DD151760A5 - HEAVY-STABILIZED POLYMERISES AND COPOLYMERISATES BASED ON VINYL CHLORIDE AND STABILIZER COMBINATION - Google Patents

Abstract

The invention relates to heat-stabilized polymers and copolymers based on vinyl chloride and the stabilizer combination used for this purpose. This is composed of a) at least one organic zinc compound, b) at least one organic compound of a metal of group 2a of the Periodic Table, c) at least one polyol and d) at least one ester of thioglycolic acid. From the stabilized polymers and copolymers it is possible to produce transparent and colorless products.

Description

Heat-stabilized polymers and copolymers based on vinyl chloride and stabilizer combination used therefor,

Field of application of the invention:

The invention relates to stabilizer combinations for polymers based on polyvinyl chloride, to a process for stabilizing the polymers and to the polymers stabilized by means of the combinations themselves.

The polymers based on vinyl chloride have to be processed at temperatures in the series of 160 to 180 ⁰ C and at even higher temperatures in Beieich of 190 C • if the work cycles to be accelerated.

Characteristic of the known technical solutions:

Numerous references refer to the use of sulfur compounds to stabilize faeces. "The majority of these publications relate to" thiozine compounds which, in addition to more or less pronounced toxicity, may have a number of disadvantages. "

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A recent publication has even pointed to their possibly destabilizing effect on PVC, since thiol compounds can be formed by the decomposition of the "thio-tin" compounds (W, H. STARNES Polymer Preprints, Bd, 19, No. 1, p 623, March 1978).

The use of thiols and thioglycolates as stabilizers for PVC is the subject of various patents, which can be divided into four families or groups:

1) Use of mercaptopropionates alone (JA-OS KOKAI 76 11 77 41) or in the presence of unsaturated terpene compounds (US Pat. No. 3,242,133). The heat stabilizing effect is real, but insufficient.

2) Treatment of PVC with a thioglycolate in Lösungsmediuni at 80 ° C for 3 hours and subsequent use or use of the treated PVC in the presence of metal salts (JA-OS KOKAI 77 13 91 59). The gain in terms of the duration of the stabilization is small, since in the specified experiment, the time is extended from 75 to 90 minutes without any indication that the

25 initial staining is significantly improved.

3) use of thiols or Mercaptocarboxylaten (mercaptopropionate or thioglycolate) in the presence of a primary stabilizer, organotin (U.S. Patent No. 3,928,285 _f GB-PS 1,349,913, DE-OS 21 49 323, US-PS 4,021,407, JA OS KOKAI 73 26 839) c Apart from the fact that the use of organotin compounds is increasingly limited because of the toxicity of these products, the results are not satisfactory.

2 2 217 3

The use of combinations of the two types of products is less effective than the use of the corresponding tin mercaptides (Polymer Letters, Vol. 9 »p. 373, 1971 - Edition J. Wiley and Sons).

4) Use of metal mercaptides. Other mercaptides as organotin compounds have no appreciable effectiveness.

YOSHIRO NAKAMURA has described in several patents and other publications the stabilizing effect achieved by using calcium and zinc salts as well as 2-amino-4,6-dimercapto-S-triazine (JA-OS KOIiAI 78 00 245 and 77 139 160 Journal of Macromolecule Sciences Chem. A 12 (2), pp. 323-326 (1979).

The results achieved with such a stabilizer system are much weaker than those achieved with the stabilizer system according to the invention.

In GB-PS 1 001 344 there are claimed compositions based on F / C which contain:

a) one or more organometallic compounds of lithium, sodium, potassium, magnesium, calcium, zinc, strontium, cadmium, barium, aluminum, tin or lead,

b) an organic or organometallic sulfur compound having a boiling point at atmospheric pressure not lower than 200 ⁰ C; this may be an alkyl sulfide or aryl sulfide, a kercaptocarboxylic acid or an ester of these acids;

c) an organic antioxidant which inhibits the chain

Settling reactions of the PVC prevented; this is mainly a substituted phenolic compound.

5 The products made from these materials are still slightly colored.

Object of the invention

The invention was based on the object, starting from the known prior art, the heat stabilization of vinyl chloride polymers and copolymers to improve so that colorless products can be prepared from the thus stabilized masses.

Explanation of the essence of the invention

It has surprisingly been found that there is a remarkable synergistic effect between organic zinc compounds, organic compounds of the metals of group 2a of the Periodic Table, polyols and esters of thioglycolic acid, in view of the heat stabilization of polymers based on polyvinyl chloride Create certificates of excellent thermal stability.

In the following description, the lower alkyl group is an alkyl group having 1 to 4 carbon atoms and the lower alkoxy group is an alkoxy group having 1 to 4 carbon atoms.

The invention first relates to heat-stabilizing combinations for polymers based on polyvinyl chloride, which are characterized in that

they contain:

a) at least one organic zinc compound,

b) at least one organic compound of a metal of group 2a of the periodic table,

c) at least one polyol and

d) at least one ester of thioglycolic acid of general formula I in the:

η is the integer 1, 2, 3 or k ,

R represents a monovalent or polyvalent group _; which can be:

a linear or branched aliphatic group which is saturated or has one or more ethylenic double bonds and which may have one or more - 0 -, - S - in the chain,

a cycloaliphatic group which optionally carries one or more alkyl or alkoxy substituents and which optionally has one or more ethylenic double bonds,

an aryl group or an aryl-aliphatic group whose ring moiety optionally carries one or more alkyl or alkoxy substituents and which may be bonded to the aliphatic moiety via an oxygen atom,

a trisalkylene isocyanurate group,

12 1

a group -R-COO - R - when η = 2, where R and

p ~

R are linear or branched aliphatic groups, the

- 6 - ii 2 I / w

are saturated or contain one or more ethylenically unsaturated double bonds,

and a chain of several of the above groups *

As organic zinc compound as well as organic compound of a metal of group 2a of the periodic table: salts with the anion of an aliphatic monocarboxylic or dicarboxylic acid having 2 to 24 carbon atoms which is saturated or not saturated and substituted and unsubstituted or with the anion of aromatic monocarboxylic acids or alicyclic carboxylic acids which are optionally substituted. The most common anions are the anions of maleic, acetic, diacetic, propionic, hexanoic, 2-ethylhexanoic, octanoic, decanoic, undecanoic, lauric, myristic, paliaitic, stearic, oleic, ricinoleic, behenic, hydroxy-stearic, hydroxyundecanoic, benzoic, phenylacetic , Alkylbenzoic acid, p-tert-butylbenzoic acid, and salicylic acid; Metal derivatives of optionally substituted phenolic compounds such as phenol or substituted phenols with an alkyl group preferably containing from 4 to 24 carbon atoms; Mercaptides, for example, isooctyl-2-zinc mercaptoacetate, chelates of β-dicarbonyl compounds.

