DE2546900A1 - LIQUID STABILIZER MIXTURE AND THEREFORE STABILIZED CHLORINE-CONTAINING THERMOPLASTICS - Google Patents

Description

It is known to contain chlorine-containing thermoplastics, for example Polyvinyl chloride to add stabilizers to avoid damage caused by thermal stress and / or to suppress discoloration in the substrate. In general, liquid and solid stabilizers are used applied, liquid stabilizers having the advantages of good incorporation and distribution.

Among the most effective known thermal stabilizers are for example organic metal compounds of magnesium, calcium, strontium, barium, zinc, cadmium, tin, lead and antimony. Mixtures of some of these compounds are also known. The heavy metals barium, cadmium and. lead are relatively toxic and there has therefore been no lack of attempts to use suitable stabilizer mixtures for these metals to replace.

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Thus, 'in Japanese Patent 4840843 becomes a combination of Organotin maleate, calcium, zinc and potassium stearate and magnesium hydroxide are described. This mix is but only available in powder form. Furthermore, at higher temperatures, maleates can cause irritation than R. Form known maleic anhydride, which is problematic from a commercial toxicological point of view.

In American patent 3,644,246 is a mixture of dialkyltin carboxylates and sodium, magnesium, calcium or Aluminum salts of half-esters of unsaturated dicarboxylic acids, for example maleic acid described. In addition to the anhydride formation already mentioned, it is disadvantageous that liquid stabilizers on this basis are not storage-stable when combined with phosphates. '

Organotin mercaptides, which also contain calcium, magnesium or Barium compounds are included in the Japanese U.S. Patent 4,723,442, British Patents 1,229,521 and 1,229,522 and in German Offenlegungsschrift 2,334,833 proposed. However, these combinations are known to be used during processing Lead to odor formation. Another disadvantage is their low light stabilizing effect.

The object of the present invention is to provide a liquid, storage-stable stabilizer that is sulfur-free contains no barium, cadmium and lead, develops little or no volatile irritants during processing and in chlorine-containing thermoplastics an effective protection against degradation in the heat at the same time good light stabilizing effect. .

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The subject of the present invention is a fTOssxge Containing stabilizer mixture

a) Salts of aliphatic saturated and branched monocarboxylic acids, aliphatic unsaturated linear or branched monocarboxylic acids, aliphatically substituted aromatic monocarboxylic acids and / or aliphatically substituted phenols and the cations zinc, calcium and R ^ Sn -, where R is an alkyl group with 1 to 12 carbon atoms or the benzyl radical, wherein the metal concentrations in the stabilizer mixture is 0.1 - 2.0 wt .-% zinc, 0.5 - 4.5 wt .-% tin - 3.0 parts by weight calcium and 1.5 7 _O , and

b) a liquid organic phosphite.

Preference is given to stabilizer mixtures in which the aliphatic monocarboxylic acid is branched on the o-carbon atom and has 6 to 18 carbon atoms. In particular The unsaturated, aliphatic monocarboxylic acid preferably contains 16 to 18 carbon atoms and the saturated, aliphatic monocarboxylic acid 8 to 13 carbon atoms.

The aromatic monocarboxylic acids and also the phenols are preferably with one or two, especially with substituted by an aliphatic group. The aliphatic group is preferably an alkyl group, in the case of the carboxylic acids especially with 1 to 12 carbon atoms, which are in particular branched and in the case of phenols with 8 to 12 carbon atoms. Among the aromatic monocarboxylic acids, preference is given to those which have a phenyl radical as the aromatic The remainder contain, but in particular derivatives of benzoic acid.

The monocarboxylic acids and phenols are known compounds. Examples are:

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1. Branched aliphatic monocarboxylic acids:
Isobutyric acid, ß-pheny! Butyric acid, isovaleric acid, methylethyl acetic acid, trimethyl acetic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, isotridecanoic acid, 2-propylundecanoic acid ₃ isopalmitic acid, isostearic acid, 10-methylstearic acid (manufacturers of branched monocarboxylic or neural acids) Esso).

2. Unsaturated monocarboxylic acids:

Crotonic acid, 2-ethyl-crotonic acid, oleic acid, linoleic acid.

The saturated and unsaturated monocarboxylic acids are preferably short-chain branched, i.e. that the side chains can contain 1-4 carbon atoms.

