DE1093090B - Process for the production of polymers - Google Patents

Description

Process for the preparation of polymers It has been found that polymers and copolymers with valuable properties are obtained if 6,7-bis-methylene-i, 2,3,4, 10,10-hexachloro-1, 4.5 8- di-endomethylene-1, 4,4 a, 5,6,7,8,8 a-octahydronaphthalene (hereinafter referred to as BHDO for short in the text) of the formula polymerized alone or with other monomeric polymerizable compounds to form homopolymers or copolymers.

Suitable polymerizable compounds with which BHDO co-polymerizes are, for example, vinyl compounds such as styrene, methyl styrene, - Halostyrenes or vinyl naphthalene, also vinyl pyridine, N-vinyl carbazoles, vinyl ketones, such as vinyl methyl ketone, vinyl sulfones, e.g. B. methyl vinyl sulfone or divinyl sulfone, Vinyl esters of saturated and unsaturated mono- or polycarboxylic acids, e.g. B. Vinyl acetate, vinyl propionate or divinyl succinate, N-vinyl lactams, such as N-vinyl pyrrolidone or N-vinyl caprolactam. Also vinyl chloride and vinyl ether from Mono- and polyoxy compounds, e.g. B. Isobutyl vinyl ether or butan-diol-i, 4-divinyl ether, or vinylidene compounds such as vinylidene chloride or vinylidenecyanide are suitable. Α, β-Unsaturated mono- or dicarboxylic acids can also be used as comonomers and their derivatives, such as esters, amides or nitriles, e.g. B. acrylic acid, acrylic acid methyl ester, Acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid amide, N-substituted acrylic acid amides, Acrylic acid nitrile, methacrylic acid, methacrylic acid ethyl ester, methacrylic acid amide, N-substituted methacrylic acid amides, methacrylic acid nitrile, glycol dimethacrylate, a-chloroacrylic acid methyl ester, maleic anhydride or maleic acid diethyl ester, and allyl compounds, e.g. B. allyl esters of saturated or unsaturated mono- or polycarboxylic acids or inorganic acids, such as allyl acetate, allyl acrylate, Diallyl phthalate, diallyl maleate or diallyl phosphate, and allyl ethers of mono- or polyoxy compounds, allyl butyl ether, diallyl ether, glycol diallyl ether, pentaerythritol tetraallyl ether or butadiene and its derivatives, e.g. B. chloroprene, isoprene or dimethylbutadiene.

Particularly valuable products are obtained if, in addition to BHDO, as Copolymerization component unsaturated polyester, preferably in a mixture with other polymerizable compounds, e.g. B. with styrene used. Unsaturated Polyesters are used in a known manner, for. B. by polycondensation a "B-un- more saturated Dicarboxylic acids prepared with preferably dihydric saturated alcohols. Some of the α, β-unsaturated dicarboxylic acids can be replaced by saturated polycarboxylic acids be replaced. Suitable α, ß-unsaturated dicarboxylic acids come, for. B. in question: Maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid or their substitution products, z. B. chloromaleic acid or anhydrides of these acids. The possibly also used Saturated, non-polymerizable polycarboxylic acids can be aliphatic or cycloaliphatic or mixed aliphatic-cycloaliphatic, optionally substituted carboxylic acids be e.g. B.

Succinic acid, fumaric acid, adipic acid, pimelic acid, sebacic acid, Suberic acid, a-methylglutaric acid, oxadibutyric acid, sulfondibutyric acid, phthalic acid, Endomethylene tetrahydrophthalic acid, hexachloroendomethylene tetrahydrophthalic acid, tetrachlorophthalic acid, Tetrabromophthalic acid or phenylenedibutyric acid.

Instead of the free acids, their esters with low molecular weight Alcohols can be used in the manufacture of unsaturated polyesters. By Use of monohydric carboxylic acids or alcohols in the polycondensation the degree of polymerization of the unsaturated polyester and thus the viscosity their solutions in the monomeric compounds are adjusted.