For practical and economical reasons, among the abovementioned organometallic compounds, the compounds derived from carboxylic acids or phenol compounds are generally selected »

Thus, frequently used as compound a) the zinc salts of propionic acid, octanoic acid, lauric acid, stearic acid »

• 7 O 9 9 1 7 Q

acid. Oleic acid, ricinoleic acid, benzoic acid, p-tert-butylbenzoic acid, salicylic acid and the mono-2-Ethylhexylinaleats ^ as compound b) is often used the calcium, magnesium, barium or strontium salts of propionic acid, octanoic acid, lauric acid, stearic acid, oleic acid , Ricinoleic acid, benzoic acid, p-tert-butylbenzoic acid, salicylic acid and mono-2-ethylhexyl maleate So

A proportion of component a) of 0.005 to 1 % by weight, based on the polymer which is to be stabilized, preferably of 0.01 to 0.6 % , gives very good results *

Of the compounds mentioned under b) the calcium, barium, strontium or magnesium compounds are very often used; preferred are the calcium and magnesium compounds, especially the calcium compounds which lead to excellent results. These compounds or derivatives are usually used in admixture with one another, for example Ca and Ba or Ca and Mg. For reasons of effectiveness, the mixture Ca-Mg is preferably used. A proportion of this component b) of from 0.01 to 5% by weight. Jo, based on the polymer to be stabilized, Preferably from 0.03 to 1 % results in combination with the other stabilizers to very good results «

The polyols are suitable for this purpose the stabilizing effect of the inventively provided metal / organic compounds. lengthen connections. However, a reasonable compromise must be found since these products tend to discolor the polymer compositions. In view of the problems of processing the polymer compositions based on polyvinyl chloride at high temperature are preferred

such polyols used as a stabilizer component whose boiling point is above 150 ⁰ C and usually above 170 ° C.

Examples of such polyols are triols such as trimethylolpropane glycerol, hexane-1,2,6-triol, butane-1,2,4-triol, trishydroxyethyl isocyanurate; Tetrols, such as pentaerythritol, diglycerol, pentitols, such as xylitol; Hexitols such as sorbitol, mannitol and dipentaerythritol; Polyols having 8 0H ~ _f groups as well as polymers with Tripentaaerythrit

10 free OH groups, such as polyvinyl alcohols, especially

those polyvinyl alcohols in which less than 30 mol% of ester groups are present, based on the total number of OH and ester groups, which determines a viscosity at 20 ⁰ C with a 4-w _e - o o-igen aqueous solution of

15 have about 4 to 60 Pa · s.

In general, 0.005 to 1% by weight of polyol, based on the polymer to be stabilized, is used, preferably 0.01 to 0.6 % _e 20

It has been found that the polyols with more than 4 OH groups in the molecule lead to particularly favorable results.

Thus, polyols such as sorbitol, mannitol and xylitol have been found to be particularly effective in the polymer compositions and stabilizer combinations of the present invention, even when used in low dose. The preferred dosage for these compounds is 0.01 to 0.25 parts by weight, based on the polymer; However, the stabilizing effect is already very clear without unwanted side effects with regard to discoloration. occur if their share only Q, CÖ5 to 0.01 % by weight , based on the polymer.

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Among the thioglycolic acid esters of general formula I,. the the component. ; d) usually those are used in which in the formula η the integer is 1,2 or 3 and R stands for a monovalent or divalent group such as:

an aliphatic, linear or branched group which is saturated or has one or more ethylenically unsaturated bonds and may have from 2 to 36 carbon atoms in the molecule and also one or more chain members - 0 or S S -,

a cycloaliphatic group having 5 to 12 carbon atoms, which is optionally substituted by one or more lower alkyl groups or lower alkoxy groups,

a cycloaliphatic or cycloalkenyl aliphatic group having 6 to 16 carbon atoms, the ring portion of which is optionally substituted by one or more lower alkyl groups or lower alkoxy groups and the aliphatic portion of which comprises 1 to 6 carbon atoms and may be bonded to the ring via an oxygen atom;

an aryl group or araliphatic group ^ whose ring is optionally substituted with one or more lower alkyl groups or lower alkoxy groups and their optionally present aliphatic part comprises 1 to 6 carbon atoms and is attached to the ring via an acid moiety "

30 can be bound to the atomic substance 0,

a trisalkylene isocyanurate group whose alkylene groups have 1 to 4 carbon atoms,

1 o 12

a group -R-COO ™ R -, where R and R are the same

2 1 73

or are different and each represents a linear or branched aliphatic group having 1 to 18 carbon atoms which is saturated or has one or more ethylenically unsaturated bonds, 5

and a chain of several of the aforementioned groups *

With regard to the processing of the polymers based on polyvinyl chloride at elevated temperatures, the thioglycolic acid esters used should preferably have a boiling point above 15O ⁰ C and usually above 170 ° C "

The thioglycolic acid esters of general formula I are easily obtained by esterification of thioglycolic acid with various mono- or polyhydroxy compounds. The latter include in particular the following:

1) When η = 1, R is derived from a monoalcohol R-OH,

R may be a linear or branched alkyl group or alkenyl group having preferably 6 to 36 carbon atoms, _s

In this case, starting from linear or non-linear alcohols such as isooctyl alcohol, dodecyl alcohol, octadecyl alcohol, stearyl alcohol, undecyl alcohol or Gernische from C ^ ,, - C i c alcohols, such as those sold under the trade name SYNPROL alcohols.

R can still be a phenyl group. or phenylalkyl group or a cyclohexyl group or cyclohexylalkyl group

whose ring moiety is optionally substituted with one or more lower alkyl groups or lower alkoxy groups and whose optionally present aliphatic moiety comprises 1 to 6 carbon atoms and may be bonded to the ring moiety via an oxygen atom-O- *

In this case, it is assumed that cyclohexanol, optionally substituted benzyl alcohol, nonylphenol, the Phenäthylalkoholen, ß ~ Phenoxyäthylalkohol or Aiiisolalkohol.

R can also be a concatenation of several of the abovementioned groups or radicals.

2) When η = 2, R is derived from a diol R (OH) ₂ ,

R may be a linear or branched alkylene group having 2 to 24 carbon atoms,

In this case, one starts from diols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, pentanediol. 1,5, 1,6-hexanediol, 2,2,4-trimethylpentanediol-1,3 or of diols of general formula II in which R ^f and R ¹ 'are the same or different and each represents lower alkyl groups, for example, neopentyl glycol.