3. Substituted aromatic monocarboxylic acids:

ρ-methylbenzoic acid, o-ethylbenzoic acid, 3-tert
Butyl-5-methylbenzoic acid, p-tert. Buty! Benzoic acid, isooctylbenzoic acid, tert.-octy! Benzoic acid, p-dodecylbenzoic acid, p-octadecylbenzoic acid,
P- (tert-buty! Phenyl) acetic acid, ß- (3,5-dimethylphenyl) propionic acid. It is particularly preferred
p-tert-butylbenzoic acid.

4. Substituted phenols:

Cresol, 4-ethy! Phenol, p-tert.-butylphenol, thymol, 4-methyl-2- (n-hexyl) phenol, p-isooctylphenol, nonylphenol, Dodecylphenol, methyldecylphenol, didodecylphenol, p-tert-octylphenol.

Mixtures of the saturated, unsaturated

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saturated or aromatic motio carboxylic acids and / or Phenols may be contained in the stabilizer mixture.

The alkyl radicals of the R ^ Sn groups preferably contain 1 up to 8, in particular 1 to 4 carbon atoms and further R in this group is preferably a benzyl radical. The metal concentrations in the stabilizer mixture are in particular 0.1 to 1.2% by weight zinc, 0.5 to 2.5 wt% Ca and 2.0 to 4.0 "wt% tin.

Of the liquid phosphates that act as light stabilizers and solvents are used, the alkylary! phosphites are preferred, especially alkylphenylphosphites, dialkylphenylphosphites, in particular those with 8 to 14 carbon atoms in the alkyl group are particularly valuable, The phosphite is generally present in amounts of 10 to 60, in particular 15 to 40% by weight on the overall mix. The phenyl can preferably have 1 to 2 alkyl radicals having 1 to 22, in particular 1 to 18, carbon atoms be substituted.

Examples include: Trilaurylphosph.it, Trioctadecylphosphit, Diphenylhexyl phosphite, diphenyl dodecyl phosphite, Diphenyl tetradecyl phosphite, dioctyl phenyl phosphite, didecyl phenyl phosphite, didodecyl phenyl phosphite, Dinonylphenyltetradecyl phosphite, ditetradecylphenyl phosphite, Tri (nonylphenyl) phosphite, isooctyldiphenylpho sphit.

The stabilizer mixture according to the invention can be preferred in addition to the liquid phosphite contain another solvent. Preferred solvents are Glycol ethers such as from Aetnylglykol, Diethylen-

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glycol, propyl glycol, bxityl glycol, or such as butylene glycol monomethyl ether and in particular aromatic solvents such as benzene, tolxiol, xylene, ethyl benzene or isopropyl benzene. Generally up to 30, in particular 5 to 30% by weight, based on the total mixture Solvents are added.

The stabilizer mixture according to the invention can also be used also contain antioxidants, also in addition to a solvent. Preference is given to sterically hindered alkylphenols, especially those whose alkyl groups are used for Hydroxy group are adjacent.

For economic reasons it is easy to manufacture
and cheap 3,5-di-tert-butyl-4-hydroxytoluene (BHT) are particularly preferred. The stabilizer mixture can
in this case up to 20, preferably 2 to 10% by weight, antioxidants are added.

Examples of phenolic antioxidants are:

1.1. 2,6-di'alkylphenols , such as ζ .B.

2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-dioctadecyl-4-methylphenol.

1.2. Derivatives of alkylated hydroquinones , such as 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-di-tert-butyl-hydroquinone, 2,5- Di-tert-butyl-4-hydroxy-anisole, 3,5-di-tert-butyl-4-

• hydroxy anisole, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, 3,5-di-tert-butyl-4-hydroxyphenyl-

• stearate, bis- (3,5-di ~ tert-butyl-4-hydroxyphenyl) - · adipate.

