DE695756C - Process for the production of copolymers - Google Patents

Description

Process for the preparation of mixed polymers It is known that dienes combine with substances with an activated double or triple carbon bond to form cyclic unsaturated compounds. For example, the tetrahydroplithalic acid anhydride is obtained from butadiene and 1 @ Ialeinic anhydride according to the following formula: The addition products obtained in this way cannot be polymerized by the customary polymerization processes.

It has now been found that the addition products of dienes common to compounds with activated double or triple carbon bond can polymerize with polymerizable compounds. Addition compounds of the type mentioned are, for example, those of butadiene and its substitution products, such as isoprene, dimethylbutadiene, l-chlorobutadiene, also cyclopentadiene and -hexadiene on maleic anhydride, maleic acid ester, maleic acid imide, vinyl l compounds with a carbonyl group adjacent to the vinyl group, such as acrolein, Vinyl methyl ketone, also crotonaldehyde, cinnamaldehyde, cinnamic acid ester, acrylic acid or methacrylic acid and its derivatives, also vinyl esters, vinyl chloride, vinyl ether, N-vinyl compounds, such as N-vinyl carbazole, N-vinyl pyrrole, acetylenedicarboxylic acid ester, Mono- and divinylacetvlen.

As polymerizable compounds used for interpolymerization with the said addition products are suitable, let = n styrene, acrylic and methacrylic compounds, in particular their esters, vinyl esters. Vinyl chloride, vinyl ether, N-vinyl carbazole, Butadiene and chlorobutarlien mentioned.

The copolymerization of the addition compounds mentioned with the polymerizable compounds can be prepared by any of the known polymerization processes, z. B. by heating, if necessary in the presence of rolvmerisationsbeschletinigern, such as benzene peroxide, acetylperoxy d, hydrogen peroxide or acidic inorganic Halides, e.g. B. boron fluoride. It is often useful to carry out the polymerization in aqueous emulsion with the addition of dispersing substances, for example allcylated naphthalene; see below: foanoic acids, sulfuric acid esters of higher fatty alcohols, Addition products of several molecules of ethylene oxide with hydroxyl or amino groups containing, long-chain organic compounds, also of taurides of higher fatty acids or sulfated fatty acid amides to perform. In some cases it turns out to be expedient by: post-treatment with basic substances, such as diluted caustic alkali or Saäa1äsngen to stabilize the polymers.

The copolymers obtained depend on the used Starting materials are soft, rubber-like to hard masses. The harder polymers can be drawn out into films in the manner customary in the celluloid industry or extrusion into tubes, rods or other shaped bodies.

The soft copolymers can be processed in a similar way to rubber. EXAMPLE i An emulsion of zoo parts of Stvrol and 50 parts of tetrahydrophthalic acid ether in 75o parts of water containing 10 to 12 parts of sodium oleate in solution is mixed with 2 to 5 parts of a mixture of hydrogen oxide and potassium persulfate and at the same pH as the hydrogen ion concentration 3.5 stirred for 24 hours at 45 to 50. The dispersion of the copolymer obtained in this way is freed from monomeric components by treatment with steam. The copolymer formed in an almost quantitative yield is precipitated by adding saline solution. It is washed free of electrolytes with methanol. Treated 4o to 450 and dried in vacuo. It is a white powder and contains about 18.5 % of ethyl tetrahydrophthalate as polymerized units.

In the same way, parts of styrene and parts of methylcyclohexenecarboxylic acid ethyl ester are obtained from zoo parts a copolymer in almost quantitative yield. It will coagulate the Polymer dispersion obtained as a pale powder.

Example 2 An emulsion of Zoo parts methyl acrylate and 5o parts of ethyl tetrahydrophthalate in 75o parts of water, the 10 to 12 parts a-Oxyoctodecansulfonsaures sodium contains dissolved, is described in Example i, polymerized and the polymer dispersion obtained worked up accordingly. A light-colored, tough, rubber-like polymer is obtained in good yield.

In the same way, methyl acrylate is obtained from zoo parts and So parts of methylcyclohexenecarboxylic acid ethyl ester form a light, rubbery mass. Example 3 An emulsion of 100 parts of vinyl chloride and 25 parts of ethyl tetrahydrophthalate in 40o parts of water containing 6 parts of 7-oxyoctodecanesulfonic acid dissolved in sodium, becomes after the addition of o, 6 to i part of potassium persulfate and hydrogen peroxide in one pH equivalent to 3.5 in a pressure vessel with thorough mixing for 24 hours polymerized at 5o0. The resulting polymer dispersion is treated with aluminum sulfate solution offset. The resulting polymer is at 6o to 8o0 with about 0.5o / oiger Treated sodium hydroxide solution, centrifuged, washed neutral with water, then washed with methanol and dried. The dried material contains so, 4 per cent C1, corresponding to 88 ° / o @T inyl chloride. The copolymer obtained is a light-colored, granular powder that can be pressed into colorless moldings when heated.

In the same way, a mixed polymer with a chlorine content of 40.1 909, corresponding to 70.5% vinyl chloride, is obtained from 250 parts of ethyl tetrahydrophthalate and 250 parts of vinyl chloride. Example 4 An emulsion of zoo parts of ethyl methacrylate and 50 parts of ethyl tetrahydroplithalate in 750 parts of water containing 10 to 12 parts of sodium a-oxvoctodecanesulfonate in solution is polymerized as described in Example i. The copolymer obtained is a light-colored, granular powder which can be pressed in the heat to give colorless moldings.

In the same way, ethyl methacrylate is obtained from 200 parts and 5o parts of methylcyclohexenecarboxylic acid ethyl ester, a light-colored, granular copolymer.

Example 5 A mixture of 50 parts of styrene with 20 parts of ethyl tetrahydrophthalate and 0.5 parts of benzoyl peroxide are slowly heated to 150 to 160 °. Within It is polymerized to a crystal-clear solid mass for 2 hours.

In the same way, from 50 parts of styrene and 2o parts of methylcyclohexenecarboxylic acid ethyl ester, a solid, crystal-clear mixed poly is obtained. EXAMPLE 6 Some parts of ethyl acrylate are mixed with 20 parts of ethyl tetrahydrophthalate and, after addition of 0.5 part of benzoyl peroxide, polymerized at from 120 to 140 ° within 2 hours. A soft, tough and colorless copolymer is obtained. In the same way, 50 parts of ethyl acrylate and 20 parts of methylcyclohexenecarboxylic acid ethyl ester give a soft, tough, colorless copolymer. EXAMPLE 7 112 parts of 2-chlorobutadiene and 38 parts of tetrahydrophthalic acid diethyl ester are dissolved in 150 parts of a 4% aqueous solution of a condensation product of 1Io1 β # β'-dichlorodiethyl ether and 2 mol of an amine mixture obtained from fatty acid mixtures obtained by paraffin oxidation the nitrile was prepared, emulsified and, after the addition of 2 parts of 30% hydrogen peroxide and 0.1 part of potassium persulfate, polymerized at 40 ° with thorough stirring. After a polymerization time of 24 hours, the polymer dispersion obtained is admixed with methanol, the resulting copolymer precipitating in flaky form. These flakes are washed, dried and rolled. This gives you a firm coat. The copolymer obtained can be vulcanized in a customary manner.

Claims (1)

PATENT CLAIM: Process for the production of copolymers, characterized in that the addition products of dienes to compounds having a double or triple carbon bond activated by substituents polymerized together with polymerizable-ii monomeric compounds.