-ι ρ be λ R can also be a group - R - COO - R -, / where R and

ρ 30 R then have the meanings given above »

In this case, it is possible to start with certain polyol esters, for example neopentyl glycol hydroxypivalate or glyceryl monostearate.

R may also be a cyclohexylene or Cyclohexylenalkyl- or a Cyclohexylendialkylgruppe whose ring member is optionally substituted with one or more lower alkyl groups or lower alkoxy and whose optionally present aliphatic parts comprise 1 to 6 carbon atoms and via an oxygen atom-O- at the. Ring part can be tied.

In this case, starting from dihydroxy compounds such as 1,2-bis (hydroxymethylcyclohexane., 1,3-bis (hydroxymethyl) cyclohexane, 1-, 4-bis (hydroxymethyl) cyclohexane and 1,4-dihydroxycyclohexane.

R may also be a phenylene group or a phenylene alkyl group or a phenylenedialkyl group whose ring moiety is optionally substituted with one or more lower alkyl groups or lower alkoxy groups and their optionally present aliphatic moieties comprise from 1 to 6 carbon atoms and bonded to the ring by an oxygen atom can"

In this case one starts, for example, from 1,4-bis (hydroxymethyl) benzene,

R can also be a concatenation (combination) of several of the above groups.

One can then proceed, for example, hydrogenated bisphenol A or of 4.4 ^l -bis (2-hydroxypropoxy) ~ 2J2-diphenylpropane (BHPDP) or of 4.4 ^I-bis (2-hydroxyethoxy} -2,2-diphenylpropane (BHEDP It is furthermore possible to use, as dihydroxy compounds for the preparation of the dihydric esters of thioglycolic acid, OH-terminated polyethers, such as polyethylene glycols or polyols.

35 propylene glycols of low molecular weight or

linear polyesters with terminal OH groups also having low molecular mass «

3) If η is greater than 2i 5

R may be a trivalent aliphatic, linear or branched group having 3 to 24 carbon atoms.

In this case, one starts from simple triols, such as 1,2- 6-hexanetriol or 1,2,4-butanetriol, or from trimethylolpropane or glycerol. Tetrols may also be used, such as pentaerythritol or hexols, such as sorbitol optionally 1, 2 or 3 OH groups can be esterified «.

R may furthermore be a Trisalkylenisocyanuratgruppe whose alkylene groups each have 1 to 4 carbon atoms., In this case, one can assume, for example, trishydroxyethyl isocyanurate (THEIC).

20 ..-- ·

The preferred thioglycolic acid esters generally include the compounds where η is 2 and which generally give the best results. The compounds in which η is the number 1 also give very good results, which in any case are superior to those obtained with compounds in which η is greater than 2, especially in the case of plasticized polymer compounds. «

Among the compounds are well suited for the practice of the invention include, in 1,2-propanediol alone j-thioglycolate, propane-1,3-tbioglykolat, butane-1,2-thioglycolate, butane-1 _f 3-thioglycolate, Butanediol-1,4-thioglycolate, hexanediol-1,6-thioglycolate, isooctyl thioglycolate, lauryl thioglycolate, cetyl thioglycolate,

222173

Octadecyl thioglycolate, 2 ~ methyl-2-propyl-propanediol ~ 1,3-thioglycolate, ethylene glycol thioglycolate, neopentyl glycol thioglycolate, 2,2,4-trimethylpentanediol ~ 1,3-thioglycolate »1,2,6-trimethylhexanediol thioglycolate, trimethylolpropane thioglycolate, 1, 2,6-Hexantriolthioglykolat, Benzylthioglykolat, hydrogenated bisphenol A-thioglycolate, 1,4-bis (hydroxymethy3) c; yclohexan thioglycolate, Trimethyloläthantristhioglykolat, trimethylolpropane tristhioglykolat, pentaerythritol tetrakis thioglycolate, Glycerylmonoricinoleabmonothioglykolat, Trishydroxyäthylisocyanurat thioglycolate and neopentyl glycol thioglycolate ,,

This Thioglykolester be used in proportions which depend on their molecular weight and generally in the range of 0.005 to 5 Ge \ i "-% _f are preferably 0.05 to 1 wt .- ^, based on the polymer.

In general, it can be stated that the proportion by weight of each of the stabilizer components according to the invention will be the higher in the polymer compositions to be stabilized, the stiffer they are, i. the less plasticizers they contain. Within the range of the various proportions for the individual components a), b), c) and d) of the stabilizer combination according to the invention, the skilled person will select the relative proportions of the various components so that he achieves the desired best possible result for each particular formulation "

The invention also relates to a verifier for stabilizing polymers based on polyvinyl chloride, which is characterized in that the components of the stabilizer combination described above are used.

35 nations used together.

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Finally, the invention also relates to the polymer compositions based on vinyl chloride stabilized with the aid of the combination according to the invention.

As a polymer compound based on vinyl chloride 'or Polyvinyl chloride shall be understood to mean all polymer compositions which contain a vinyl chloride homopolymer or a vinyl alcohol copolymer, a copolymer of vinyl chloride with other monomers or a mixture of polymerizate and copolymer obtained predominantly from vinyl chloride.

In general, all vinyl chloride homopolymers are independent of the manner of their preparation: bulk polymerization suspension polymerization, dispersion polymerization or any other polymerization techniques and regardless of the intrinsic viscosity. These homopolymers may also be chemically modified, such as the postchlorinated vinyl chloride polymers. The stabilizer combination according to the invention is particularly effective when used with a polymer produced by bulk polymerization based on PVC.

Numerous vinyl chloride copolymers can also be stabilized according to the invention against the effects of heat: yellowing and degradation. These include the copolymers obtained by copolymerizing vinyl chloride with other monomers having a polymerizable ethylenic double bond, for example with vinyl esters such as vinyl acetate ₃ with vinylidene chloride, with maleic acid or fumaric acid or the corresponding esters, with olefins such as ethylene , Propylene and hexene, with acrylic esters, with

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Styrene or with vinyl ethers, such as n-vinyldodecyl ether.

These copolymers usually contain at least 50 % by weight of yliyl chloride units. The invention is particularly suitable for copolymers which contain at least 80% by weight of vinyl chloride units.

