FR2746405A1 - COMBINATIONS OF STABILIZERS BASED ON 2,2,6,6-TETRAMETHYLPIPERIDINE DERIVATIVES AND ORGANIC ZINC COMPOUNDS FOR CHLORINATED POLYMERS - Google Patents

Abstract

The subject of the invention is a combination of stabilizers for halogenated polymers, containing at least one organic zinc compound with a Zn-O bond and at least one compound of formula: (CF DRAWING IN BOPI), (CF DRAWING IN BOPI) in which in particular: X = O or S; A => CO, - (CH2) m-, - (CH2) d -CO- or NH (CH2) n -CO-; m = 0 or 1; n = 2 to 12; p = 0 or 1; r = 2 to 50; (CF DRAWING IN BOPI) Y = -CH2 -CH (0H) -CH2 -; q = 1 or 2; S = 3 to 60.

Description

The invention relates to a combination of stabilizers suitable for

  stabilizing chlorinated polymers, in particular PVC, and consisting of an organic zinc compound having a Zn-O or Zn-S bond, in particular a zinc carboxylate, and at least one compound having one formulas I, II, III and IV shown below. PVC can be stabilized by a variety of additives. Lead compounds, barium and cadmium are particularly suitable for this purpose, but are now controversial for ecological reasons (see "Taschenbuch der Kunststoffadditive", published by R. Gachter and H. Mler, Editions Carl Hanser ,

  3 "edition, 1989, pages 303-311, and KunststoffHandbuch PVC, volume 2/1, G.W.

  Becker, D. Braun, Carl Hanser Editions 1985, pp. 531-538). Stabilizers and active stabilizer compositions are therefore still sought without disadvantageous properties. Sterically hindered amines have already been added to the PVC as light stabilizers. The thermal stability also can be advantageously

  influenced (see, for example, EP-A-366271 and EPA-488951).

  It has now been found that organic zinc compounds, such as, for example, zinc carboxylates, can advantageously be combined with compounds having the formulas (CO 2 R 3 R 3 -N-CX-R 2) n H) 1 1; 1 NNA JiCHN Lw, (I) m (N) m {0N-R1 (111) efou Q> (IV)

NOT

  RR R7 o C - C-H -}; oc L N - (Y) m (N) m N-R1 (III) and / or Q (IV)

O _ RI

  for stabilizing chlorinated polymers. In these formulas, the remains and symbols have the following meanings: X represents O or S;

  R. is H or C1-C8 alkyl, C3-C8 alkenyl, C7-C7 phenylalkyl

  or C5-C8 cycloalkyl; R2 is a C1-C8 alkyl, -NH2, R3NG-, R4-O-, [R3-NG-CX] .E-, (C1-C4) alkyl2N (CH2-CX-), phenyl or phenyl substituted by OH, C 1 -C 4 alkoxy or C 1 -C 4 alkyl; G is N-R 1; R 3 is H or C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 5 -C 8 cycloalkyl, R 2 -CX-NG- (CH 1 -C 4 -alkyl) 2N (CH 2) k- or G; R 4 is a C 1 -C 4 alkyl radical, cyclohexyl or benzyl; E is (CH 2) 2 = CH -, -CH (OH) -CH (OH) -, -CH2-CH (OH) - or -NH (CH2) bNHI-; A is - (CH2) m-,> CO, - (CH2) d-CO or -NH (CH2) -CO-; a is a number from 0 to 8; b is a number from 2 to 12; c is 1 or 2; d is a number from 1 to 8; k is a number of 2; at 6, m is 0 or 1, n is a number from 2 to 12, p is 0 or 1, q is 1 or 2, r is a number from 2 to 50, and when p is 0, A is> CO - (CH2) m-, - (CH2) d-CO-, -NH (CH2) .- CO-, and when p is 1, A is - (CH2) m-, the group L is -CH2- CHR6-, - (CH2) 3-, -CH = CH-, G- (N) mY'-NC = O,

/ II.

  or R 5 is H or C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 5 -C 8 cycloalkyl or G; R6 is H or C1-C12 alkyl; R7 is H or CH3; Q is -O- or> NH; Y is -CH2-CH (OH) -CH2-; and

s is a number from 3 to 60.

  In the above formulas: a C 1 -C 4 alkyl residue is a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or t-butyl residue;

  a C 1 -C 8 alkyl residue represents the same residues and, for example, a remainder n

  pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-ethylhexyl, noctyle or isooctyl; a C 5 -C 8 cycloalkyl radical represents, for example, a cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl residue; the cyclopentyl remains and in particular

cyclohexyl are preferred.

  When substituents represent a C3-C5 alkenyl residue, it may be a linear or branched alkenyl such as, for example, allyl residues,

  crotonyl, 2-methylallyl or hexenyl.

  A C 1 -C 4 alkoxy radical for example means a methoxy or ethoxy radical,

  propoxy, isopropoxy, butoxy or isobutoxy.

  A C 7 -C 9 phenylalkyl radical is, for example, a benzyl radical, 1- or 2-

  phenylethyl, 3-phenylpropyl, α, β-dimethylbenzyl or 2-phenylisopropyl,

preferably benzyl.

  The combination of stabilizers preferably comprises compounds of formula I to IV wherein X is O or S; R. is H or a C 1 -C 8 alkyl radical; R2 is (C1-C8) alkyl, -NH2, R3NG-, [R3-NG-CX], E- or (C1-C4) alkyl2N (CH2-CX); R3is H or a C1-C4 alkyl radical; -C, R2-CX-NG- (CH) b, (C1-C4) alkyl2N (CH1- or -G; E is (CH2) n-, -CH = CH- or -NH ( CH) bNH-; R5 is H or a C1-C8 alkyl residue or G; A is -CO-, - (CH2) m-, - (CH2) d-CO- or -NH (CH2) n-CO -; a is a number from 0 to 4, b is a number from 2 to 6, c is equal to 1 or 2, d is a number from 1 to 4, k is equal to 2 or 3, m is 0 or 1 n is a number from 2 to 6; p is 0 or 1; q is 1 or 2; r is a number from 2 to 50; and when p is 0, A is -CO-, - (CH 2) n; - (CH2) d-CO- or -NH (CH2) n-CO- and when p is 1, A is - (CH2) m-, L is -CH2-CHR6-, - (CH2) 3 -, G- (N) mYe-N C = O or I 11L R6 is H or a C1-C12 alkyl residue; Y is -CH2-CH (OH) -CH2-; R7 is H or CH3; Q is -O- or> NH;

s is a number from 3 to 60.

  Compounds of formula I to IV are particularly preferred in which: X is O; R represents H or a C 1 -C 6 alkyl radical; R2 is a residue [R3-NG-CX], E-; R3 is H or (C1-C8) alkyl, R2-CX-NG- (CH2) b, or -G; E is (CH2) 1, or -NH (CH2) bNH-; R1 is G; A is (CH2) m-; a is a number from 0 to 4; b is a number from 2 to 6; c is 1; m is 0 or 1; n is a number from 2 to 6; p is 0; q is 1 or 2; r is a number from 2 to 50; L is -CH2-CHIR6-, - (CH2) 3- or -CH = CH-; R6 is H; Y is -CH2-CH (OH) -CH2-; R7 is H; Q is> NH; and

s is a number from 3 to 60.

