DE1494998B2 - STABILIZATION OF CHLORINE-CONTAINING VINYL POLYMERISATES - Google Patents

Description

Lead salts of C ₆ - to C ₂ 2 -carboxylic acids with at least one quaternary carbon atom and

B. cadmium, barium, strontium, calcium or

Zinc salts of C ₆ - to C ₂₂ -carboxylic acids with

at least one quaternary carbon atom such as A

for stabilizing chlorine-containing vinyl polymers found. Used in suspension polyvinyl chloride, these result in stabilizer combinations complete transparency, which is retained even after long thermal treatment. Such results were not to be expected, since pure calcium soaps are known to be used alone as stabilizers a very poor thermal stability, pure zinc soaps a blackening after a short thermal load, pure cadmium soaps have a good initial color, but no long-term stabilization and pure Barium soaps cause the polymeric material to have a poor initial color. But if you use smaller amounts of liquid cadmium, barium, strontium, calcium or zinc soaps together with the Liquid lead soaps according to the invention as stabilizers, a polymeric one is obtained in all cases Material with complete transparency, good initial color and good permanent heat stability, what with none of the stabilization components mentioned last can be achieved alone. As acids for manufacturing pasty cadmium, barium, strontium, calcium and soluble in organic solvents Zinc soaps are also carboxylic acids with one or more quaternary carbon atoms, unsaturated Carboxylic acids, such as oleic acid, cycloaliphatic carboxylic acids, such as naphthenic acid, branched aliphatic carboxylic acids without a quaternary carbon atom, such as 2-ethylhexanoic acid or alkylphenols, suitable.

In general, additions of stabilizers from 0.1 to 10.0, preferably from 0.2 to 5.0 percent by weight, based on the halogen-containing polymer.

In particular, pasty-liquid preparations in which the lead soap content is used are used as stabilizers at least 40, but preferably more than 50 percent by weight, based on the total soap content, matters.

Compared to the usual lead abattoirs the stabilizers according to the invention also offer further advantages:

No tendency to form deposits on calenders, cooling and embossing rollers, spray heads, Nozzles or calibration devices.

Better light stabilization than with most of the conventional lead stabilizers.

No change in the theological properties in plastisols.

No increase in electrical conductivity in electrical insulation compounds. In contrast to lead soaps, which are produced by double conversion and contain residues of inorganic electrolytes the stabilizers according to the invention are electrolyte-free.

The synergetic effect between the lead soaps based on carboxylic acids having quaternary carbon atoms on the one hand and soluble in organic solvents, cadmium, barium, strontium, calcium and zinc soaps other hand, gives the polyvinyl halides good initial color and E>! Tzestabilität V ^uer ^ and perfect , permanent transparency. This result can be derived from the properties ^nscna f ^th not of the individual components erwarten-. The stabilizers of the invention may be liquid, ^"3 epoxy compounds and esters of phosphorous acid are added and other conventional additives known per se.

example 1

ίο 158 g of 2,2-diliethylheptanoic acid (1 mol), 50 g of hexylene glycol and 50 g of mineral spirits are placed in a closed vessel with a stirrer, reflux condenser and water separator heated to about 80 ° C and mixed with 111.6 g Jjleiglatte (0.5 mol). It will

continue to heat up and stir until the black lead is praised ^{nat UQ} d 9 ml of water have separated. It is cooled ft ^{about 11} * 60 ° C and filtered to remove slight Verurifeinigunge. ¹¹ The Reakti # ^ns P ^r ° kt d ^u i ^st a light yellow solution of lead-2 2-dif ^{n m} & ethylheptanat a theoretical Bleigehalt'von ¹ 28.7%; found: 28.5%.

Example 2

186 g of 2-methyl-2-propylheptanoic acid (1 mol) are treated with 50 g of HexyteQgtyk ⁰¹ » ⁵⁰ E white spirit and 111.6 g of black lead (0.5 M ⁰ D ^w * ^e ™ Example 1).

The Reak'titfflsprodukt is a light yellow solution of lead 2-me # ^i-2-yl propylheptanat with a theoretical BleigSeh ^ t ^{of 26>} 6%; found: 26.3%.

Example 3

186 g 2-yl METK ⁱ "2-pr ° pylheptansäure (1 mol) are treated with 50 g of hexyl ^ nglykol, ⁵⁰ grams of mineral spirits and 64.2 g of cadmium Φ £ mol) as in Example. 1 The ^{Reakti6> Ils} P ^{r0 (} iukt is a pale yellow solution of Cadmiurri ^ -methyl ^ -propylheptanate with a theoretical (jadmium content of 16.4%; found: 16.3%.