Also suitable are mixtures of polymers which contain a small proportion of other polymers, such as halogenated polyolefins or acrylonitrile-butadiene-styrene copolymers _; or the mixtures of the abovementioned homopolymers or copolymers ^

The polymer compositions may be either rigid or rigid polymers or flexible or plasticized polymers. If rigid polymer compositions are used, these may contain, in addition to the polymer and the various stabilizers or auxiliaries, agents for improving the impact resistance, pigments and / or fillers and lubricants for improving the processability.

Be plasticized Polymerisatmassen used, they primary or secondary plasticizer may contain, as well as pigments and / or fillers, lubricants and other more, in addition to the polymer and various stabilizers or adjuvants "These stabilizers are substantially antioxidants, light stabilizers or UV stabilizers u _e a «Compounds whose effect on heat stabilization is known, such as epoxides, phosphites and phenolic compounds ·

The epoxides are generally complex compounds, usually epoxidized polyglycerides such as epoxidized

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Soybean oil, epoxidized linseed oil or epoxidized fish oil, epoxidized tall oil or epoxidized esters of fatty acids, or epoxidized hydrocarbons, such as epoxidized polybutadiene or epoxidized ether. Various alkylphosphites or arylphosphites are also known for their stabilizing effect, for example phenylphosphite and 2-ethylhexylphosphite, triisodecylphosphite or daxisoctyldiphosphite and pentaerythritol diphosphite.

10.

Phenolic compounds have also been used as heat stabilizers. "These are mainly butylated hydroxytoluene (BHT) and other substituted phenols.

Other known stabilizers may also be added in small amounts, for example β-diketo compounds or organic nitrogen compounds, such as β-aminocrotonic acid esters or β-phenylindole derivatives, or derivatives of substituted dihydropyridines.

The inventively provided four stabilizer components can be incorporated simultaneously with the other additives in the Polyiaerisatinassen _o They can also be mixed first with each other or with certain other additives and then incorporated subsequently in the polymer. All conventional procedures in this field are suitable for the preparation of the mixture of components. The final Komogenisierung can be carried out advantageously on a kneader or a roll mixer at a temperature such that the Polymerisatmasse is flowable, usually between 150 and 170 ⁰ C for PVC and during

because of a sufficient time / with a good homogenization

35 is obtained, d _s h "for about 3 to 20 minutes,"

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The polymer compositions based on polyvinyl chloride which are stabilized in accordance with the invention can be further processed with the aid of all shaping methods customary for PVC and vinyl chloride copolymers, for example by injection molding, extrusion, blow molding, calendering and rotary press molding.

The inventive. Stabilizer combination makes it possible to significantly delay or completely suppress the occurrence of yellowing during the period of time in which the vinyl chloride-based polymerizate mass is heated to 18 ° C. and higher, so as to obtain transparent, colorless, homogeneous end products, which may not Exuding _o

In the following examples, the various compositions were prepared by mixing the various components in powdered or optionally liquid manner in a ball mill which was run on the roll mill during the time required for good homogenization, generally at least 5 minutes.

Starting from these homogeneous masses, 1 mm thick foils were then produced by calandering at 150 to 180 ° C. for 3 minutes, from which rectangular test pieces approximately 1 × 2 cm in size were cut out; these were held in the ventilated oven at 175 ° C, 180 ⁰ C or 19O ⁰ C for different lengths of time periods

Finally, the discoloration of the specimens was determined by comparison with a Lovibond disc according to the Gardner scale

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EMBODIMENTS Example 1

These first experiments serve to demonstrate the synergistic effect of the various components of the stabilizer combination according to the invention »

The following Grimdmischung A was produced: 10

654 g of powdered polyvinyl chloride with a viscosity number of 95 (French standard NF T 51 013), obtained by bulk polymerization, trade name LUCOVYL GB 9550, 326 g of dioctyl phthalate,

10 g of epoxidized soybean oil.

In each case 100 g of this masterbatch A were admixed with the stabilizers or stabilizer combinations listed in Table 1 below, and 1 mm thick films were produced with each of the molding compositions obtained in this manner by means of calendering for 8 minutes at 150 ^° C. Then the films thermally aged in the oven at 180 C and the discoloration evaluated according to the Gardner scale. "The results are summarized in Table 1. Only example 1 was carried out with a stabilizer combination according to the invention.

In all the following tables is thioglycolate with

TG abbreviated., ·

These experiments also serve to synergistic

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To show effect of the stabilizer combinations according to the invention. A masterbatch B of the following composition was prepared:

5 665 g of the same FVC powder as in Example 1,

320 g of dioctyl phthalate,

8.6 g of epoxidized soybean oil,

1.7 g of trinonylphenyl phosphite.

In each case 100 g of base mixture B were added to the stabilizers listed in the following Table 2 and then calendered for 4 minutes at 16O ° C to obtain films in a thickness of 1 mm. The subsequent heat treatment was carried out as in Example 1 in an oven at 180 ⁰ C. The discoloration was evaluated according to Gardner; the results are summarized in Table 2.

(Only example 2 was carried out with a stabilizer combination according to the invention). 20

Examples 5 to 20

The following basic mixture C was first prepared:

25 1, 308 g. FVC powder according to Example 1, 652 g of dioctyl phthalate, 20 g of epoxidized soybean oil, 1.4 g of zinc stearate, 2.4 g of calcium stearate, 30 0.4 g of sorbitol.

To each 100 g of base mixture C was one of In

Table 3 listed stabilizers.

From the stabilized mixtures, 1 mm thick foils were

/ 21

- 21 - 2 2 2 17 3

It was prepared by calendering at 150 ° C for 8 minutes.

The heat test was carried out as in Example 1 at 180 ⁰ C. Gardner's color values are summarized in Table 3.

Examples 21 to 24 10 A base mixture D was prepared from;

654 g of PVC powder according to Example 1, 326 g of dioctyl phthalate,

10 g epoxidized soybean oil, 15 0.7 g zinc stearate, 1.2 g calcium stearate, 0.1 g sorbitol.

To four portions a 100 g of the base mixture D were each one of the in the. Table 4 given stabilizers. The stabilized Grundmisehungen were then calendered for 8 minutes at 150 ⁰ C and with the obtained 1 mm thick films, the same thermal aging tests performed at 180 C as in Example 1. The measured Gardner color numbers are summarized in Table 4.

In these examples, another anion was used in the calcium compound. It was a basic mixture E prepared from:

654 g of PVC powder according to Example 1, 35 326 g of dioctyl phthalate,

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10 g of epoxidized soybean oil, 3.2 g of bis-4,4- (2-hydroxyethoxy) -2,2-diphenylpropane

thioglycolate (BHEDP), 0.2 g sorbitol, 5 0.7 g zinc stearate.