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1.3. Alkylidene bisphenols, such as

2,2 '-Methylenbis- (6-tert-butyl-4-inethylphenol), 2,2'-methylenebis (6-tert .butyl ~ 4-ethylphenol), 4,4 ^f -Methylenbis- tert 6 (. butyl-2-methy! phenol), 4,4'-methylenebis (2,6 ~ di-tert-butylphenol), 2,6-di- (3-tert-butyl-5 ~ methyl-2-hydroxybenzyl) - 4-methylpheno1, 2,2'-methylenebis [4-methyl-6 - («- methylcyclohexyl) phenol], 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 1- Bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) propane ,. 1,1,3-tris- (5-tert-butyl-4-hydroxy-2-methy! Phenyl) -butane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) - butane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane, ethylene glycol bis- [3,3-bis (3 ^r -tert.butyl-4 '-hydroxyphenyl) butyrate].

! • 4. O- and N-Benzy! Compounds , such as

3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzy1-ether, Tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine.

1.5. Hydroxy be nylated malonic esters, such as

2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonic acid dioctadecyl ester, 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonic acid dioctadecyl ester, 2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid di [4- (1,1,3,3-tetramethylbutyl) -phenyl] ester.

1.6. Hydroxybenzyl aromatics, such as 1,3,5-tri- (3,5-di-tert-butyl ~ 4 ~ hydroxybenzyl) -2,4,6- trimethylbenzene, 1,4-di- (3 , 5-di-tert-butyl-4-hydroxy-

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benzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tri- (3,5-di-1ert.butyl-4-hydro xybenzy 1) -pheno1.

· 7. ^ S ₁ 7 Tr i azinverb in fertilize _r such as

2,4 "bis-octoxy ~ 6- (3,5-di-tert-butyl-4-Ivyxlroxyanilino) · s-triazine, 2 ~ octoxy-4,6 ~ bis- (3,5 ~ di ~ tert-butyl-4-hydroxy-anilino) -s-triazine, 2-octoxy-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenylethyl) -s-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.

· ^ · Amides of β- (3 , 5-di-tert.buty l-4-hydroxyphenyl ) propionic acid , such as

1,3,5 ~ Tris- (3,5-di-tert-butyl-4-hydroxyphei ^ l-propionyl) -hexahydro-s-triazine, N, N'-di- (3,5-di-tert. butyl-4-hydroxyphenyl-propionyl) -hexamethylenediamine.

· ⁹ · Esters of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols such as with

Methanol, ethanol, octadecanol, 1,6-He.xanediol, 1,9-conanediol, ethylene glycol, 1,2-propanediol, di-methylene glycol, Neopentyl glycol, pentaerythritol, trimethylhexanediol, trimethylol'athane, trimethylolpropane, Tris-hydroxya ^^ l-isocyanurate, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyelo [2,2,2] octane.

1.10. Esters of the ß ~ ( 5- tert.b ut yl-4- hydroxy -3-meth

pro pionic acid with mono- or polyhydric alcohols

such as with

Methanol, ethanol, octadecanol, 1,6-hexanediol,

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1,9-nonanediol, ethylene glycol, l, 2 ~ propanediol, di- ■ "ethylene glycol, neopentyl glycol, pentaerythritol, TrimethyLhexanedio1, TrimethyIoIUthan, TrimethyIo1-propane, Trishydroxyethyl isocyanurate, 4-hydroxy-methyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane.

1.11. Esters of 3,5-di-tert-b ^ ltyl · ~ 4-hydroxyphenyl · acetic acid with mono- or polyhydric alcohols, eg with

Methanol, ethanol, octadecanol, 1,6-IIexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, Diethylene glycol, neopentyl glycol, pentaerythritol, ■ trimethylhexanediol, trimethylolethane, trfmethylolpropane, Tris-hydroxyethyl isocyanurate, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] -octane,

1.12. Acylaminophenols _? such as

N- (3,5-di-tert-butyl-4-hydroxyphenyl) -stearic acid amide, N, N ¹ -di (3,5-di-tert-butyl-4-hydroxyphenyl) -bisacetamide.

1.13. Benzyl phosphonates such as

3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3,5-di-tert-butyl-4-hydrocybenzyl-phosphonic acid dioctadecyl ester, 5-tert-butyl ^ -hydroxy-S-methylbenzyl-phosphonic acid dioctadecyl ester.