Example 4

186 g of 2-methyl- ² -P ^ro Py ^me p ^{tansä ure} (1 mol), 50 g of hexylene glycol ^ ^{n <} ^ 50 g of mineral spirits are in a closed 'vessel with water separator, reflux condenser and! Stirrer heated to about 80 ° C and washed successively ^ 7.4 g of hydrated lime (0.1 mole) and 89.3 g of litharge (0.4 mol) was added. It is heated up until sicf? ^{1 have dissolved} the black lead and the white lime hydrate ι ^ ^{η (} 1 10.8 ml of water are deposited.

Minor? Impurities are removed by filtration. The reaction product is a light yellow solution of lead and calcium soaps of 2-methyl-2-propylphenic ^acid in the molar ratio used.

Theoretical ** lead content: 22.3%; found 22.0%.

Theoretical content of calcium: 1.07%; found: 0.9% ..

Example 5

72 g of 2,2-Dim * ^etn yl-3,3-dimethylbutanoic acid (0.5 mole), 86 g of 2-methyl ^ - ² -P ^r ° py ^ln ex ^a acid tert. (0.5 mole), 75 g of benzyl alcohol ^and 75 g of mineral spirits are heated to around 80 ° C e? ^rwarm t and then one after the other with 31.5 g of barium ⁸ hydrate (0.1 mol) and 89.3 g of lead

smoothing (0.4 MOPO added. About be deposited with stirring 25.2 ΐ && water provided with a reflux condenser, ¹¹ a water separator. After cooling to 60 ⁰ ^ C is of minor contamination

filtered off. The reaction product is a light yellow solution with a theoretical lead content of 20.5% (found: "20.2%)" and one theoretical barium content of 3.4% "!; (found: 3.3%)

Example 6

55 g of oleic acid are placed in a closed flask equipped with a stirrer, reflux condenser and water separator a saponification number of 204 (0.2 mol), 107 g of naphthenic acid a saponification number of 158 (0.3 mol), 93 g of 2-methyl-2-propylheptanoic acid (0.5 mol), 40 g of hexylene glycol and 120 g of mineral spirits to about 80 ° C heated and treated with 157.5 g of barium 8 hydrate (0.5 mol). It is further heated up to 90 ml of water are deposited. The temperature is increased to 140 ° C. towards the end of the reaction. After cooling down 30 g of ethylene glycol monoethyl ether are stirred in to 120 ° C. Last will be minor impurities removed by filtration. The reaction product, a brown, viscous solution of the mixed barium soaps of the carboxylic acids used, has a theoretical barium content of 13.3%; Findings: 13.0%.

With the inventively produced Ve,
• fertilizers were used to test the stabilizing effect.
Heat tests with a mixture of

. 100 parts by weight of polyvinyl chloride
. 45 parts by weight of diisooctyl phthalate
-. 0.3 parts by weight of whale rat

and changing parts by weight of stabilizer

ίο carried out. These mixtures were at 175 ° C Rolled into foils for 5 minutes, samples of which in a circulating drying cabinet of one temperature of 180 ° C and continuously observed. The stabilization was made by tracking the temporal Increased color intensification of the samples examined. The stabilization time was in each case recorded the time after which the first discoloration of the sample is noticeable from the time it was placed in the Drying cabinet counted. A stabilization time of 0 minutes accordingly means that the film discolored during the rolling process.

The following overview shows some stabilization values specific to the stabilizers according to the invention :

Suspension polyvinyl chloride K value

I Π. I.

III

Emulsion polyvinyl chloride
K value 70

IV I V

Parts by weight based on 100 parts of PVC

Monobasic lead stearate ...
Barium soap

according to example 6

Cadmium soap

according to example 3

Lead soap according to Example 2

Lead / calcium soap

according to example 4

- 0.2 - - ^: - - - 1.0 - 1.0 0.2 1.8 1.8 0.2 1.8 0.2
1.8 2.0 - - 1.0 1.0 - - - - - - - 2.0 ■ - - - -

Stabilization time (minutes) 35 I 5 I 50 I 15 I 5 I 55 IV 1 48 I 0 I 30 I 50 I 15 I 45

1.8

A synergy exists when the joint use of several products has a better effect results than can be expected additively from the effect of the individual components. The synergetic improvement can be recorded as a percentage. In Experiment II, for example, the stabilization with 0.2% results in Cadmium soap according to Example 3 a stabilization time of 15 minutes and the stabilization with 1.8% Lead soap according to Example 2 has a stabilization time of 5 minutes. Additive is calculated from this theoretical stabilization time of 20 minutes for the combined use of 0.2% cadmium soap and 1.8% lead soap. The actual stabilization time is 55 minutes, which is an improvement by 35 minutes or 175%. Example V shows the superiority of lead soaps based on carboxylic acids with quaternary carbon atoms compared to the conventional one Lead stearate in emulsion polyvinyl chloride. While the one stabilized with 1.8% monobasic lead stearate, The lead soap according to the invention stabilizes the cloudy film already after 15 minutes the material about three times the time with perfect transparency.