In each case 100 g of basic mixture E, various calcium salts were added. The thermal aging at 180 ⁰ C v / urde vrie forth in Example 1, with 1 mm thick test specimens by calendering at 150 ⁰ C for 8 minutes were obtained. The measured Gardner color numbers are summarized in Table 5 below.

15 examples 50 to 35

A basic mixture F of the following composition was prepared:

20 654 g of PVC powder according to Example 1, 326 g of dioctyl phthalate, 10 g of epoxidized soybean oil, 2.8 g of 1,4-bis (hydroxymethyl) cyclohexane 0.7 g of zinc stearate, 25 0.2 g of sorbitol.

Four portions of each 100 g of basic mixture F were admixed with one of the four calcium salts indicated in Table 6 below. With the mixtures stabilized in this way, 1 mm thick films were prepared by calendering at 150 ° C for 8 minutes.

The oven test at 180 ⁰ C was carried out as in Example. 1 The Gardner color number is given in Table 6

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Example 34 '. ·

To 10Og of basic mixture E 0.12 g of magnesium salt of mono-2-ethylhexylmaleats were added. The oven test at 180 C was carried out using 1 mm thick test specimens, which were obtained by calendering at 150 ⁰ C for 8 minutes. Gardner color numbers are listed in Table 7.

10 examples 35 to 37 ·

Other magnesium salts were used as the organic derivative of a Group 2a metal of the Periodic Table. The following basic mixture G was prepared:

654 g of PYC powder according to Example 1,

326 g of dioctyl phthalate,

10 g of epoxidized soybean oil,

0.7 g of zinc stearate,

20 0.2 g of sorbitol,

2.8 g of neopentyl glycol thioglycolate.

Three portions a of 100 g each of G were mixed with one of the various magnesium salts listed in Table 8 below. With the mixtures stabilized in this way, 1 mm thick films were prepared, by calendering for 8 minutes at 150 ^o C. The oven test was carried out as described at 180 ⁰ C. The Gardner color numbers are in the table

30 summarized.

Examples 38 and 39

In these examples, with barium salts as organic

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worked sches derivative of a metal of group 2a of the periodic table.

In each case 100 g of basic mixture E were admixed with one of the two barium salts indicated in Table 9 below.

With the stabilized mixtures 1 mm thick films were prepared by calendering at 150 ⁰ C for 8 minutes and carried out with the test specimens of the oven test as described at 180 C. Gardner color numbers are summarized in Table 9.

Examples 40 to 44

In these examples, binary or ternary combinations of metal salts of group 2a of the periodic table were used.

Five portions a of 100 g each of G were admixed with one of the combinations of metal salts of group 2a listed in Table 10 below.

The stabilized mixtures were calendered 8 minutes at 150 ⁰ C and cut the test pieces from the obtained 1 mm thick films; with which the oven test was carried out at 180 C. Gardner color numbers are summarized in Table 10 below.

30 examples 45 to 50

In these examples, the anion of the zinc salts was changed in the stabilizer combination according to the invention.

35 First, the following basic mixture H was prepared:

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654 g of PVC powder according to Example 1, 326 g of dioctyl phthalate, 10 g of epoxidized soybean oil, 3 g * 2 4.4 ^f-bis (2-hyaroxyäthoxy) ~ 2,2-diphenyl ~

'thioglycolate' (BHEDP), 1.2 g calcium stearate, 0.2 g sorbitol.

100 g of base mixture H were admixed with one of the six organic zinc compounds listed in Table 11 below. The stabilized mixtures were calendered 8 minutes at 150 ⁰ C and the oven test at 180 ⁰ C made using the 1 mm thick films "The Gardner color numbers are summarized in the following Table 11 below.

Examples 51 to 61

Experiments were carried out with various pairs of organozinc compounds and organic calcium compounds.

First, the following basic mixture J was prepared:

25 981 g of PVC powder according to Example 1, 489 g of dioctyl phthalate, 15 g of epoxidized soybean oil,

4-j2 g of 1,4-bis (hydroxymethyl) cyclohexane-thioglycolate ^ 0.3 g of sorbitol

 30

To eleven., Shares a each 100 g of base mixture J was added to one of the pairs of zinc and calcium compounds listed in Table 12 below. With the stabilized masses obtained in this way, 1 mm thick films were produced by means of calendering during

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-22- 222173

8 minutes at 15O ⁰ C. ·

The thermal aging was performed at 175 ° C this time. The color numbers according to Gardner are summarized in the table.

Examples 62 'to 68

These examples relate to the use of different polyols in the stabilizer combinations of the invention.

The masterbatch K of the following composition was prepared:

654 g of PVC powder according to Example 1,

326 g of dioctyl phthalate, 10 g of epoxidized soybean oil,

1.2 g calcium stearate, 20 0.7 g zinc stearate, 2.8 g thioglycolate of hydrogenated bisphenol A.

Seven portions a of 100 g each of basic mixture K were admixed with one of the polyols listed in Table 13 below.

With the stabilized mixtures and with a sample of the basic mixture K 1 mm thick films were prepared by calendering for 8 minutes at 150 ⁰ C. The entest was carried out at 180 C. Gardner color numbers are summarized in Table 13.

• Example 69

This example illustrates the use of an invented

-27- 222173

A combination of stabilizer and stabilizer combination together with a highly protected PVC.

The following basic mixture was prepared:

g PVC powder according to Example 1,

42.3 g of dioctyl phthalate,

3.0 g epoxidized soybean oil,

0.20 g of trinonylphenyl phosphite,

0.07 g of zinc stearate,

0.15 g calcium stearate,

0.21 g of thioglycolate of hydrogenated bisphenol A,

0.03 g of sorbitol.

15 This mixture was calendered for 4 minutes at 150 ⁰ C and 1 em thick sheet for the oven test at 190 ⁰ C used * The color numbers Gardner are in the following Table 14 summarizes zusa m quantitative.

It was prepared the following basic mixture:

75.3 g of PVC powder according to Example 1,

22.8 g of dioctyl phthalate,

1.15 g of epoxidized soybean oil,

0.23 g of trinonylphenyl phosphite,

0.09 g of zinc stearate,

0.18 g calcium stearate,

30 Ο, 23 g of thioglycolate of hydrogenated bisphenol A,

Ο, 04 g of sorbitol.