The inventive stabilizer mixture can by Mixing of the individual components, if necessary with simultaneous heating, can be produced. The individual components can be purchased or manufactured using known processes

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bar. The salts of the monocarboxylic acids and phenols are made for example by converting oxides or hydroxides of the metals zinc and calcium and of dialkyl or dibenzyl tin oxides with the corresponding monocarboxylic acids or phenols in a suitable solvent Obtain removal of the resulting water. For example, by direct reaction of tin with alkyl halides dialkyl or dibenzyltin oxides obtained by hydrolytic work-up or benzyl chloride can still use small amounts of monorganotin oxides (Stannonic acids). Particularly preferred organotin oxides are dimethyl, di-n-btityl, di-n-octyl and Dibenzyl tin oxides.

In a particularly preferred embodiment, the Salts prepared in a solvent, which can also be contained in the stabilizer mixture, wherein then a liquid phosphite and optionally an antioxidant can be dissolved. Be that way the particularly preferred mixtures of the corresponding salts, a phosphite, a solvent and an antioxidant.

The inventive stabilizer mixture is for Suitable for stabilizing chlorine-containing thermoplastics against degradation caused by heat or light.

The present invention therefore also provides a stabilized mixture containing a chlorine-containing thermoplastic polymer and 0.5 to 10% by weight ₉ based on the total mixture, in particular 1-5% by weight, of a stabilizer mixture according to the invention.

Thermoplastics made from or based on vinyl chloride, in particular polyvinyl chloride, are particularly preferred those made by bulk or suspension polymerization. It is further preferred that the chlorine

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containing thermoplastic contains a plasticizer. In particular polyvinyl chloride containing plasticizers is preferred.

Suitable comonomers for vinyl chloride are e.g. ethylene, Propylene, 1,2-butene, vinylidene chloride, acrylonitrile, acrylic acid esters or styrene.

The inventive stabilizer mixture has opposite known to calcium / zinc stabilizers a higher thermostabilizing effect, in particular a better long-term stability. Their relatively low toxicity due to the choice of metals is advantageous and that it does not form volatile and irritant anhydrides during processing, such as for example diorganotin maleic acid half-esters. Besides that the thermostabilizing effect is higher, especially in relation to the initial staff! Iitat, than with the the latter organotin maleates. The light stabilizing effect is very good and better than, for example in the case of the diorganotin mercaptides, which result from the for Tend to develop a mercaptide odor. Another advantage is the high storage stability without this the good effectiveness is lost, which is surprising, since diorganotin maleic acid half-esters are stored with phosphates the thermostabilizing one Effect is diminished.

It is known that calcium / zinc carboxylates in combination with phosphites have a relatively good initial stability but convey too little long-term stability for a longer processing time.

As is generally known, diorganotin carboxylates of monocarboxylic acids are insufficiently stabilized in relation to Initial and long-term stability. Surprisingly, the combination of the two stabilizers according to the invention also leads to improved long-term stability, in addition to the already

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given improvement in initial stability.

The following examples explain the invention in more detail. The percentages given are% by weight and the parts are parts by weight.

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production examples

Example Ά

205.7 g ρ-t-But} '! Benzoic acid, 137.4 g isostearic acid

and 160.0 g of butyl glycol are in a 2-1 three-necked flask heated to 80 °. While stirring, 63.0 g of dibutyltin oxide, 12.4 g of ZnO and 29.4 g of Ca (OH ^ added and implemented at 130 ° with separation of the reaction water. 362.9 g of ditetradecylphenyl phosphite and 50.0 g of 3,5-di-tert-butyl-p-hydroxytoluene are dissolved. the The filtered solution is a clear liquid which is stable in storage. Metal concentration: Ca 1.6% by weight, * Zn 1.0% by weight, Sn 3.0 wt. 7o.

Example B.

By an analogous reaction to Example A of 399.9 g of isostearic acid with 46.9 g of dibutyltin oxide, 9.9 g of ZnO and 24.7 g of Ca (OH) ^ using 150.0 g of butyl glycol, 350.0 g of ditetradecylphenyl phosphite and 50.0 g of 3,5-di-tert-butyl-p-hydroxytoluene, a liquid stabilizer of the following composition is obtained:

16.5% dibutyl tin diisostearate

7.7 % Zn isostearate 20.8 % Ca isostearate 35.0 7o ditetradecylphenyl phosphite

5.0 % 3,5-di-tert-butyl-p-hydroxytoluene 15.0 % butyl glycol

Metal concentration: Ca 1.3% by weight, Zn 0.8% by weight,

. S _n 2.1 wt%.

