaders, extruders and the like, the stabilizer components and if necessary, other additives mixed with the PVC.

The invention also relates to those stabilized in this way Polymer compositions containing the invention Stabilizer mix. They can be made in the desired manner in known ways Be brought into shape. Such processes are, for example, calendering, Extrusion, injection molding, sintering or spinning, also extrusion blowing or processing according to the plastisol process. The Polymer compositions can also be made into foams will.

The invention also relates to the use of the stabilized Polymer compositions for the production of halogen-containing Polymer moldings. The invention Polymer compositions are suitable for semi-hard and soft Recipes such as B. for soft formulations for wire jackets and Cable insulation. They are suitable in the form of semi-hard formulations polymer compositions according to the invention for decorative films, Foams, agricultural foils, hoses, sealing profiles, office foils extruded profiles and sheets, flooring sheets and sheets, spreads and Synthetic leather and crashpad foils (for use in the automotive sector).

The formulations according to the invention are suitable in the form of hard formulations Polymer compositions for hollow bodies (bottles), packaging films (Thermoformed films), blown films, crash pad films (automobiles), pipes, Foams, heavy profiles (window frames), light wall profiles, building profiles, Sidings, fittings, and equipment housings (computers, household appliances) as well other injection molded articles.

Examples of the use of those stabilized according to the invention Polymer compositions as plastisol are synthetic leather, floors, Textile coatings, wallpaper, coil coatings and underbody protection for Motor vehicles.  

Examples of sintering applications of the stabilized according to the invention Polymer compositions are slush, slush mold and coll coatings.

The preparation of the N-piperidinyl-triazines is known from the literature (cf. e.g. Houben-Weyl "Methods of Organic Chemistry" Vol. VIII, pp. 233-237, OXYGEN COMPOUNDS III, 3rd edition, Thieme Verlag Stuttgart 1952). As Starting material for the reaction with various N-piperidinyl amines can be cyanuric chloride, diamino-chloro-1,3,5-triazine or various substituted bisdiaikylamino-chloro-1,3,5-triazines or dialkylamino or Alkylamino-dichloro-1,3,5-triazines can be used.

The following examples further illustrate the invention without restricting it. As in the rest of the description, parts and percentages relate to the weight, unless stated otherwise.
Example 1: N, N'-bis- [2,2,6,6-tetramethylpiperidin-4-yl] oxamide
56.1 g (0.4 mol) of diethyl oxalate are slowly mixed with stirring with 156.3 g (0.8 mol) of 4-amino-2,2,6,6-tetramethylpiperidine, the aminolysis taking place with vigorous generation of heat. The temperature rises to approx. 100 ° C. After adding 150 ml of xylene, ethanol is distilled off at 88-137 ° C. in the course of 18.5 hours. The mixture is then taken up in 1500 ml of xylene, filtered hot and cooled. The precipitated crystals are filtered off and recrystallized from xylene.
Yield 120 g (82% of theory) mp 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 reaction of bis-2,2,6,6-tetramethylpiperidinyl 1,6-hexanediamine made with acetic anhydride:

Example 9: To produce stabilizers I and II, a Zn / Ca Stearate mixture with a commercial beta-diketone (rod. I) and on with the piperidine compound 5 in the ratio 8: 2: 1.5 (rod II) on one Tumble mixer mixed intensively over a period of 1.5 hours. Of these Stabilizer mixtures are each 1.0 parts (rod I) or 1.15 parts (Rod II) with 100 parts of S-PVC (K value 70) and 21 parts of a mixture of Dioctyl phthalate / epoxidized soybean oil and a commercially available liquid Aryl-alkyl phosphite mixed and 5 minutes at 190 ° C on one Mixing mill plasticized. From the foils thus obtained (thickness 0.2 mm) test specimens are cut and in a Mathis thermo clock at 180 ° C thermally over the period specified in Table 1 below charged. Then the Yellowness Index (YI) according to ASTM-1925-70 certainly.