  Examples of piperidine derivatives of formula I 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-diformamide; 03) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) adipamide; 04) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) oxamide; 4-hydroxybenzamido-2,2,6,6-tetramethylpiperidine;

- CH2-CO-N (CH2) 6 N '

06)

N N

-HH r

0 0

07) HN NH-C - C-NH N

CH3-CO-N (CH2) 3 N CO-CH3

08)

N N

H H

o 09) -N NHi-C-CH3

H H

I I

N N

  ) - CH 2 -CO N- (CH 2) 6 N-CO-CH 2 -N (CH 2) 2 N

N N

H H r

H H

I I

N N

  11) - CH 2 -CO-N (CH 2) 3 N-CO-CH 2 -N (CH 2) - 3 N

N N

H H r

O OH

12) HN NH-C

HN CO- NH

13)

N N

H H

he

14) HIN NH-C-CH3

  (II) HN NH-C-C-NH- (CH2) / - N (i-Pr) 2

CO- (CH 2) 6 -CO-N (CH 2) 6 N

16)

N N

- H H -r CH3 C-CH2

17) O

NHi r o o II He

N (CH2) 3 N C-C-

18)

N N

-H H r

O O

He He

N (CH 2) 2 N C- (CH 2) -C

19)

N N

r

O O -

o o He He

N (CH 2) 6 N C -NH- (CH 2) -NH-C -

)

N N

H H

21) (H-N NH) 2CS

  o o in 1 1 r1 22) HN NH-C C-NHt Ni o o I

A .. A

23) -N NH-C-CH-CH-C-NH N-

Y 1

o o He He

24) H-N N-C-CH = CH-C-N N-H

  C4Hg 4C Hg oII (i-Pr) 2N-CH2-CH2-N-C-CH3) N O

H-N N-C-CH12-

H H -2 6 - at N H

28) 1 N -

O

CH3-C-N-

I 29) N

0 0

) H-N N Q N N-H

0 0

  ## STR5 ## NH NH OH

O O

o # x 34) o O

C12H25. X

) N N-H

0 0

II I

36)

I I II

H H H H r O

37) NN -

O

38) NN-

it i 39) N C2H5

) -H

O O / \ o O He He

N (CH 2) 3 N -C - N-CH 2 - N - CH-C--

41) H

L ir

H H

O O

\\ //

C-N (CH2) 6 N-C

II

42) H H

NN

H H

  The compounds of formula I to IV may be present in the polymer

  chlorinated at from 0.005 to 5, preferably from 0.01 to 2 and in particular from 0.01 to 1%.

  Zinc compounds Zinc organic enolates, zinc phenolates and / or zinc carboxylates are used for zinc-containing organic compounds containing Zn-O. The latter are compounds of the series of saturated or unsaturated aliphatic C, -C 4 carboxylates, saturated or unsaturated aliphatic C2-C22 carboxylates, substituted by at least one OH group or the chain of which is interrupted by one or more oxygen atoms (oxaacids), cyclic and bicyclic carboxylates of 5 to 22 carbon atoms, unsubstituted phenoxycarboxylates, substituted by at least one OH group and / or substituted by C 1 -C 16 alkyl, phenyl (C.sub.1 -C.sub.6 alkyl) carboxylates or phenolates optionally substituted with C.sub.1 -C.sub.2 alkyl or abietic acid. The Zn-S compounds are, for example,

  Zn mercaptides, Zn-mercaptocarboxylates and Zn-

  mercaptocarboxylic. Of particular note are zinc salts of monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristyl acid, palmitic acid, lauric acid , isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid,

  oleic acid, ricinoleic acid, 3,6-dioxaheptanoic acid,

  trioxadecanoic acid, behenic acid, benzoic acid, p-tertbutylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid,

  tolyl acid, dimethyl benzoic acid, ethyl benzoic acid, n

  propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid, cinnamic acid, mandelic acid, glycolic acid; zinc salts of dicarboxylic acids or their monoesters such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-1 acid, 5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, acid

  heptane-1,7-dicarboxylic acid, octane-1,8-dicarboxylic acid, 3,6,9-

  trioxadecane-1,10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, malic acid, salicylic acid, polyglycoldicarboxylic acid (n = 10, 12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and di- or triesters of tri- or tetracarboxylic acids such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid or overbased zinc carboxylates or

  zinc lauryl mercaptide, zinc thioglycolate, zinc thiosalicylate, bis-i-

  zinc octylthioglycolate, zinc mercaptopropionate, zinc thiolactate, zinc thiomalate, zinc bis-octylmercaptopropionate, bis-isooctylthiolactate

  of zinc and zinc bis-laurylthiomalate.

  The zinc enolates are preferably enolates of acetylacetone, benzoylacetone, dibenzoylmethane, and enolates of esters of acetoacetic acid or benzoylacetic acid, as well as dehydracetic acid. In addition, inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate, or zinc can also be used.

zinc sulphide.

  Neutral or basic zinc carboxylates of a carboxylic acid of 2 to 22 carbon atoms (zinc soaps) are preferred such as, for example, benzoates or alkanoates, preferably C 8 alkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearates and

  hydroxyoleates, dihydroxystearates, p-tert-butylbenzoate, or (iso) octanoate.

  Stearate, oleate, versatate, benzoate, p-tert-butylbenzoate and 2-

  ethylhexanoate are particularly preferred.

  In addition to the aforementioned zinc compounds, it is also possible to consider (in) organic aluminum compounds containing an Al-O bond. Useful and preferred aluminum compounds include, inter alia, preferably aluminum enolates and aluminum carboxylates. Examples of carboxylate and enolate residues can be deduced correspondingly from those

indicated above for zinc.

  Examples of inorganic aluminum compounds are hydroxide

  aluminum and aluminum phosphates.

  The described organic zinc compounds or mixtures thereof may be used in amounts of, for example, from 0.001 to 10, preferably from 0.01 to 5, preferably from 0.01 to 3 parts by weight per 100 parts by weight.

chlorinated polymers.

  They can also be in the form of mixed salts (coprecipitates).

  The combination of stabilizers according to the invention can be used with other conventional additives for shaping and treating chlorinated polymers, for example: 1. stabilizers: 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 metal and alkaline earth metal compounds; perchlorates; zeolites; hydrotalcites; dawsonites; 2. other common PVC additives such as, for example: lubricants, plasticizers, impact modifiers; fitness assistants; blowing agents; charges; antistatic agents; biocides; anti-sail products; pigments and dyes; of the

  metal deactivators; flame retardants (see the Handbook of PVC-

  Formulating E.J. Wickson, John Wiley & Sons, New York 1993).

  Examples of such additives are known to those skilled in the art and

  found in the specialized literature. We quote here, in a nonlimiting way, some

  one of the known additives and processing aids: phosphites: organic phosphites are known costabilizers for chlorinated polymers. Examples thereof are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl, triphenyl, tricresyl, tris-nonylphenyl, tris-2,4-t-butylphenyl phosphites, or tricyclohexyl. Other suitable phosphites are various mixed phosphites of aryl and dialkyl or alkyl and diaryl such as phenyl and dioctyl phosphites, phenyl and didecyl, phenyl and didodecyl, phenyl and ditridecyl, phenyl and ditetradecyl, phenyl and the like. and dipentadecyl, octyl and diphenyl, decyl and diphenyl, undecyl and diphenyl, dodecyl and diphenyl, tridecyl and diphenyl, tetradecyl and diphenyl, pentadecyl and diphenyl, oleyl and

  diphenyl, stearyl and diphenyl and dodecyl and bis (2,4-di-tbutylphenyl).