This mixture was. Calibrated for 4 minutes at 170 C, to a 1 mm. strong foil. The oven test was carried out at 180 ° C 35. The color numbers according to Gardner are summarized in the following Table 15,

/ 28

- 28 - 2 2 2 17 3

Example 71

The following mixture was produced:

78.6 g of powdery PVC, viscosity number 80 according to the French standard NF T51O13> obtained by mass polymerization, trade name LUCOVYL RB 8010, 15 »3 g dioctyl phthalate, 3.7 g epoxidized soybean oil,

0.75 g of trinonylphenyl phosphite, 0.26 g of zinc stearate, 0.53 g of calcium stearate,

0.75 g hydrogenated bisphenol A thioglycolate, 15 0.11 g sorbitol,

The mixture was calendered for 4 minutes at 170 ° C to a 1 minute film. The thermal aging was carried out at 190 ⁰ C. The color numbers according to Gardner are. summarized in Table 16.

Examples 72 to 74

These examples illustrate the use of stabilizer combinations according to the invention together with rigid PVC.

The following basic mixture L was prepared:

30 1000 g FVC powder, viscosity number 80 according to standard

NF T51O13j obtained by suspension poly-. , merisation, trade name LUVOVYL FtS

8000,

100 g Impact resistance improver, in the form of a copolymer of butadiene

- 29 - Zd Z / O

Styrene and methyl methacrylate,

10 g of lubricant or lubricant, namely a colophony ester wax (trade name wax E)

30 g epoxidized soybean oil, 5 g zinc stearate, 5 g calcium stearate.

To each of six portions a of each 100 g of Base Mix L were added either sorbitol alone or a mixture of sorbitol and 1-A-bis (hydroxymethyl) cyclohexane-thioglycolate (BPMC-TG) as shown in Table 17 below.

The experiments with sorbitol alone (72a, 73a and 74a) serve for comparison and show the advantages / achievable with the four-component stabilizer combination according to the invention compared to mixtures which contain only a three-component StaMLisator combination *,

The obtained mixtures were made 1 mm thick sheets by 3-minute long calendering at 180 ⁰ C. The furnace test was carried out at 180 ⁰ C. The color numbers are summarized in Table 17.

/ 30

Ex. Comp. tries ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ 0 7 14 21 30 40 50 60 70 1 Zinc stearate 0.07 Calcium stearate 0.12 Sorbitol 0.03 Bisphenol A-TG hydrogenated 0.28 0 0 0 0 0 0 0 0 1 brown 85 min la Bisphenol A-TG hydrogenates 0.28 0 0.5 1 3 VJL 7 brown 1b Bisphenol A-TG hydrogenates 0.28 calcium stearate 0.12 0 0 0.5 3 5 6 brown a 1c Zinc stearate 0.07 calcium stearate 0.12 0 1 3 scfcwa * - 23 Rand black 1d Zinc stearate 0.07 calcium stearate 0.12 sorbitol 0.03 2 6 7 7 8th 8th Brown black 1e Zinc stearate 0.07 Calcium stearate 0.12 Bisphenol A-TG hydrogenates 0.28 0 0 1 2 3 black alien black

TABLE 2

Example and comparative experiments ^ v time, stabilizers min 0 · 7 14 21 30 40 50 60 2 Zinc stearate calcium stearate sorbitol bisphenol A-TG hydrogenated 0.12 0.24 0.05 0.17 0 0 0 , 0 0 0 1 3 black after 80 min 2a Bisphenol A-TG hydrogenated 0.17 1,5 going to the pink 4 5 11 12 13 14 brown 2 B Zinc stearate calcium stearate sorbitol 0.12 0.24 0.05 1.5 j VJl 6 7 7 7 black edges black

Examples 1 7 ^^ "" ^ "^ - ^ _ time, min 0.28 0 7 14 21 30 40 0.5 50 black edges after 70 min black after 62 min 8th Stabilizers, g ~ * 0.56 2 black ^ edges after 53 min black edges after 80 min 9 only * basic mix..G ., I 0.40 0.5 3 4 5 5 ₇ 3 3 4-80 min 3 Neopentylglycol TG 0.28 0 0 0 0 0 0.5 0.5 2 black edges at 70 min Lauryl TG 0.28 0 0 0 O. 0 0.5 Sch was i 0.5 black 3 black at 70 min 5 Synprol-TG 0.28 0 0 0 0 0 0.5 0.5 Butane-diol-1,3-TG 0.28 0 0 0 1 2 3 Hexanediol -1,6-TG 0 0 0 0 2 2-methyl-2-propylpropanediol-1,3-TG 0 0 0 0 0 Neopentylglycol hydroxypivalate TG 0 0 0 0 0

VM fV)

TABLE 3 (continued)

Belap. S t ab i 1 isat ο re "^^^^^ Jlti ^ Time 0 , min 7 * 0 • ft * · 14 21 0 40 0.5 3 at 70 min 10 Neopentylglycol hydroxypivalate TG 0.40 0 0 0 0 0 0 0 0 1 at 70 min 11: • Neopentylglycol hydroxypivalate TG 0.40 + sorbitol 0.01 0 0 0 0 0 0 0 3 black 12 2,2,4-Trimethyl-pentanediol-1,3-TG 0.28 0 0 0 0 0 1 at 70 min 0 2 black 13 Bisphenol A-TG, hydrogenated 0.28 0 0 0 0 1 at 70 min 0 1 2 at 70 min 14 Bisphenol A-TG, hydrogenated 0.28 peas &&httββ> j 0 0 0 0 0.5 0 1 at 70 min 15 Bisphenol A-TG, hydrogenated 0.44 pfus So / 6 / έ OO "7 0 0 0 0 0 0 1 at 70 min 16 Bis-1,4- (hydroxy-methyl) cyclohexane O, 28 0 0 0 0 0 0 0.5 at 70 min 17 Bis-1,4- (ihydroxy-methyl) -cyclohexane O, 40 0 0 0 0

τ A ü Hi Jb JU is:?