The ratio of the BHDO to the other monomers in the polymerizable Mixtures can be changed in a very wide range and can, for example, between 1: 100 and 100: 1 are.

The polymerization of the BHDO and its interpolymerization with others polymerizable compounds can be done by all common polymerisation processes, such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or precipitation polymerization. The polymerization or copolymerization can be triggered solely by thermal activation. Advantageously accelerated however, the reaction by exposure to radiation, e.g. B. with light, in particular UV light and 'or by adding polymerization catalysts that are capable are to break down into polymerization-triggering radicals. Suitable polymerization catalysts of this type are z. B. Benzoyl peroxide, lauroyl peroxide, tertiary butyl hydroperoxide, Di-tert-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide or azodiisobutyronitrile. In emulsion polymerization, it is advantageous to use water-soluble catalysts, such as hydrogen peroxide or potassium persulfate. The polymerization can also be carried out in the usual way Accelerated by using redox systems or metal redox systems, by combining the above-mentioned per compounds with reducing agents such as benzoin, Sodium formaldehyde sulfoxylate, sugar or optionally with metal compounds, combined.

The polymers and copolymers of the BHDO are valuable Properties. The homopolymer has a high softening point, and in Copolymers, the softening point of the comonomers, z. B. of styrene, strong raised. You can e.g. B. depending on the degree of polymerization and structure both on the Plastics area as well as paint raw materials are used.

Polymerizable mixtures which, in addition to BHDO, are unsaturated polyesters containing a, S-unsaturated dicarboxylic acid esters can, for example, be used as casting resins for the production of moldings, glass fiber laminates, corrugated glasses or components to serve. Due to the high chlorine content, the polymers and copolymers are flame retardant. By incorporating phosphorus-containing substances or antimony trioxide the flame resistance can be increased even further.

The parts mentioned in the examples are parts by weight.

Example 1 A mixture of 25 parts of BHDO and 75 parts of styrene with 0.1 part of azodiisobutyric acid dinitrile and 0.1 part Benzoyl peroxide is 6 hours heated to 45 "C, another 6 hours at 80" C and 2 hours at 100 "C and polymerized. A hard, tough polymer is obtained which has a weak yellow color. with a k value (after Fikentscher: Zellulosechemie, 13, p. 58 [1932]) of 55 and a softening point of 125 "C.

Example 2 98 parts of maleic anhydride, 304 parts of tetrachlorophthalic acid and 167 parts of 1,2-propylene glycol are at 180 "C while passing nitrogen through condenses until the acid number of the resulting polyester has dropped to 35.

60 parts of the unsaturated polyester are mixed with 20 parts of styrene and 20 parts of BHDO mixed homogeneously. A highly viscous polymerizable one is obtained Mixture that prevents premature polymerization with 0.01 0J0 hydroquinone stabilized.

100 parts of the polymerizable mixture are mixed with 4 parts of cyclohexanone peroxide paste (400 / in in dibutyl phthalate) and 0.8 parts cobalt naphthenate solution (10 0zig in styrene) offset and poured into molds. After standing for about 30 minutes at room temperature the mass begins to gel and then hardens through self-heating. Hard and solid moldings are obtained, which are post-tempered at 100 ° C. for 24 hours.

The polymers have a softening point of 102 ° C. They are self-extinguishing, i.e. they do not continue to burn after the pilot flame has been removed.

Also glass fiber reinforced laminates made using the described polymerizable mixture are prepared, are - despite the known very strong wicking effect of the glass fibers - self-extinguishing.

PTETNSPROCHE: 1. Process for the production of polymers and Copolymers, characterized in that 6,7-bis-methylene-1,2,3,4,10,10-hexachloro-1,4,5,8-di-endomethylene-1,4,4a, 5,6 , 7.8.8 α-octahydronaphthalene alone or together with other monomeric polymerizable Polymerizes compounds.

Claims (1)

2. The method according to claim 1, characterized in that as Mischpolymen.sationsverbindungen unsaturated polyester, preferably with other polymerizable compounds are used.