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' Example C

The components 1 to 10 are according to the following Process mixed and implemented:

(1) 43, Og methyl branched ^ co-monocarboxylic acid

(Trade name Cekanoic 8)

(2) 91.0g benzene acid

(3) 71.4 g of oleic acid

(4) 41.1 grams of butyl glycol

(5) 164.5 g cycloaliphatic hydrocarbon,

Boiling range 180-21O ⁰ C (trade name ESSO Varsol 180/210 E)

(6) 62.9 grams of dibutyl dimoxide

(7) 55.6 g zinc ~ (2 ~ ethylhexoate)

(8) 29.5 grams of calcium hydroxide

(9) 40.0 grams of BHT

(10) 420.0 grams of diphenyl mirystyl phosphite

(1), (2), (3), (4) and 5 are mixed and heated to 80 ° C. Then 6 is added and ^{reacted for 30 minutes at 110 °} C. (reflux condenser, water separator). Then it is added at 80 ^° C. (8), reacted at 120 to 130 ^° C. and the water is removed under a weak vacuum. After mixing with (7) and (9) at 80 ⁰ C is filtered through Gelite.

Calcium content: 1.6% Zinc content: 1.0% Tin content: 3.0%

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Application examples

example 1

The stabilizing effect of the inventive stabilizers produced according to Examples A and B is tested in a long-term fatigue test suitable as a test method for calender processing using a commercially available Ba / Gd / Zn stabilizer with a metal content of about 5.3 % barium, which has proven itself in calender processing. 3.2 "I ₀ cadmium and 0.5% zinc (Irgastab BC 231) compared. For this, 100 g suspension PVC (KW 70) with 50 g dioctyl phthalate (DOP), 0.5 g paraffin wax and 2.0 g stabilizer mixed in a high-speed mixer and the mixture subjected to a thermal test on a laboratory roller mill at 190 ° C. A sample is taken from the rolled sheet formed every 5 minutes, the degree of discoloration of which is determined by determining the yellowness index. The results are shown in Table 1.

Table 1

stabilizer Valzfell , 6 9 5 ¹ 10 ' , 7 15th ' ? 0 ' , 9 25th - 30 ' 35 ' 40 ' 45 ' 50- Ba / Cd / Zn- 5 , 6 11 IH, 0 15th 15, 2 15.2 31.1 Brown stabilizer , 2 3 ,1 , 6 Example A. 2 , 7 11 , 6 5 , 5 5, 9 6th , 9 7, 1 23.9 Brown Example B. S. ,8th 14th 16, 2 15th 15, 8th 16.0 18.4 25.7 »7.5 Brown

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According to Table 1, that produced according to Example A is found Stabilizer With regard to the brightness of the film made from it in the practically important phases superior to the comparative stabilizer in the continuous rolling test, while the stabilizer described in Example B was compared to the comparative stabilizer a slightly higher degree of discoloration causes a significantly higher long-term stability.

Example 2

To test the usability of the stabilizers according to the invention for stabilizing PVC pastes, ground 100 g of PVC suitable for paste processing with an IC value of 68-72 with 65 g of DOP and 2 g of stabilizer to form a paste, and the paste to form a film of the same thickness (0.5 iran) on a flat glass surface and subjected to a heat test in an oven at a constant temperature of 170 °. For this purpose, samples are taken from the oven every 15 minutes and their discoloration is measured (yellowness index). As a comparative stabilizer for the. Paste processing of suitable liquid Ca / Zn rod with approx. 2.6 % calcium and 2.4% zinc used (Irgastab CZ 57). The results are shown in Table 2.

Table 2 15th Min. 30th Min. 45 Min. 60 min. 75 min. stabilizer 3
2 ,8th 5
3 , 2
, 3 94
3 , 2
, 9 Brown
5.4 Brown liquid Ca / Zn
stabilizer
Example A.

Table 2 shows the superiority of the invention Stabilizer recognizable.

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Example 3

In 2 paste-pye types (paste type I with KKi 68-72 and paste type II with KW 70), a comparison of a comparison stabilizer (18.6 % Sn) based on butyltin maleic acid dibutyl ester is also carried out in the heat test according to Example 2 a stabilizer according to the invention prepared according to Example A, ditetradecylphenyl phosphite being replaced by didecylphenyl phosphite. The amount of Dibutylzinnmaleinsäurehalbesters _s was 1% of he invention 2% sgem'as sen stabilizers. The results are shown in Table 3.