Ex. Stabilizers | y ~> Time 0 , min 7 14 21 30 40 50 18 TG of technical 1,2,6-trimethylhexanediol 0, 28 0. 0 0 0 0 0.5 2 black edges at 70 min 19 BIiEDP-TG 0, 40 0 0 0 0 0 0 0.5 black edges at 70 min 20 BHPDP-TG 0, 40 0 ... 0 0 0 0 0 3 black at 64 min

BHEP = bis-4,4- (2-hydroxyethoxy) -2,2-diphenylpropane BHPDP = bis-4,4 ^f - (2-hydroxypropoxy) -2,2-diphenylpropane

TABLE

I example ^ -Nv time, min 0.4 0 7 14 21 30 40 50 70 Stabilizers, gV. 0.4 21 Hexane-triol-1,2,6-TG 0.4 0 0 0 1 1 1 2 I 3 22 Butane-triol-1,2,4-TG 0.4 0 0 0 0 0 0 i 1 23 Trishydroxyethyl isocyanate TG 0 0 0 1 1 2 3 4 , 24 Trimethylolpropane TG 0 0 0 0 0 0 1 Ί

TABLE S 5

Examples ^ * \ Time, min 0 7 14 21 30 40 55 black edges at 75 min Calcium salts, £ N ^ black at 75 min 25 Calcium stearate 0.12 0 0 0 0 0 0 1 black at 75 min 26 CalciumoctanoatO, 08 0 0 0 0 0 0 1 5 5 to 75 min 27 Calcium p-tert-butylbenzoate 0.09 0 0 0 0 0 0 1 brown at 65 min 28 Calcium p-tert-butylbenzoate 0.16 0 0 0 0 0 0 O, 29 Ζ Calcium salt of mono-2-ethylhexylmaleate 0.09 0 0 0 0.5 1 ! 1 4

TABSLLE "'6

S examples ^ - \ time, min 0 7 14 21 30 , 0 40 60 brown  I ' 100 min Calciuine salts, '£ K. 0 . brown at 100 min 30 Calcium stearate 0.12 0 0 0 0 0 0 0 0 brown brown at 90 70 min 31 Calcium p-tert-butylbenzoate 0.12 0 0 0 0 0 0 at at 32 33 Calcium salicylate 0.08 calcium benzoate 0.12 0 0 0 0 0 0 0 0 0 0 0 1

TABLE

Examples ^ s ^ time, min 0 7 14 21 30 40 55 Ma gne s ium - ^ v. salt g 34 Magnesiumsalζ Mono 2 - ethylhexyl maleats O, 12 0 0 0 0.5 1 3 "brown

VJJ VD

TABLE 8

Examples \. Time, έ min 0 7 14 21 30 40 50 brown Magnesium-> s at salt 0 \ 70 min 35 Magnesium- salicylate 16 0 0 0 0 0.5 brown VI «Ir - O Γ XtJrL "· ken brown 36 Magnesium- at stearate 12 0 0 0 0 0 O • 70 min brown 37 Magnesium- 0 μ-tert-butyl 1 benzoate 12 0 0 0 0 Q 0.5 2

TABLE 9

Examples ^ \ ^^ time » min 0 7 14 21 5 30 40 55 black barium salt at 38 Barium- 60 min stearate 0 , 09 0 1 2 2, 1 1 black margins 5 black 39 Barium p.- at tert-butyl 63 min benzoate 0 , 09 0 1 2.5 1, 1.5 1 black margins

TABLE 10

Beispiele i examples ^ - ^ time, min 0 7 14 21 30 40 50 70 Combination of Metal Salts of Group 2a 40 Calcium stearate Magnesium stea- rat 0.06 0.06 0 0 0 0 0 0 0.5 black edges 41 Calcium stearate Magnesium p, - tert-butyl benzoate 0.06 0.06 0 0 0 0 0 0 0.5 black edges 42 ι Calcium p-tert-butylbenzoate Magnesium stearate 0.06 0.06 0 0 0 0 0 0 1 black edges 43 Calcium p-tert-butyl benzoate magnesium salicylate 0.06 0.06 0 0 0 0 0 0 0.5 black 44 Calcium salicylate Magnesium salicylate 0.5 0 0 0 O 0 0 O black

TABLE 11

"^ \ ^^ time, min 0 7 14 21 30 40 55 ' ^i; ''"""''"'' 3 at 75 min Examples Stabilizers ^ " brown at 75 min zinc stearate 0.07 0 0 0 0 0 0 1 .i; ·, black at 64 min 45 Zinc-2-ethylhexanoate 0.03 0 0 0 0 0 0 black edges bej 75 min black at 63 min 46 Zinc p-tert-butylbenzoate 0.05 0 1 2 2 2 1 black edges 47 Zinc salt of mono-2-ethylhexyl maleate 0.05 0 0 0 5 2 2 2 1 48 Zinc nonylphenolate 0.1 0 0 0 0 0 0 3 49 Isooctyl acetate 2-zinc mercaptide 0.09 0 0 0 0 0 0 2 50 - · ³ <

TABLE "12

"" --- ^^^ time, ι -, J I 7 ' ' 21 0 0 4UE ¹ '. w · "*: black 100 min black 100 min ¹ '' '*'. '' * Examples stabilizers, min 0 14 0 bu brown at Zinc stearate Calcium stearate Zinc stearate Calcium p-tert. butylbenzoate 0 0 0 0 0 0 0 brown at 51 52 Zinc stearate Calcium salicylate 0.07 0.12 0.07 0.12 0 0 0 0 0 0 . 0 '>*>^"":.: 1 0 0 0 3 at 100 Margins at edges at 53 Zinc stearate calcium benzoate 0.07 0.06 0 0 0 0 0 0.5 99 min 54 Zinc-2-ethylhexanoate calcium stearate: \ 0.07 0.12 0 0 \ ' 0 0! j j * 0 1 73 min 55 0.03 0.15 0 0 0 min

TABLE 12 (continued)

Ex. stabilizers 0.03 0.09 Time, 0 min 7 14 21 30 40 60 4 at 100 min 56 Zinc-2-ethylhexanoate Caicium octanoate 0.03 0.15 0 0 0 0.5 0.5 0.5 0.5 3 at 100 min 57 Zinc-2-ethylhexanoate Calcium p-tert-butylbenzoate 0.08 0.16 0 0 0 0 0 0 0.5 brown at 97 min 58 Zinc nonyl phenol Calcine p-tert. - butyl benzoate ' 0.08 0.18 0 0 0 0 0 0 0 brown at 99min 59 Zinc nonylphenol Caicium octanoate 0.08 0.12 0 0.5 0.5 0.5 0.5 0.5 0.5 brown at 92 min 60 Zinc p-tert-butylbenzoate Calcium p-tert-butylbenzoate 0.07 0.12 0 0 0 0 0 0 0 brown at 98 min 61 Isooctylacetate-2-zincmerteoptad calcium-p-tert. - butyl benzoate 0 0 0 0 0 0 0.5

TABLE

13

Examples ^, ^^ time, min 0 7 14 21 I 30 40 0 • Polyols ^ ^{s> v} -> ^^. 0 black at 85 min only basic mix K 0 0 -1 2 3 1 black at 85 min 62 Sorbitol 0.03 0 0 0 0 0 black black at 70 min 63 Mannite 0.03 0 0 0 0 0 black edges brown spots 64 Xylitol 0.03 0 0 0 0 0 0 5 65 Trimethylolpropane 0.08 0 0 0 0 0 0 4 7 at 80 min 66 Pentaerythritol 0.12 0 0 0 0 0 0 black edges at 80 min 67 DipentaerythritO, 04 0 0 0 0 0 3 68 Diglycerin 0.06 0 0 0 0 2 5 3 3

222 173

T AB ELLE 14

Time, min O 7 14 21 30 40 55 80

Gardner rating 0 0 0 002 6 7

TABLE 15

Time, min 0 7 14 21 30 40 55 80

0.5 1 3 schv / arz

Gardner rating 0 0 0 0

TABLE 16

Time, min 0 7 14 21 30 40 55 90

Gardner rating 0 0 0 0 0,51 3 black

/ 47

22 2 173

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724968

222 1 73 -5 ¹ * -

formula sheet

(HS - CH ₂ - COO - R (I).