  It is also possible to use advantageously phosphites of different diols or polyols, for example tetraphenyldipropylene glycol diphosphite, phosphite

  polydipropylene glycol-phenyl, diphosphite of tetramethylolcyclohexanol-

  decyl, tetramethylolcyclohexanol-butoxyethoxyethyl diphosphite,

  tetramethylolcyclohexanol-nonylphenyl diphosphite, diphosphite

  nonylphenyl-di (trimethylolpropane), bis-2-butoxyethyl diphosphite

  di (trimethylolpropane), trishydroxyethylisocyanuratehexadecyl triphosphite, didecylpentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis-2,4-di-tert-butylphenylpentaerythritol diphosphite, and mixtures of these phosphites and mixtures of aryl phosphites and alkyl having the statistical composition (H, 9C9-C6H,) O, .5P (OC, 2,3H2527), or [C8H, 7-C6H4-O] 2P [i-C8H, 70] or

(HgC9-C6H4) 0I, 5P (OC9, 1H9, 23) 1.5.

  The organic phosphites can be used in an amount of, for example, between 0.01 and 10, advantageously between 0.05 and 5 and in particular between 0.1.

  and 3 parts by weight per 100 parts by weight of PVC.

  polyols: As compounds of this type, particular consideration is given to: pentaerythritol, dipentaerythritol, tripentaerythritol, bis-trimethylolpropane, trimethylolethane, bis-trimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinitol, tetramethylolcyclohexanol (TMCH), tetramethylolcyclopentanol, tetramethylolcyclopyranol, glycerol,

  diglycerol, polyglycerol, thiodiglycerol, or 1-O-α-dihydrate

  glycopyranosyl-D-mannitol, as well as polyvinyl alcohol and cyclodextrins.

  Among them are preferred TMCH and disaccharide alcohols. The polyols may be used in an amount of, for example, from 0.01 to 20, preferably from 0.1 to 20, and in particular from 0.1 to 10 parts by weight.

  mass per 100 parts by weight of PVC.

  1,3-dicarbonyl compounds: examples of 1,3-dicarbonyl compounds are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tertnonylthioheptanedione-2,4,

  benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoyl-

  Benzoylmethane, stearoyl-benzoylmethane, isooctanoyl-benzoylmethane, 5-

  hydroxycapronyl-benzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) -

  methane, benzoyl-p-chlorobenzoylmethane, bis (2hydroxybenzoyl) methane,

  4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoyl) methane, i-

  benzoyl-1-acetylnonane, benzoylacetylphenylmethane, stearoyl-

  methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformyl-

  methane, benzoyl-phenylacetylmethane, bis (cyclohexanoyl) methane, di (pivaloyl) methane, methyl, ethyl, hexyl, octyl, dodecyl or octadecyl acetoacetate, benzoylacetate; ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl, ethyl, propyl, butyl, hexyl or octyl stearoylacetate and dehydroacetic acid and its alkali metal salts of zinc , from

  alkaline earth metals or aluminum.

  The 1,3-dicarbonyl compounds can be used in an amount of, for example, between 0.01 and 10, advantageously between 0.01 and 3 and in particular between

  0.01 and 2 parts by weight per 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 DE 2809492, EP 090770 and EP Examples are trihexyl trithiophosphite, trioctyl trithiophosphite, trithiophosphite

  trilauryl, tribenzyl trithiophosphite, tris (carboxy) trithiophosphite,

  octyloxy] methyl, S, S, S-tris (ioctyloxycarbonylmethyl) trithiophosphate, S, S, S-tris (2-ethylhexyloxycarbonylmethyl) trithiophosphate, trithiophosphate

  S, S, S-tris (1-hexyloxycarbonylethyl), S, S, Stris [1- (2-

  ethylhexylcarbonyl) ethyl], S, S, S-tris [2- (2-ethylhexyl) trithiophosphate

  carbonyl) ethyl]. The thiophosphites and the thiophosphates may be in the chlorinated polymer in an amount advantageously between 0.01 and 20,

  preferably between 0.1 and 5, in particular between 0.1 and 1%.

  esters of mercaptocarboxylic acids: examples of these compounds are: esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, mercaptobenzoic acids or thiolactic acid, as described in the documents FR 2459816, EP 90748, FR 2552440 and EP 365483. The esters of mercaptocarboxylic acids also comprise the esters of

  corresponding polyols and their partial esters.

  They may be in the chlorinated polymer in an amount advantageously between 0.01 and 10, preferably between 0.1 and 5, in particular between 0.1.

and 1%.

  epoxides and epoxidized fatty acid esters: the combination of stabilizers according to the invention may further contain at least one epoxidized fatty acid ester. For this purpose, we mainly take into consideration esters of fatty acids of natural origin

  like soybean oil or rapeseed oil.

  The epoxidized compounds are used in amounts, for example, greater than 0.1 parts per 100 parts by weight of composition, preferably 0.1 to 30 parts, preferably 0.5 to 25 parts by weight. Other examples are epoxidized polybutadiene, epoxidized linseed oil, epoxidized fish oil, epoxidized tallow, methylbutyl epoxystearate or 2-ethylhexyl, tris (epoxypropyl) isocyanurate, epoxidized epoxidized castor oil, epoxidized sunflower oil, 3-phenoxy-1,2-epoxypropane, diglycidyl ether of bisphenol A,

  vinylcyclohexene diepoxide, dicyclopentadiene diepoxide and 3,4-dicyclopentadiene

  3,4-epoxycyclohexylmethyl epoxycyclohexanecarboxylate.

  It is also possible to take into consideration, as epoxides, the bisphenol A and bisphenol F derivatives as described, for example, in the

South African patent ZA-2600/94.

  Dihydropyridines and polydihydropyridines: As monomeric dihydropyridines, it is possible to take into account compounds such as those described in patent documents FR 2039496, EP 2007, EP 362012 and EP 24754. Those of the formula in which Z is CO2CH 3 are preferred. CO2C-2H,

H3C N CH3

CO2 "C12HZ, or -CO2C2H4-S-" C12H25.

  As polydihydropyridines, the compounds of general formula are especially taken into account.

T0 0 0 0 0 0

/ R R ',

T-- 0- O L

  I 1H3C N CH3 C N C n N CH | Where T represents an unsubstituted C 1 -C 2 alkyl radical, L has the same meaning as T, m and n are numbers from 0 to 20, k is equal to 0 or 1, R and R 'represent independently of each other an ethylene, propylene, butylene or an alkylene- or cycloalkylenebismethylene group of the type - (CPH2p-X-) tCMH2p-1 p is a number from 2 to 8, t is a number from 0 to 10, and

X is oxygen or sulfur.

  Such compounds are described in EP 0286887.

  The (poly) dihydropyridines can be used in the chlorinated polymer in an amount advantageously between 0.001 and 5 and in particular between 0.005

  and 1 part by weight relative to the polymer.

  Bis (5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-

  carboxylate) of thiodiethylene is particularly preferred.

  alkali metal and alkaline earth metal compounds: these compounds are understood to mean, above all, the carboxylates of the acids described above, but also the corresponding oxides or hydroxides, carbonates or basic carbonates. Their mixtures with organic acids are also considered. Examples are NaOH, KOH, CaO, Ca (OH) 2, MgO, Mg (OH) 2, CaCO 3, MgCO 3,

  dolomite, huntite, as well as Na, K, Ca or Mg salts of fatty acids.

  In the case of alkaline earth metal carboxylates and Zn, one can also use their adducts with MO or M (OH) 2 (M = Ca, Mg, Sr or Zn),

so-called "overbased" compounds.