Table 3

stabilizer Pastes
type I
Pastes
type II 15 minutes. 30 min. 45 "min. 60 min. 75 min. Dibutyl tin
maleins a "ur e-
dibutyl ester Pastes
type I
Paste
type II 4.7
4.2 9.1
7.9 12.3
13.8 21.6
23.7 30.5
27.8 according to
game 3 3.0
2.8 5.2
3.8 8.8
3.8 14.1
4.0 33.7
12.7

From Table 3 it can be seen that the initial stability, which is important for the production of light-colored finished articles, is achieved easily achieved the types of stabilizers according to the invention can be.

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Example 4

The stabilizers given in Table 4 are at 180 ° C in one. Heat test tested according to Example 1. The recipe consists of 100 parts of PVC (KW 70) and 50 parts of dioctyl phthalate, always 2 parts of stabilizer be admitted. For comparison, the result with a liquid Ba / Cd / Zn stabilizer (Irgastab BC 231) is also given.

Butyl glycol (B) was used as the solvent, dimyristyl phosphite (D) as the phosphite and 3,5-di-tert-butyl-p-4-hydroxytoluene as the antioxidant (BHT) is used. The amounts of these components (in wt.%) Are also in Table 4 (B: D: BHT). The dibutyltin group is included as an organotin group.

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Tabel

3 lot
D. BHT Metal concentrations
(Wt%)
Ca Zn Sn : 33: 8th 1.6 1.0 3.1 Anions
A4 / A26 X X
(1: (Relationship)
AlO A911 A196 X
D. X
D. X • X
1.4: IS IPS Heat test result
(Time in minutes /
Yello ^ Tnes sindex)
Rolling 15 ^! 34 '45' 60 '
fur 9.5 12.1 19.9 liquid Ba / Cd / Zn stabilizer
(Comparative example) : 38: 8th 1.5 1.2 2.8 X
(1.6: 2.2 2.3 3.6 6.6 17th ; 38: 8th 1.5 1.2 2.8 X X
(-1.5: 0.7 9.6 9.3 14.2 20th : 38: 8th 1.0 0.8 2.1 3.1 7.7 8.6 21.1 16 : 38: 8th Λ ⁹ ι, ο 3.0 X
(1.8 X 3.2 9.7 9.6 14.3 16 : 38 *: 5 1.6 0.8 3.0 X
(1: χ ■ 2.4. 4.6 7.4 12.2 14th : 38: 5 1.6 ι, ο 3.0 X
(1: 1.2. 3.4 6.5 14.5 16 : 36: 5 1.6 ι, ο 3.0 0.7 2.6 4.6 9.2 16 : 36 * 5 1.7 1.1 3.1 ■ «·
D. 0.2 7.3 9.2 11.5 16 40 4th 2.0 1.5 Comparison
example X 4.0 2.6 4.6 9.2 18th 36 5 1.6 1.0 3.0 X
• i) 0.2 2.1 5.1 Brown 20th 1.3) 1.0 4.6 6.3 10.9
N 16 X
■ 1.6) 1.5 bra it M. ti ti dd " dd JI dd dd dd

* ■ Diphenylnyris tylpho sphit A47 p-t-butybenzoic acid A26 2-ethylhexanoic acid AlO Shell Versatic 10

A911 Shell Versatic 911

A196 Oleic Acid

IS isostearic acid

IPS isopalmitic acid

CD CD O O

Example 5

In a formulation of 100 parts of polyvinyl chloride (KW 70), 50 parts of dioctyl phthalate and 2 parts of the stabilizer mixtures specified in Table 5, the dependence of the stabilizer action on the organotin group is determined. It is a heat test at 180 ⁰ C made according to Example 1, wherein the yellowness index is determined after 15 Hinuten. The results are shown in Table 5. The amount in% by weight of solvent (B), phosphate (D) and antioxidant (BHT) are also given.