Claims (2)

1 2 claims claimed a special combination of lead soaps of carboxylic acids with at least one qua- 1. Use of a stabilizer combination of ternary carbon atoms with, on the other hand, cadmium, ._...., _,. _ _, ... Barium, strontium, calcium or zinc soaps, especially A. Lead salts from C ₆ - to carboxylic acids with _{5 special acids of light kind can the doctrine} at least one quaternary carbon _d i _it, he will, however, not taken patent atom and today, in addition to organotin compounds, B. cadmium, barium, strontium, calcium _{d esters of phosphorous acidj epoxide} . or zinc salts of C ₆ - to ^ carboxylic acid compounds, organic nitrogenous bases, with at least one quaternary carbon- _{10 again soaps of cadmiumS7} barium, strontium, stottatom such as calcium, zinc, lithium and sodium and especially to stabilize chlorine-containing vinyl poly- special lead compounds as stabilizers, merizaten. . But the possible uses of these lead compounds 2. Embodiment according to claim 1, characterized in that fertilize by the fact that the that a stabilizer combination 15 conventional lead stabilizers are powdery, he uses in which the lead salt is at least significantly restricted. The toxicity of lead compounds-40 Percentage by weight of the total stabilizer fertilizer comes from the dusting of the powdery combination matters. Materials especially to the effect. Furthermore tarnish or pigment the polymeric material ao more or less strong; lead stabilizers can therefore be used for transparent or crystal-clear objects not yet used. Your effectiveness in The invention relates to the use of various polymers, e.g. B. Emulsionspolyeiner stabilizer combination on the one hand lead salts vinyl chloride, is only moderate; emulsion polyvinylchloride quaternary carbon atom treated with conventional lead from C ₆ to C ₂₂ carboxylic acids with at least one stabilizer and on the other hand cad tends to yellow even after a short thermal treatment mium, barium, strontium, calcium or zinc. Attempts have therefore been made to produce lead stabilizer salts of C ₆ to C ₂₂ carboxylic acids with at least catalysts which enable the processing of the one quaternary carbon atom to stabilize halogen-containing polymers, in particular chlorine hydrogenation of chlorine-containing vinyl polymers. 30 term vinyl polymers, for transparent and glass Under the influence of heat and light, clear material suffers and which in all polyhalogenous materials Polymers, in particular chlorhalerizates of this type, ie z. B. also in emulsion dough Polymers such as polyvinyl chloride, polyvinylidene polyvinyl chloride, are fully effective. Chloride if possible and the like, decomposition, which is mostly due to the risk of lead poisoning, Discoloration and deterioration of the mechanical 35 which the conventional powdery lead niches Properties of the polymeric material stabilizers particularly adhered, are switched off, make noticeable. In particular, it was found that, surprisingly, for processing necessary high temperatures up to over 200 ° C, sun - the disadvantages of the known processes simply Irradiation and the effects of the weather can be avoided by using lead soaps Stabilization of the chlorine-containing polymers of preferably branched carboxylic acids with inferior. . at least one quaternary carbon atom in the From the German patent specification 850 228, the halogen-containing polymer or shows that the stabilization of chlorine-containing polymer masses consisting of them are incorporated. Such sate using the then common carboxylic acids with quaternary carbon atoms Lead, zinc or cadmium salts are ultimately unsatisfied- 45 result in pasty, organic solvents. was gend. borrowed lead soaps, which compared to the previously known Contrary to this view, types would now have superior properties. Without found that lead soaps still use other stabilizers marked stabilization can be achieved if lead soaps are also fully Lead soaps of a very specific type, namely such 50 resulting, permanent transparency result and of carboxylic acids with at least one quaternary tend to at most after long heat treatment Carbon atom with cadmium, barium, Stron yellowing. When used in suspension tium, calcium or zinc soaps can be combined. polyvinyl chloride is obtained after "processing The subject of the invention is therefore a special corresponding completely transparent product, Combination, whereby additional advantages can then be achieved, some of which can only be treated with subsequent heat treatment when the lead soaps slowly become cloudy in liquid form. This superiority is be followed. both in the plasticizer-free and in the In the German patent specification 850 228, plasticizer-containing processing of polyvinyl after the unsatisfactory stabilizing effect given halides. the then known zinc and lead soaps in detail 60 It was also surprisingly found that is discussed, recommended instead of such soaps a particularly favorable stabilizing effect in the sense the alkaline earth metal salts alpha- and beta-substituted a long-term stabilization is achieved when of aliphatic carboxylic acids, such as trimethyl acetic acid, in addition to the liquid lead soaps based to use the one quaternary carbon atom of carboxylic acids with quaternary carbon atom contains. In such a case, 65 liquid cadmium, barium, strontium, calcium the usual zinc or zinc soaps, which are unsatisfactory as stabilizers, the halogen-containing polymers and lead salts can be used. can be added. So it became the use According to the present invention, a stabilizer combination is made from