  Alkali metal, alkaline earth metal and / or alkali metal carboxylates are preferably added to the stabilizer combinations according to the invention.

  aluminum such as, for example, stearates of Na, K, Ca or Al.

  perchlorate type salts: examples are those of formula M (ClOJ) in which M is Li, Na, K, Mg, Ca, Ba, Zn, Al, Ce or La. The index n is, according to the valence of M, equal to 1, 2 or 3. The perchlorates can be complexed with alcohols or ether-alcohols. The various perchlorates can also be used in various common preparation forms, for example in the form of a salt or an aqueous solution fixed on a support such as PVC, calcium silicate, a zeolite or a hydrotalcite. , or obtain them by chemical reaction of a

  hydrotalcite with perchloric acid.

  The perchlorates can be used in an amount of, for example, between 0.001 and 5, advantageously between 0.01 and 3, particularly preferably

  between 0.01 and 2 parts by weight per 100 parts by weight of PVC.

  hydrotaleites and zeolites: the chemical composition of these compounds is known to those skilled in the art, for example from patent documents DE

  3843581, US 4000100, EP 062813, WO 93/20135.

  The compounds of the hydrotalcite series can be described by the general formula VI, M2 + 1 '. M3 +, - (OH) - (A "" -) e.mH: O (VI) wherein M2 represents one or several metals of the group consisting of Mg, Ca, Sr, Zn and Sn, M3 is AI or B, A "represents an anion of valence n, n is 1 or 2, 0 <x <0.5, m is a number from 0 to 20 and COO-A- represents OH-, ClO4, HCO3-, CH3COO-, C6H5COO-, CO32-, SO42, HSO4-, COO,

  (CHOHCOO) 22-, (CH2COO) 22-, CH3CHOHCOO-, HPO32- or HPO42-.

  Examples of hydrotalcites are Al 2 O 3 · 6 MgO · CO 2 · 12H 2 O; Mg4. 5A12 (OH), 3.CO3.3,5H20; 4MgO.A1203.CO2.9H20; 4MgO.A1203.CO2.6H20;

  ZnO.3MgO.AI203.CO2.8-9H20; and ZnO.3MgO.AI203.CO2.5-6-H20.

  The compounds of the zeolite series (aluminosilicates of alkali metals or of alkaline earth metals) may be represented by the general formula (VI) M, [(AlO 2) x (SiOn) y] -wH 2 O (VII) in which n is the charge of the cation M; M is an element of the first or second major group, such as Li, Na, K, Mg, Ca, Sr or Ba, or is Zn, y: x is a number of 0.8 to 15, preferably 0.8 at 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30. For example, structures will be found in the Atlas of Zeolite Structures.

  by W. M. Meier and D. H. Olson, Butterworth-Heinemann, 3rd edition 1992.

  Examples of zeolites are sodium aluminosilicates having the formulas Na, Al12Si, 2048. 27 H2O [zeolite A], NaA16Si6024. 2 NaX. 7.5 H2O, X = OH, halogen, C104 [sodalite]; Na6A16Si3072O. 24 H 2 O; NaAlsSi4nO9. 24 H 2 O; Na 6Al6Si2408. 16 H2O; Na16Al, 6Si32096. 16 H2O; Na A156Si3603M4. 250 H 2 O [zeolite Y]; Na ,, Al86Si, 06038. 264 H 2 O [zeolite X]; or zeolites obtainable by exchange of all or part of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na, K), oAloSi22064. 20 H2O; Ca4n5Na3 [(AlO2) 12 (SiO2), 2] H2O;

K9Na3 [(AlO2), 2 (SiO2), 2] 27H2O.

  Other suitable zeolites are: Na2O. A1203. (2 to 5) SiO2. (3.5-10) H2O [zeoliteP] Na2O. A1203. 2 SiO2. (3.5 to 10) H 2 O [zeolite MAP] or zeolites obtainable by exchange of all or part of the Na atoms by Li, K or H atoms, such as (Li, Na, K, H), Al , oSi22064. 20 H2O; KoNa3 [(AL02) 2 (Si02) 12]. 27 H2O; K4AI4Si40,6. 6H20 [K-F zeolite], NaAl8Si40O9. 24 H 2 O [zeolite D], as described by Barrer et al., J. Chem. Soc. 1952, 1561-71, and in the US Patent

* 2,950,952.

  In addition, the following zeolites can be taken into consideration:

  offretite, described in EP-A-400 961; zeolite R, described in GB 841812; zeolite LZ-217, described in US Patent 4,503,023; zeolite LZ-218 without calcium, described in US Pat. No. 4,333,869; zeolite T, zeolite LZ-220, described in US Patent 4,503,023; Na3K6A4Si27072.21 H20 [zeolite L]; zeolite LZ-211, described in US Patent 4,503,023; zeolite LZ-212, described in US Patent 4,503,023; zeolite O, zeolite LZ-217, described in US Patent 4,503,023; zeolite LZ-219, described in US Patent 4,503,023; Rho zeolite, zeolite LZ-214, described in US Patent 4,503,023; zeolite ZK-19, described in Am. Mineral. 54, 1607 (1969); zeolite W (K-M), described by Barrer et al. J. Chem. Soc. 1956, 2882;

  Na30A3Si60,92. 98 H 2 O [zeolite ZK-5, zeolite Q].

  Particularly preferred are the zeolite P types of formula VII wherein x is 2 to 5 and y is 3.5 to 10, and most preferably the MAP zeolite of formula VII wherein x is a number of 2 to and y is 3.5 to 10. In particular, these are NaP zeolites, i.e., M is Na. This zeolite is generally in the form of the NaP-1, NaP-2 and NaP-3 variants, which are distinguished by their cubic, tetragonal or orthorhombic structure (RM Barrer, BM Munday, J.Chem.Soc.A 1971, 2909). -14). In the literature just mentioned, the preparation of zeolites P-1 and P-2 is also described. Zeolite P-3 is, according to this literature, rather rare and therefore of little practical interest. The structure of zeolite P-1 corresponds to the known structure of gismondite according to the aforementioned Atlas of Zeolite Structures. In the recent literature (EP-A-384 070), the distinction is made between cubic zeolite (zeolite B or Pc) and tetragonal zeolites (zeolite P). There are also more recent P-type zeolites with Si: Al ratios of less than 1.07: 1. It's about

  in this case zeolites called MAP or MA-P for "Maximum Aluminum t".

  According to the process of preparation, zeolite P may contain small amounts of other zeolites. A very pure zeolite P has been described in the patent document WO

94/26662.

  In the context of the invention, it is also possible to use finely divided sodium aluminosilicates, which are insoluble in water, which have been precipitated and crystallized in the presence of water-soluble inorganic or organic dispersing agents. They can be incorporated into the reaction mixture either before or after

  after precipitation or crystallization.

  Zeolite Na-A and zeolite Na-P are preferred.

  Hydrotalcites and zeolites can be mineral products

  or compounds synthesized by synthesis.

  The hydrotalcites and / or the zeolites may be used in amounts of, for example, between 0.1 and 50, advantageously between 0.1 and 10 and in particular between 0.1 and 5 parts by weight, per 100 parts by weight of halogenated polymer. . alkali metal aluminocarbonates (dawsonites): these compounds may be represented by the formula {(M20) = - (AO2O3) .. Zo-pH2O} (V) in which M is H, Li, Na, K, Mg, 2 Ca, a, Sr2 or Zn%; Z is CO2, SO2, (Cl207) 1m, B406, S202 (thiosulfate), or C202 (oxalate); when M is Mg ,, 2 or Ca ,, m is a number between 1 and 2, and in other cases m is a number between 1 and 3; n is a number from 1 to 4; o is a number between 2 and

  4; and p is a number from 0 to 30.