Table 5

lot BHT 1 Metal concentration (Wt. -Ji) ■ ation Organotin Anions IS Heat test 3.0 (Discoloration 45 ' 0 me;. ) D. 5 1 Zn group (Relationship) : 1 3.1 HH 3 B. 35 5 0 Approx 1.0 Sn A47 : 1 2.9 '30' 13th 8th 60 ' 16 36 5 2 , 6 1.0 3.0 (n-octyl) Sn 1.5 : 1 Rolled head 15 3.5 5.5 21 2 brew. 18th 55 * 5 , 6 0.5 3.0 Methyl Sn 1.5 : 1 0.9 4.3 11 Ir ^; 20th 39 ,8th 0.7 1.8 (η-butyl) Pn 3 0.8 6.1 π 20th , 2 3.5 11 3 0.9 6.6 H 0.8

B = butyl glycol D - Ditnyris tylphenylpho sphi t * = Didecylphenyl phosphite BHT = 3,5-di-tert-butyl-4-hydroxytoluene.

609820/1174

Claims (1)

Claims a) Salts of aliphatic saturated and branched monocarboxylic acids, aliphatic unsaturated linear or branched monocarboxylic acids, aliphatically substituted aromatic monocarboxylic acids and / or aliphatically substituted phenols and the cations zinc, calcium and the radical E ^ Sn -, where R is a Alkyl group with 1 to 12 carbon atoms or the benzyl radical, especially the metal concentrations in of the stabilizer mixture are 0.1-2.0% by weight zinc, 0.5-3.0% by weight, -7o calcium and 1.5 ~ 4.5% by weight tin, and b) a liquid organic phosphite. 2. Mixture according to claim 1, characterized in that the aliphatic monocarboxylic acid on the α-carbon atom is branched. 3. Mixture according to claim 1, characterized in that that the aliphatic monocarboxylic acid contains 6 to 18 carbon atoms. 4. Mixture according to claim 1, characterized in that that the unsaturated aliphatic monocarboxylic acid contains 16 to 18 carbon atoms. 5. - Mixture according to claim 1, characterized in that the aliphatic monocarboxylic acid is saturated ■ and contains 8 to 13 carbon atoms. 609820/1174 6. Mixture according to claim 1, characterized in that that the aromatic monocarboxylic acids and phenols are mono- or disubstituted. 7. Mixture according to claim 1, characterized in that that the ai'omatic carboxylic acid with 1 or 2 alkyl groups is substituted. 8. Mixture according to claim 7, characterized in that that the alkyl groups have 1 to 12 carbon atoms contain. 9. Mixture according to claim 8, characterized that the alky! group is branched. 10. Mixture according to claim 9, characterized in that it contains p-tert-butyl ¹ ·! Benzoic acid. 11. Mixture according to claim 1, characterized dadmreh, that the phenol is substituted with 1 or 2 alkyl groups. 12. Mixture according to claim 11 ,. characterized, that the alkyl radical has 8 to 12 carbon atoms contains. 13. Mixture according to claim 1, characterized in that R is an alleyl group with 1 to 8 carbon atoms or the benzyl group. .14.- Mixture according to claim 1, characterized in that that 0.1-1.2% by weight zinc, 0.5-2.5% by weight Ca and 2.0 to 4.0 wt% tin is contained. 603820/1174 15; Mixture according to claim 1, characterized in that that an alkylaryl phosphite is included as component b). 16. Mixture according to claim 15, characterized in that it contains a dialkylphenylpho3ph.it. 17. Mixture according to claim 15, characterized in that the Alley group contains 8 to 14 carbon atoms . 18. Mixture according to claim 17, characterized in that that they are ditetradecylphenylphosphite, didecylphenylphosphite, dimyristylphenylphosphite, myristyldiphenylphosphite or Contains (Dinonylphenyl) isotridecylphosphite. 19. Mixture according to claim 1, characterized in that it also contains a solvent. 20. Mixture according to claim! Or 19, characterized in that that it also contains an antioxidant. 21. A stabilized mixture containing a chlorine-containing thermoplastic polymer and 0.5 to 10 Gev7.-7o of the stabilizer mixture according to claim 1, 19 or 20 based on the total mixture. 22. Stabilized mixture according to claim 21, characterized in that a polymer of or on the Based on vinyl chloride is included. 23. Stabilized mixture according to claim 22, characterized in that the mixture also has a ■ Contains plasticizers. 609820/1174 24. Stabilized mixture according to claim 22, characterized characterized in that the polymer is suspension or bulk polyvinyl chloride. 609820/1174