The lower the YI value found, the more effectively the stabilizer system prevents yellowing and thus damage to the material. The long-term thermal stability of the stabilized polymer can be recognized from the sudden onset of massive discoloration. A stabilizer is more effective the longer this discoloration is delayed under thermal stress.
Heat test: YI of the test specimen at 1 80 ° C

table

Claims (10)

1. Stabilizer combination for halogen-containing polymers containing

• A) at least one organic zinc compound with a Zn-O bond;
• B) at least one compound of the formula wherein
  X: O or S;
  a: 0 to 8; b: 2 to 12; c: 1 or 2; k: 2 to 6;
  R₁: H or C₁-C₈-alkyl, C₃-C₈-alkenyl, C₇-C₉-phenylalkyl or C₅-C₈-cycloalkyl;

R₂: C₁-C₈-alkyl, -NH₂, R₃NG-, R₄-O-, [R₃-NG-CX] _c E-, (C₁-C₄-alkyl) ₂N (CH₂) _k -CX-, phenyl or with 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 , (C₁-C₄-alkyl) ₂N (CH₂) _k - or G;
R₄: C₁-C₄ alkyl, cyclohexyl or benzyl; A: <CO, - (CH₂) _m -, - (CH₂) _d -CO- or NH (CH₂) _n -CO- m: 0 or 1; n: 2 to 12; p: 0 or 1; d: 1 to 8; q: 1 or 2; r: 2 to 50;
where, when p is 0, A: <CO, - (CH₂) - _m , - (CH₂) _d -CO-, -NH (CH₂) _n -CO- when p is 1, A: (CH₂) _m ,
group L: means.
R₅: H, C₁-C₈ alkyl, C₃-C₈ alkenyl, C₅-C₈ cycloalkyl or G;
R₆: H, C₁-C₁₂ alkyl;
R₇: H or CH₃;
Q: -O- or <NH;
Y: -CH₂-CH (OH) -CH₂-; and s: 3 to 60. 2. Stabilizer combination according to claim i, wherein
X: O or S;
a: 0 to 4; b: 2 to 6; c: 1 or 2; k: 2 or 3;
R¹: H or C₁-C₈ alkyl;
R₂: C₁-C₈-alkyl, -NH₂, R₃-NG-, [R₃-NG-CX] _c E- 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; R₅: H, C₁-C₈ alkyl or G;
A: -CO-, - (CH₂) _m -, - (CH₂) d-CO- or -NH (CH₂) _n -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;
where, when p is 0, A: -CO-, - (CH 2) _m -, - (CH₂) _d -CO- or -NH (CH₂) _n -CO-,
if p is 1, A: is (CH₂) _m -,
group L: means
R₆: H or C₁-C₁₂ alkyl;
Y: -CH₂-CH (OH) -CH₂-;
R₇: H or CH₃;
Q: -O- or <NH, and s: 3 to 60. 3. Stabilizer combination according to claim 1, wherein
X: O;
a: 0 to 4; b: 2 to 6; c: 1;
R₁: H or C₁-C₈ alkyl;
R₂: [R₃-NG-CX] _c E-;
R₃: H, C₁-C₈ alkyl, R₂-CX-NG- (CH₂) _b or G;
E: (CH₂) _a or -NH- (CH₂) _b NH-;
R₅: G;
A: - (CH₂) _m -;
m: 0 or 1; n: 2 to 6; p: 0; q: 1 or 2; r: 2 to 50;
the group L: -CH₂-CHR₆-, - (CH₂) -₃, or -CH = CH-,
R₆: H;
Y: -CH₂-CH (OH) -CH₂-;
R₇: H;
Q: <NH; and s: 3 to 60. 4. Stabilizer combination according to claim 1, which additionally alkali and / or alkaline earth compounds and / or aluminum compounds contains. 5. Stabilizer combination according to claim 1, which additionally Contains calcium carboxylates. 6. Stabilizer combination according to claim 1, which additionally Contains aluminum carboxylates. 7. Stabilizer combination according to claim 1, which additionally at least one further substance from the group of epoxides and epoxidized fatty acid esters, phosphites, thiophosphites and Thiophosphates, polyols, 1,3-dicarbonyl compounds, Mercaptocarboxylic acid esters, dihydropyridines, antioxidants, Light stabilizers and UV absorbers, alkali and alkaline earth compounds, Contains perchlorate salts, zeolites, hydrotalcites or dawsonites. 8. Composition containing a halogen-containing polymer and Stabilizer combination according to claim 1. 9. A method for stabilizing halogen-containing polymers, thereby characterized in that one according to a stabilizer combination Adds claim 1.