  The aluminosel compounds of formula (V) may be natural mineral products or compounds prepared by synthesis. Metals can be partially exchanged between them. The cited aluminosel compounds are crystalline, partially crystalline or amorphous, or may be in the form of dried gels. The aluminosal compounds may also exist as rare crystalline modifications. A process for preparing such compounds is described in EP 394670. Examples of compounds

  of natural aluminosels are indigirite, tunisite, alumohydrocalcite, para-

  alumohydrocalcite, strontiodressitis and hydrostrontiodressitis. Other examples of aluminosal compounds are potassium aluminocarbonate {(K 2 O)} (Al 2 O 3) (CO2) 2.2H 2 O}, sodium aluminothiosulfate {(Na 2 O)} (Al 2 O 3). (S 2 O 2) 2.2H 2 O } potassium aluminosulphite {(K20). (A1203). (SO2) 2.2H2O}, calcium aluminoxalate {(CaO)} (Al2O3). (C202) 2.5H2O}, magnesium aluminotetraborate {(MgO). (Al2O3). (B406) 2. 5H 2 O 3, ((Mg 2 N 6 O 6) 2 O) (Al 2 O 3) (CO 2) 2.4, 1H 2 O, {([Mgo 2)] 0.60). (A1203). (CO2) 2.4.3H2O}, and

  {([Mgo3Nao.4] 20). (A1203). (CO2) 2.4,9H2O}.

  The mixed aluminosal compounds may be obtained by methods known per se by cation exchange, preferably from the alkali metal aluminosalt compounds or by combined precipitation (see for example

U.S. Patent No. 5,055,284).

  Aluminosal compounds of the above formula wherein M is Na or K are preferred; Z is CO2, SO2 or (Cl207), 1; m is a number from 1 to 3, n is a number from 1 to 4, o is a number from 2 to 4 and is a number from 0 to 20. Zest

  particularly preferred way CO2.

  In addition, the compounds which can be represented by the following formulas: M20.A1203 (CO2) 2.pH2O (Ia), (M20) 2. (A1203) 2. (C02) 2.pH2O (Ib), M20 (Al2O3) 2. (CO2) 2.pH2O (Ic), wherein M is a metal such as Na, K, Mg2, Ca, 1, Sra2 or Zn ,,, and p is a

number from 0 to 12.

  Sodium aluminodihydroxycarbonate (DASC) and the

  homologous potassium (DAPC) are particularly preferred.

  The dawsonites may be used in an amount of, for example, from 0.01 to 50, advantageously from 0.1 to 10, particularly preferably

  between 0.1 and 5 parts by weight per 100 parts by weight of halogenated polymer.

  The combination of stabilizers according to the invention can be used with other common additives for the shaping and stabilization of chlorinated polymers, such as, for example: Antioxidants: as antioxidants, for example:

  1. alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-

  butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-ditert-butyl-4-n-

  butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl4-methyl-.

  phenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl4-

  methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethyl

  phenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (methyl)

  yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1-yl) phenol, 2,4-dimethyl-6-yl

  methyltridec-1-yl) phenol and mixtures thereof.

  2. Alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6tert-

  butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-

  ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

  3. hydroquinones and alkylated hydroquinones, for example 2,6di-tert-butyl-

  4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tertamylhydroquinone,

  2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-

  tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-stearate

  di-tert-butyl-4-hydroxyphenyl, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

  4. tocopherols, for example, α-tocopherol, β-tocopherol, ytocopherol, -

  tocopherol and their mixtures (vitamin E).

  5. hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-

  methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-

  methylphenol), 4,4'-thiobis (6-tert-butyl-2-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-tertbutyl-4-

  methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylene

  bis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-ethylenebis (4-methyl-6-

  cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-

  methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tertbutylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-

  methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, adimethylbenzyl) -4-

  nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (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-4hydroxy-2-

  methylphenyl) -3-n-dodecylmercaptobutane, bis [3,3-bis (3'-tert-butyl-4-hydroxy)

  phenyl) butyrate] ethylene glycol, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) -

  dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methyl) terephthalate

  benzyl) -6-tert-butyl-4-methylphenyl], 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -

  butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2bis (5-tert-butyl-

  4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl)

4-hydroxy-2-methylphenyl) pentane.

  7. O- compounds. N- and S-benzylated e.g. 3,5,3 'oxide, 5'tetra-tert-

  butyl-4,4'-dihydroxydibenzyl, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, dithioterephthalate,

  bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), bis (3,5-di-tert-butyl-4-

  hydroxybenzyl), isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

  8. hydroxybenzyl malonates, for example 2,2-bis (3,5-di-tertbutyl-2-

  hydroxybenzyl) dioctadecyl malonate, 2- (3-tert-butyl-4-hydroxy-5-methyl-

  benzyl) dioctadecyl malonate, 2,2-bis (3,5-di-tert-butyl-4hydroxybenzyl) -

  didodecylmercaptoethyl malonate, 2,2-bis (3,5-di-tert-butyl-4hydroxy)

  benzyl) di [4- (1,1,3,3-tetramethylbutyl) phenyl] malonate].

  9. aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-

  butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-ditert-butyl) -4-

  hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-

benzyl) phenol.

  10. triazine compounds, for example 2,4-bis (octylmercapto) -6 (3,5-di-tert-

  butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl)

  4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-ditert-butyl) -4-

  hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4hydroxyphenoxy) -

  1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4hydroxybenzyl) isocyanurate, 1,3,5-diisopropyl

  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 (3,5-di-tert-butyl-4-hydroxy-

  phenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl) -hydroxy-

  benzyl) isocyanurate. 11. Benzylphosphonates, eg dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5di-tert-butyl-4-hydroxybenzylphosphonate

  Di-tert-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 5-

  dioctadecyl tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt

  monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

  12. Acylaminophenols, for example 4-hydroxyanilide of lauric acid, 4-

  hydroxyanilide of stearic acid, N- (3,5-di-tert-butyl-4hydroxyphenyl) -

octyl carbamate.

  13. esters of 3- (3,5-di-tert-butyl-4hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example 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) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-lphospha-2,6,7-

trioxabicyclo [2.2.2] octane.

  14. esters of 3- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyalcohols, for example 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) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha2,6,7-

  trioxabicyclo [2.2.2] octane. 15. esters of 13- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyalcohols, for example 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) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha2,6,7-

trioxabicyclo [2.2.2] octane.

  16. esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono-

  or polyalcohols, for example 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) oxamide, 3thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,

  trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2. 2.2] octane.

  17. amides of 6- (3,5-di-tert-butyl-4hydroxyphenyl) propionic acid, by

  for example N, N-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene

  diamine, N, N'-bis (3,5-di-tert-butyl-4hydroxyphenylpropionyl) trimethylene

  diamine, N, N'-bis (3,5-di-tert-butyl-4hydroxyphenylpropionyl) hydrazine.

  It is also possible to use a mixture of antioxidants of

different structures.

  The antioxidants can be used in an amount of, for example, from 0.01 to 10, preferably from 0.05 to 10 and in particular from 0.05 to 5.

  parts by weight per 100 parts by weight of PVC.

