DE1018224B - Process for the production of stable and crystal clear processable polymers and copolymers of chlorine-containing vinyl compounds in aqueous emulsion - Google Patents

Description

GERMAN

It is known that salts of polybasic phosphoric acids, z. B. secondary sodium phosphate, as a buffer in the polymerization of chlorine-containing vinyl compounds, to be used to weaken the effectiveness of the hydrogen chloride released during the reaction. At the same time practice these salts in the finished Polymers have a certain stabilizing effect, especially against exposure to light. During the Light stabilization small amounts of phosphonic acids Salts are sufficient, stabilization against the effects of heat requires considerably higher amounts, which give the products other undesirable properties. They cloud clear films and, increase, the water absorption capacity and the electrical conductivity. As the emulsifiers used for emulsion polymerization Usually used, the buffer must have no buffering effect can also be used, which increases the foreign matter content of the polymer noticeably.

In the production of flexible films, neutral esters, such as tricresylphoisphate, are also esters of the type of dioctyl phthalate known as additives. The emulsifiers commonly used, e.g. B. long chain Sulphonates, show poor solubility in these plasticizers, so the processed products become cloudy milky.

On the one hand, the optimal conditions during the polymerization with regard to buffer capacity and: emulsifying effect to achieve, and on the other hand, the desired properties in relation to the end product Stability against light and heat, manageability, pasteability, glass clarity of the processed product To achieve this, one has to work with various additives, which are inevitable act in the finished polymer as disruptive foreign substances or through special processing of the Dispersion must be eliminated.

It has now been found that stable and crystal-clear processable polymers and copolymers can be obtained of chlorine-containing vinyl compounds in aqueous emulsion, thereby producing, that one. the monomers in the presence of salts of the alkali or Alkaline earth metals with partial esters of polybasic acids of phosphorus, their. Alcohol component at least Contains 8 carbon atoms and in which the ratio the phosphorus to the oxygen atoms is smaller than 1: 4, polymerizes. In the buffering effect in the In the polymerization mixture, the ester salts mentioned act in the same way as the purely inorganic ones Salts of the corresponding phosphoric acids. Your partial esterification with higher alcohols, gives them excellent properties as emulsifiers. At concentrations from 0.2 to 3%, which, however, can optionally be increased to 5 to 10% Process for the production of stable and crystal-clear processable polymers and copolymers of chlorine-containing vinyl compounds in aqueous emulsion

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M., Brüningstr. 45

Dr. Günter Scheffel, Burgkirchen / AIz,
has been named as the inventor

on the weight of the monomers or polymers, they act as excellent stabilizers against that Exposure to light as well as heat. The products made by polymerization in the presence of the ester salts mentioned are obtained, can be processed more easily into pastes than those under Use of sulfonate emulsifiers. won; will. The ester salts take effect during further processing as a lubricant and guarantee with or without the addition of plasticizers, in contrast to the Sulphonates », the processing of crystal clear products.

This is particularly important when working up aqueous dispersions of the polymers without removing the water-soluble components (e.g. spraying :) are important. Surprisingly, it has an effect during the polymerization the relatively low solubility of the ester acids in the aqueous phase is not a disadvantage. By varying the organic. Residues of the ester acids you can influence the degree of polymerization.

In the context of the invention, partial ester salts of pyrophosphoric acid and those of the more highly condensed phosphoric acids, e.g. B. H ₅ P ₃ O ₁₀ and H ₆ P ₄ O ₁₃ , but also those of phosphorous acid etc.

As alcohol components of these esters, the aliphatic alcohols such. B. caprylic,

Lauryl, myristyl, cetyl, stearyl alcohol and; the higher homologues, the series of unsaturated alcohols, e.g. B. oleyl alcohol, also substituted Phenols and alkoxylated products of the alcohols and phenols mentioned. When the alcohols become unsaturated

7 (B, 757/353

no stress whitening occurs in rigid films made with their esters.

Easily available esters are those of the following To name constitutional forms:

R ₁ -O,

-O'

I.