R ·

HO - CH ₂ --C - CH ₂ --OH (II)

R "

Claims (9)

invention claim 1 * Heat-stabilized polymer compositions based on vinyl chloride, characterized in that they are stabilizers 5 a) at least one organic zinc compound, b) at least one organic compound of a group 2a metal of the periodic system, c) at least one polyol and d) contain at least one ester of thioglycolic acid. 10 2. Claim according to item 1, characterized in that the polymer compositions, based on the weight of the polymer, 0.005 to 1 wt - . % And in particular 0.01 to 0.6 wt .-% organic zinc compound 15 included. 3. Claim according to item 1 or 2, characterized in that the polymer compositions, based on the weight of the polymer, .0.01 to 5 wt .-% and in particular 0.03 to 1 wt .- % organic compound of a metal of group 2a of the periodic table. 4. Claim according to one of the items 1 to 3 g characterized in that the polymerisate 3? - 2 mass, based on the weight of the polymer 0.005 to 1 wt. 56 and in particular 0.01 to 0.6 wt. 5. Claim according to one of the items 1 to ^ +, characterized in that the polymer compositions, based on the weight of the polymer 0.005 to 5 wt .- $ 6 and in particular 0.05 to 1.5 wt. -96 Thioglykolsäureester included.
10 6 _e claim according to one of the items 1 to 5 »ge kennzei chnet characterized in that the polymer compositions, based on the weight of the polymer 5 to 120 parts by weight of plasticizer. 7 «stabilizer combination for the preparation of the heat-stabilized molding compositions based on vinyl chloride according to one of the items 1 to 6, characterized in that they a) at least one organic zinc compound, b) at least one organic compound of a metal of group 2a of the periodic table, c) at least one polyol, d) contain at least one ester of thioglycolic acid. 8. Claim according to item 7 », characterized in that the thioglycolic ester d) corresponds to the general formula I in which: η is the integer 1, 2, 3 or 4 _s R represents a monovalent or polyvalent group which can be: 2 2 2 17 3 a linear or branched aliphatic group which is saturated or has one or more ethylenic double bonds and which may have one or more - 0 -, - S - in the chain,
5 a cycloaliphatic group which optionally carries one or more alkyl or alkoxy substituents and which optionally has one or more ethylenic double bonds,
, an aryl group or an aryl-aliphatic group whose ring moiety optionally bears one or more alkyl or alkoxy substituents and which may be bonded to the aliphatic moiety via an oxygen atom, a trisalkylene isocyanurate group, 12 1 a group -R-COO - R - when η = 2, where R and R are linear or branched aliphatic groups, the 20 are saturated or contain one or more ethylenically unsaturated double bonds, and a chain of several of the above groups. 9. Claim according to item 7 or 8, characterized in that the organic zinc compound a) is selected from the group of carboxylic acid salts, the derivatives of phenolic compounds, the mercaptides and the 30 chelates of β-dicarbonyl compounds, that b) the organic compound of a metal of group 2a of the periodic table is a calcium, magnesium, barium or strontium compound from the group of the carboxylic acid salts, derivatives of phenol compounds, 9 9 O 1 7 Mercaptides and chelates of ß-dicarbonyl compounds and that d) the thioglycolic acid ester of the general formula I corresponds, in the η is the integer 1,2 or 3 and if η = 1, R has one of the following meanings: a linear or branched alkyl or alkenyl group having 6 to 36 carbon atoms, a phenyl group or phenylalkyl group or cyclohexyl group, or cyclohexylalkyl group, the ring member of which is optionally substituted with one or more lower alkyl groups or lower alkoxy groups and their optionally present aliphatic portion contains 1 to 6 carbon atoms and may be bonded to the ring portion via an oxygen atom O, and a chain of several of the above groups; when η = 2, R represents a linear or branched alkylene group having 2 to 24 carbon atoms, a cyclohexylene group or a cyclohexylenealkyl or cyclohexylenedialkyl group, the ring portion of which is optionally substituted with one or more lower alkyl groups or lower alkoxy groups and whose given aliphatic portion comprises from 1 to 6 carbon atoms and bonded to the ring via an oxygen atom can a phenylene group or phenylenealkyl or phenylene / 5 - 52- 22 2 173 dialkyl group whose ring is optionally substituted with one or more lower alkyl or lower alkoxy and their optionally present aliphatic part comprises 1 to 6 carbon atoms and bound to the ring via an oxygen atom-O- 1 2 1? can, a group - R - COO - R -, where R and R may be the same or different and for. linear or branched aliphatic groups having 1 to 18 carbon atoms which are saturated or may have one or more ethylenically unsaturated bonds, as well as a concatenation of several of said groups; 15 if η = 3, R stands for a trivalent linear or branched aliphatic group having 3 to 24 carbon atoms, a trisalkylene isocyanurate group whose alkylene groups each have 1 to 4 carbon atoms. 10. Claim according to one of the items 7 to 9, g e characterized in that the thioglycol acid ester of general formula I corresponds, in which η = 2. 11. Claim according to one of the items 7 to 10, characterized in that the organic zinc compound is at least one carboxylic acid salt and / or a phenolate. 12 «Claim according to any one of items 7 to 11, characterized in that the organic 2OO 1 * 7 ^ Z Z a / ο Bond of a metal of group 2a of the Periodic Table is at least one carboxylic acid salt and / or a phenolate. 13e Claim according to one of the items 7 to 12, characterized in that the organic compound of a metal of Group 2a of the Periodic Table is a calcium compound or a Magnesiumver 'bond or a mixture of calcium and magnesium compound. 14 · claim according to one of the points 7 to ^, characterized in that the polyol contains more than four OH groups.
15 Claim according to one of the items 7 to 14, characterized in that the polyol is selected from the group of sorbitol, mannitol and / or xylitol. For this iSsite formulas 7249