  UV absorbers and light stabilizers: Examples are:

  1. 2- (2'-hydroxyphenyl) benzotriazoles, for example 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-

  chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5chlorobenzoate

  triazole, 2- (3'-sec-butyl-5'-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (2'-

  hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2-hydroxyphenyl) -

  benzotriazole, 2- (3 ', 5'-bis (α-α-dimethylbenzyl) -2-hydroxyphenyl) benzotriazole,

  a mixture of 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-

  chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-

  hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '(2-methoxy)

  carbonylethyl) phenyl) -5-chlorobenzotriazole, 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-ethylhexyl) -2-

  oxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2-hydroxy-5 '

  methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2isooctyloxy)

  carbonylethyl) phenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethyl)

  butyl) -6- (benzotriazole-2-yl) phenol]; the trans-esterification product of 2- [3'-tert-

  butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole with the poly-

  ethylene glycol 300; [R-CH 2 CH 2 -COO (CH 2) 3] 2 with R = 3'-tert-butyl-4-hydroxy-5'-

(2H-benzotriazole-2-yl) phenyl.

  2. 2-hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4-

  octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy. 3. optionally substituted benzoic acid esters, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol,

  2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5di-tert-butyl-

  Hexadecyl 4-hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzoate

  of octadecyl, 3,5-di-tert-butyl-4-hydroxybenzoate of 2-methyl-4,6-ditert-

  butylphenyl. 4. acylates, for example 3,3-cyano-3,3-diphenylacrylate ethyl or isooctyl, methyl oc-carbomethoxycinnamate, ac-cyano-3-methyl-p-methoxycinnamate

  methyl or butyl, methyl c-carbomethoxy-p-methoxycinnamate, N- (13-

  carbomethoxy-Jp-cyanovinyl) -2-methylindoline.

  5. nickel compounds, for example nickel complexes with 2, 2'-

  thiobis [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 complex or the 1: 2 complex, with optional additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dithiocarbamate

  dibutylnickel, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-

  tert-butylbenzylphosphonic acid, such as methyl or ethyl esters,

  complexes of nickel with ketoximes such as 2-hydroxy-4-methylphenyl-

  undecylketoxime, nickel complexes with 1-phenyl-4-lauroyl-

  hydroxypyrazole, optionally with other ligands.

  6. sterically hindered amines, for example bis (2,6,6,6-

  tetramethylpiperidin-4-yl), bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate,

  bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, n-butyl-3,5-di-tert-butyl-

  Bis (1,2,2,6,6-pentamethylpiperidyl) 4-hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and

  succinic acid, the condensation product of N, N-bis (2,2,6,6-tetramethyl-4-

  piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-

  triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, 1,2,3,4-

  butanetetracarboxylate of tetrakis (2,2,6,6-tetramethyl-4-piperidyl), 1,1 '- (1,2-

  ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethyl-

  piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 2-n-butyl-2- (2-hydroxy)

  Bis (1,2,2,6,6-pentamethylpiperidyl) 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 sebacate (I-

  octyloxy-2,2,6,6-tetramethylpiperidyl), bis (I-octyloxy2,2,6,6-

  tetramethylpiperidyl), the condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5- triazine

  the condensation product of 2-chloro-4,6-di (4-n-butylamino-2,2,6,6-tetramethyl)

  piperidyl) -1,1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, the product of

  condensation of 2-chloro-4,6-di (4-n-butylamino-1,2,2,6,6pentamethylpiperidyl)

  1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3dodecyl-

  7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl- (12,2,6,6-

  tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-penta)

  methyl-4-piperidyl) pyrrolidine-2,5-dione.

  7. Diamides of oxalic acid, for example 4,4'dioctyloxyoxanilide, 2,2'-

  diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-

  5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of oxyanilides disubstituted with methoxy at o and p. and by ethoxy at o and p.

  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) -4,6bis (2,4-

  dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethyl)

  phenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethyl)

  phenyl) -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-butyloxypropyloxy) phenyl] -4,6-

  bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy) -2-

  propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

  The stabilizer mixture according to the invention preferably contains carboxylates of alkali metals or alkaline earth metals, in particular

  calcium carboxylates, aluminum carboxylates, 1,3-

  dicarbonyls, dihydropyridines, phosphites or combinations thereof. Plasticizers: As organic plasticizers, those of the following groups for example are taken into consideration: A) esters of phthalic acid: Examples of such plasticizers are dimethyl phthalates,

  diethyl, dibutyl, dihexyl, di (2-ethylhexyl), di-n-octyl, di-

  isooctyl, di-isononyl, di-isodecyl, di-isotridecyl, dicyclohexyl, di (methylcyclohexyl), dimethylglycol, dibutylglycol, benzylbutyl and diphenyl and mixtures of phthalates such as C 7 alkyl phthalates -C9 and C9-C4, obtained from substantially linear alcohols, phthalates of n-C6-C30 alkyl and phthalates of n-C6-C10 alkyl. Of these, we prefer

  dibutyl, dihexyl, di (2-ethylhexyl), di-n-octyl phthalates, di-

  isooctyl, di-isononyl, di-isodecyl, di-isotridecyl and benzyl and butyl,

  as well as the aforementioned mixtures of alkyl phthalates. Phthalates of di (2-

  ethylhexyl), di-isononyl and di-isodecyl, also known abbreviations DOP (dioctyl phthalate, di (2-ethylhexyl) phthalate), DINP (phthalate)

  di-isononyl), DIDP (di-isodecyl phthalate), are particularly preferred.

  B) esters of aliphatic dicarboxylic acids, in particular esters of the acid

  adipic acid, azelaic acid and sebacic acid.

  Examples of such plasticizers are di (2-ethylhexyl) adipate, di-isooctyl adipate (mixture), di-isononyl adipate (mixture), di-isodecyl adipate (mixture), benzyl and butyl adipate, benzyl adipate and octyl,

  di (2-ethylhexyl) azelate, di (2-ethylhexyl) sebacate and diisocyanate sebacate;

  isodecyl (mixture). Di (2-ethylhexyl) adipate and di-adipate are preferred.

  isooctyl. C) esters of trimellitic acid, for example tri (2-ethylhexyl) trimellitate, tri-isodecyl trimellitate (mixture), tri-isotridecyl trimellitate, triisooctyl trimellitate (mixture) and trimellitates of C 6 -C 8 trialkyl, C 6 -C 8 trialkyl, C 7 -C 9 trialkyl and C 9 -C 14 trialkyl. These latter trimellitates are formed by esterification of trimellitic acid with the mixtures

  corresponding alkanols. The preferred trimellitates are tri-trimellitate (2-

  ethylhexyl) and trimellitates obtained from the indicated alkanol mixtures.

  Common abbreviations are TOTM (trioctyl trimellitate, tri-trimellitate (2-

  ethylhexyl)), TITDM (tri-isodecyl trimellitate) and TITDTM (tri-isodecyl trimellitate)

  isotridecyl). D) Epoxy plasticizers These are essentially epoxidized unsaturated fatty acids such as

  for example, epoxidized soybean oil.

  E) Polymeric Plasticizers The most widely used raw materials for the preparation of polymeric plasticizers are: dicarboxylic acids such as adipic acid,

  phthalic acid, azelaic acid and sebacic acid; diols like 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-ethylbutyl) phosphate, tri (2-ethylhexyl) phosphate, trichloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl and diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Tri (2-ethylhexyl) phosphate is preferred

and Reofos 50 and 95 (formerly FMC).

  G) chlorinated hydrocarbons (paraffins) H) hydrocarbons I) monoesiters, eg butyl oleate, phenoxyethyl oleate, oleate

  tetrahydrofurfuryl and alkylsulfonic acid esters.

  J) glycol esters, for example diglycol benzoates.