II.

O = P-O-P = O

4. A solution of 15 parts of potassium persulfate in 000 parts of water is mixed with 1800 parts of vinyl acetate and 140 parts of dilauryl disodium pyrophosphate were placed in a stirred autoclave. This is set to 20 Torr evacuated and charged with 8,200 parts of vinyl chloride. The: mixture is heated to 55 ° C and stirred, the polymerization taking place. The work-up is carried out as in Example 2.

The products obtained according to Examples 1 to 4 can, for example, in a ratio of 70:30 'with dicctyl phthalate rolled or without additives to rigid foils. are processed. All of them received Films are water-clear and crystal clear.

R _{1 is} hydrogen or a metal, R _{2 is} a monovalent alkyl, aralkyl, substituted aryl or polyglycol ether radical containing at least 8 carbon atoms, while R ₃ and R ₄ can either correspond to the definition of R ₁ or R _2.

The salts of the partially esterified phosphoric acids mentioned are incorporated into the monomer mixture prior to polymerization. The advantage of the ester salts lies in particular, that the minimum amount used for emulsification, the effectiveness as a buffer and stabilizer includes, so that * the polymer no longer requires any additional foreign substances to achieve the desired Properties too. reach. Another advantage is that, unlike in presence of sulfoinate emulsifiers, for sure Let crystal-clear finished products work out.

Examples

1. A solution of 250 ¹ parts. Ethylhexyl sodium phosphite and 30 parts of potassium persulfite in 20,000 parts of water are placed in a stirred autoclave. This is evacuated to 20 Torr and charged with 10,000 parts of vinyl chloride. The mixture is heated to 45 ° C. and stirred, the polymerization taking place. The work-up is carried out by evaporation.

2. A solution of 270 parts of dicetyl calcium pyrophosphate and 12 parts of potassium persulfate in 18,000 parts of water is placed in a stirred autoclave. This is evacuated to 20 Torr and. charged with 10,000 parts of vinyl chloride. The mixture is 50 ^! ° C heated and stirred, whereby the polymerization takes place. After about 10 ¹ hours, the pressure drops. The work-up is done by spraying.

3. A 50O ¹ part solution. Di- (tetraethylelycol monocetyl ether) disodium pyrophoephate and 10 parts of potassium persulfate in 15,000 parts of water is poured into one. Stirring oven given. This is evacuated to 20 Torr and charged with 10,000 parts of vinyl chloride. The mixture is heated to 60 ° C. and stirred at this temperature, the polymerization taking place. The work-up is carried out as in Example 2.

Claims (4)

PATENT CLAIMS: 1. Process for the production of stable and clear processable polymers and copolymers of chlorine-containing vinyl compounds in an aqueous emulsion, characterized in that that the monomers in the presence of. Salts of the alkali and alkaline earth metals with partial esters polybasic acids of phosphorus, the alcohol component of which has at least 8 carbon atoms contains and in which the ratio of phosphorus to oxygen atoms is less than 1: 4 is polymerized. 2. The method according to claim 1, characterized in that that phosphites or pyrophosphates of the general formulas R ₁ R ₉ - O I. R ₁ R ₂ II. O ι ■ O = P ^ O-P = O O are used., where R _{1 is} hydrogen or a metal, R _{2 is} a monovalent, at least 8 Kohkn, -stoffatame containing alkyl, aralkyl, substituted aryl or polyglycol ether radical and R ₃ and R ₄ either of the definition of R ₁ or of R ₂ correspond. 3. The method according to claim 1, characterized in that salts of partially esterified higher condensed phosphoric acids. Such as H ₅ P ₃ O ₁₀ and H ₆ P ₄ O ₁₃ , are used. 4. The method according to claim 1 to 3, characterized in that the ester salts in amounts of. 0.1 to 10%, preferably from 1 to 3%, calculated on the weight of the monomers or polymers, can be applied. In, considered publications:
German Patent Nos. 873 745, 926 043;
U.S. Patent No. 2689242. © 709 757/353 10.57