  Definitions and examples of plasticisers of groups A) to J) are given in the following manuals: Taschenbuch der Kunsstoffadditive, published by R. Gachter and H. Mler, Editions Carl

  Hanser, 1989, chapter 5, pages 341-442.

  PVC Technology, published by W.V. Titow, 4th Edition, Elsevier Publishers, 1984,

Chapter 6, pages 147-180.

  It is also possible to use mixtures of different plasticizers.

  Plasticizers may be used in an amount of, for example, from 5 to 120, preferably from 10 to 100 parts by weight per 100 parts by weight.

PVC mass.

  Lubricants: for example, lignite wax, fatty acid esters, PE waxes, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps, or silicone lubricants as described in EP 225261. Useful lubricants are also described in Taschenbuch der Kunsstoffadditive, published by R.

  Gachter and H. Mler, Carl Hanser Editions, 3rd edition, 1989, pages 478488.

  Charges: Charges (EJ Wickson's Handbook of PVC-Formulating, John Wiley & Sons, New York 1993, pages 393449) and reinforcing agents (Taschenbuch der Kunsstoffadditive, published by R. Gachter and H. Muller, Carl Hanser Editions, 3 "edition, 1989, pages 549-615) may be for example: calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, glass, talc, kaolin, chalk, mica, metal oxides and hydroxides, carbon black or

graphite). We prefer chalk.

  Pigments: Suitable products are known to those skilled in the art. Examples of inorganic pigments are TiO 2, carbon black, Fe 2 O 3, Sb 2 O 3, (Ti, Ba, Sb) O 2, Cr 2 O 3, spinels such as cobalt blue and cobalt green,

  Cd (S, Se), the ultramarine blue. TiO2 is preferred, also in micronized form.

  Organic pigments are, for example, azo pigments, phthalocyanine-type pigments, quinacridone-type pigments, pigments of the type

perylene, pyrrolopyrrole pigments and anthraquinone pigments.

  Further details can be found in E.J. Wickson's Handbook of PVC-Formulating,

  John Wiley & Sons, New York 1993, pp. 449-474.

  Examples of the chlorinated polymers to be stabilized or of their recycled products are: polymers of vinyl chloride, vinyl resins containing in their structure vinyl chloride units, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids , in particular vinyl acetate, copolymers of 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, as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, chlorinated vinyl chloride polymers and copolymers, copolymers of vinyl chloride and vinylidene chloride with aldehydes, ketones and other unsaturated products, such as acrolein, crotonaldehyde, vinylmethylketone, vinylmethyl ther, vinylisobutyl 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 unsubstituted acrylic acid; polymers of chlorinated styrenes, for example dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene; superchlorinated polymers and polymers of chlorobutadiene and its copolymers with vinyl chloride, natural and synthetic chlorinated rubbers; and mixtures of these polymers with each other or with other compounds

polymerizable.

  In the context of the invention, it is also understood by PVC copolymers with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, these polymers may be polymers in suspension, bulk or emulsion. A homopolymer of PVC, also in combination, is preferred

with polyacrylates.

  Also included are graft polymers of PVC with YEVA, ABS and MBS. Preferred substrates are also mixtures of the abovementioned homo- and copolymers, in particular homopolymers of vinyl chloride, with other thermoplastic and / or elastomeric polymers, in particular mixtures with ABS, MBS, NBR, SAN, EVA, EPC, MBAS, PMA,

  PMMA, EPDM and polylactones.

  Suspended polymers and polymers are also preferred.

  mass, as well as emulsion polymers.

  As the chlorinated polymer, poly (vinyl chloride) is particularly preferred, in particular in the form of a polymer in suspension or a polymer in

mass.

  In addition, in the context of this invention, particular consideration is also given to recycled products of chlorinated polymers, which are the same polymers as those described more precisely above, and which have undergone alteration during the shaping. , use or storage. Recycled PVC is particularly preferred. Recycled products may also contain small amounts of foreign substances such as paper, pigments, glues, which are often difficult to remove. These foreign substances may also come from contact with different materials during use or shaping, such as, for example, leftover blowing agents, portions of

  paint, traces of metal and remains of initiator.

  The use of the stabilizer mixture is carried out in a known manner

the skilled person.

  For example, the stabilizer mixture can be converted, also with conventional additives, before the actual use by

  example in the form of granules or an extrusion product or a paste.

  Another object of the present invention is the use of the stabilizer mixture which has just been described - also in the form of granules, extrusion product or paste and also in connection with lubricants - for the stabilization of a halogenated polymer or a product for recycling halogenated polymers. For the different stabilizers and for the halogenated polymer itself, the preferences indicated above are valid, and one can also use in addition one of the other

components described above.

  The stabilizer mixture can be added to the polymer by known means by mixing the mentioned stabilizers and optionally other additives with the halogenated polymer using known apparatuses such as mixers, kneaders, extruders, grinders and the like. . For this purpose, the stabilizers can be added alone or in mixture, or in the form of a mixture called masterbatch. The invention therefore also relates to a method for stabilizing a halogenated polymer, characterized in that the stabilizing constituents and optionally other additives are mixed with the PVC using apparatuses such as

  calenders, mixers, kneaders, extruders and the like.

  The invention also relates to the polymer compositions thus stabilized, containing the mixture of stabilizers according to the invention. They can be put in the desired form by known means. Such processes are, for example, calendering, extrusion, injection molding, sintering or spinning, as well as

  extrusion blow molding or shaping by the plastisol molding process.

  It is also possible to convert the polymer compositions into foams.

  The invention also relates to the use of stabilized polymer compositions for the production of moldings obtainable from halogenated polymers. The polymer compositions according to the invention are suitable for semi-rigid and flexible formulations, for example for flexible formulations for yarn wrapping and cable insulation. In the form of semi-rigid formulations, the polymer compositions according to the invention are suitable for decorative sheets, foams, sheets for agriculture, pipes, profiled seals, office sheets, profiles and extruded sheets, sheets and plates for floors, artificial coatings and leathers, as well as for sheets for cushions of

  collision (to be used in the automotive field).

  In the form of hard formulations, the polymer compositions according to the invention are suitable for hollow bodies (bottles), packing sheets (stamping sheets), blown sheets, sheets for collision cushions (automobile), tubes, foams, heavy sections (window frames), apertured wall profiles, building profiles, siding, plumbing and appliance cladding (computers,

  appliances) and for other injection molded articles.

  Examples of the use of the stabilized polymer compositions according to the invention as plastisols are artificial leathers, floor coverings, textile coatings, carpets, strip coatings and the protection of

  underbody for motor vehicles.

  Examples of sintering use of the stabilized polymer compositions according to the invention are the preparation of pasta, the molding of pasta and the coating on tape. The following examples explain the invention in more detail without

  to limit it. As in the rest of the description, the parts and percentages are

  relate to the mass, unless otherwise indicated.

  Example 1: N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) oxamide

  156.3 g (0.8 mol) of 4-amino-2,2,6,6-ol are added slowly with stirring.

  tetramethylpiperidine to 56.1 g (0.4 mol) of diethyl oxalate, resulting in aminolysis with a significant release of heat. The temperature rises to about 100 ° C. After adding 150 ml of xylene, the ethanol is distilled at 88-137 ° C. over 18.5 hours. The mixture is then taken up in 1500 ml of xylene, filtered hot and cooled. The precipitated crystals are filtered off with suction and

recrystallises them in xylene.

  Yield: 120 g (82% of theory). Melting point: 225-231 ° C.

  The following products (Examples 2 to 8) were prepared by reaction of 4-

  amino-2,2,6,6-tetramethylpiperidine with the corresponding acid chlorides or by reaction of bis-2,2,6,6-tetramethylpiperidinyl, 6-hexanediamine with acetic anhydride:

Example 2

O O

  HN NH-C <C-NH N melting point: 273 C (dec.);

Example 3

  (HN NH-CO-CH 2 CH 2) 2 melting point: 217 ° C;

Example 4

  (HN 1 NH-CO-CH 2 CH 2 CH 2 CH 2) 2 melting point: 145 ° C;

Example 5

[H3C-CO-N-CH2] 2

melting point 197-199 C; > N) H

Example 6

  [n-C11H1-CO- N - (CH2) 3] 2 fission point 79-81 ° C; N H

Example 7

o

HN NH-C

  o 1 5 C'FLONHN melting point:> 300 C;

Example 8N-C

Example 8

  HN N-CO-CH3 fission point 140-1430C.

Example 9

  To prepare stabilizers I and II, a mixture of Zn and Ca stearates with a commercially available p-diketone (Stabilizer I) is mixed intensively for 1.5 hours in an eccentric mixer and further with the piperidine of Example 5 in the ratio 8: 2: 1.5 (stabilizer II). From these stabilizer mixtures, 1.0 part (stabilizer I) or 1.15 part (stabilizer II) is mixed with 100 parts of S-PVC (K 70 value) and 21 parts of a mixture consisting of dioctyl / epoxidized soybean oil and a commercial liquid alkyl aryl phosphite and plasticized for 5 minutes at 190 ° C. in a mixing mill. In the sheets thus obtained (thickness 0.2 mm), samples were cut and thermally stressed in a Mathis Thermo-Takter apparatus at 180 ° C. for the time indicated in Table 1 below. The yellowness index (YI) is then determined according to the standard

ASTM-1925-70.

  The lower the value of the yellowness index, the more effective the stabilizing system is in preventing yellowing and therefore deterioration of the material. The long-term thermal stability of the stabilized polymer is recognized by the sudden appearance of massive staining. A stabilizer is all the more active as this coloration is delayed longer under the effect of a thermal stress. Thermal test: YI samples at 180 C

Table 1

  test time [minutes] stabilizing failure time co-additive0 6 12 21 48 [minutes] I - 5.1 5.4 5.3 black black 17 II 1 component 5 5.7 6.0 6.5 7, 9 12.8 70

Claims (9)

  1. Combination of stabilizers for halogenated polymers, containing A) at least one organic zinc compound with a Zn-O bond B) at least one compound of formula R3-N-CX-R2 (C 2). __ _ ,, N N AN R1 N   R1, R7, L N- (Y) m (N) m N-R1 (IR) and / or Q (V) R1 in which: X is O or S; R1 is H or C1-C8alkyl, C3-C8alkenyl, C9-C9phenylalkyl or C8-C8cycloalkyl; R2 is a C1-C8 alkyl, -NH2, R3NG-, R4-O-, [R3-NG-CX] EU-, (CIC4 alkyl) 2N (CH2) k-CX-, phenyl or OH substituted phenyl radical; C1-C4 alkoxy or C1-C4 alkyl; Gest -Ri; R3 is H or (C1-C8) alkyl, (C3-C8) alkenyl, (C5-C8) cycloalkyl, R2-CX-NG- (CH2) b, (C1-C4) alkyl2N (CH2) kou G; R4 is a C1-C4 alkyl, cyclohexyl or benzyl residue; E is (CH2) a ,,. . -, -CH = CH-, -CH (OH) -CH (OH) -, -CH2-CH (OH) - or -NH (CH2) bNH-; A is> CO, - (CH2) m-, - (CH2) d -CO- or -NH (CHD) .- CO-; a is a number from 0 to 8; b is a number from 2 to 12; it is 1 or 2; d is a number from 1 to 8; k is a number from 2 to 6; m is 0 or 1; n is a number from 2 to 12; p is 0 or 1; q is 1 or 2; r is a number from 2 to 50; and when p is 0, A is> CO, - (CH2) m-, - (CH2) d- CO-, -NH (CH2) f-CO-; and when p is 1, A is - (CH2) m-; L is -CH2-CHR6-, - (CH3) 3-, -CH = CH-, L- (N) mY-CN = O, or R5 is H or C1-6alkyl; C8, C3-C8 alkenyl, C5-C8 cycloalkyl or G; R6 is H or C1-C2 alkyl; R7 is H or CH3; Q is -O- or> NH; Y is -CH2-CH (OH) -CH2-; and s is a number from 3 to 60.   The stabilizer combination according to claim 1, wherein X is O or S; R1 represents H or a C1-C8 alkyl residue; R2 is a C1-C8 alkyl, -NHI2, R3NG-, [R3-NG-CX], E- or (C1-C4 alkyl) 2N (CH2) k-CX-; R3 is H or (C1-C8) alkyl, R2-CX-NG (CH2) b, (C1-C4) alkyl (CH1-) or -G; E is (CH2) a, -CH = CH or -NH (CH2) bNH-; R5 is H or a C1-C8 alkyl residue or G; A is -C0-, - (CH) m, - (CH2) d-CO- or -NH (CH2) CO-, a is a number from 0 to 4, best a number from 2 to 6, it is equal to 1 or 2, d is a number from 1 to 4, k is equal to 2 or 3, m is 0 or 1; a number from 2 to 6; p is 0 or 1; q is 1 or 2; is a number from 2 to 50; and when p is 0, A is -CO-, - (CH2) m-, - (CH2) d-CO- or -NH (CH2) n-CO- when p is 1, A is - (CH2) m-; R the group L represents -CH2-CHR6-, - (CH2) 3-, - (N mYi-N -C = O or R6 is H or a C1-C12 alkyl radical; Y is -CH2-CH (OH) -CH2-; R7 is H or CH3; Q is -Oou> NH; and s is a number from 3 to 60.   The stabilizer combination according to claim 1, wherein: X is O; R. is H or a C 1 -C 6 alkyl radical; R2 is a residue [R3-NG-CX], E-; R3 is H or C1-C8alkyl, R2-CX-NG- (CH2) b, or -G; E is (CH2) a, or -NH (CH2) bNH-; Rs is G; A is (CH2) m-; a is a number from 0 to 4; best a number from 2 to 6; it is equal to 1; m is 0 or 1; is a number from 2 to 6; p is 0; q is 1 or 2; r is a number from 2 to 50; L is -CH2-CHR1- (CH2) 3- or -CH = CH-; R6 is H; Y is -CH2-CH (OH) -CH2-; R7 is H; Q is> NH; and s is a number from 3 to 60.   The stabilizer combination according to claim 1, which further contains alkali metal and / or alkaline earth metal compounds and / or aluminum compounds.   The stabilizer combination according to claim 1, which contains in in addition to calcium carboxylates.   The stabilizer combination according to claim 1, which contains in in addition to aluminum carboxylates.   The combination of stabilizers according to claim 1, which further contains at least one other substance from the group consisting of epoxides and epoxidized fatty acid esters, phosphites, thiophosphites and thiophosphates, polyols, compounds 1, 3-dicarbonyl, mercaptocarboxylic acid esters, dihydropyridines, antioxidants, light stabilizers and UV absorbers, alkali metal compounds and metals   alkaline earth metals, perchlorates, zeolites, hydrotalcites or dawsonites.   8. Composition containing a halogenated polymer and the combination of   stabilizers according to claim 1.   9. Process for stabilizing halogenated polymers, characterized in that   a combination of stabilizers according to claim 1 is added to these polymers.