Patent GB-1311315-A (GB)
Title: Heat-hardenable self-supporting films
Inventor: FOCK J
IPC: B32B21/06
Filed: 1970-12-04
Abstract: 1311315 Heat-hardenable, self-supporting polymer films TH GOLDSCHMIDT AG 4 Dec 1970 [8 Dec 1969] 57846/70 Heading C3P A heat-hardenable, self-supporting film consists of (A) an elastomeric copolymer obtained by polymerization of (a) 70 to 99% by weight of a C 1-8  alkyl acrylate, (b) 1 to 20% by weight of an unsaturated monocarboxylic acid and/or of an unsaturated dicarboxylic acid anhydride, (c) 0 to 20% by weight of a vinyl monomer which is capable upon homopolymerization of producing a hard-brittle polymer and (d) 0 to 2% by weight of a cross-linking monomer with at least 2 reactive non-conjugated double bonds in the molecule, and (B) a hard-brittle copolymer obtained by polymerization of (a) 60 to 90% by weight of styrene and/or a C 1-4  alkyl methacrylate, up to 20% by weight of said styrene and/or alkyl methacrylate being replaced by another vinyl monomer capable upon homopolymerization of producing a hard-brittle polymer, (b) 1 to 20% by weight of a glycidyl ester of acrylic or methacrylic acid, (c) 1 to 20% by weight of an unsaturated monocarboxylic acid and/or of an anhydride of an unsaturated dicarboxylic acid and (d) 0 to 3% by weight of vinyl pyridine, the weight ratio of (A) to (B) being from 1 : 20 to 1 : 3. The fibres of the invention may be prepared (a) by polymerizing the monomers for (A) and (B) separately by solution or emulsion polymerization, and in the case of emulsion polymerization, separating the copolymers from the aqueous phase, taking them up in a solvent, and mixing them in the ratio defined above, or in the case of solution polymerization, directly mixing the solutions in the required ratio, and then casting the solution and evaporating the solvent, or (b) by polymerizing the monomers for (A) first by solution or emulsion polymerization, adding the monomers for (B) to the solution or emulsion of (A) and polymerizing the monomers for (B), thereafter proceeding as for (a). The vinyl monomer may be styrene, acrylonitrile or methyl methacrylate, or a mixture of these may be used. The cross-linking monomer may be a diacrylate of a diol, or divinyl benzene, diallyl phthalate or vinyl methacrylate. In Examples 1 to 6 copolymers (A)1, (A)2, (A)3, (B)1, (B)2 and (B)3 are prepared from: (A) 1 methyl acrylate, acrylic acid and butane diol dimethacrylate; (A)2 as (A)1 except that methyl acrylate is replaced by ethyl acrylate; (A)3 as (A) 1 except that methyl acrylate is replaced by butyl acrylate; (B)1 methyl methacrylate, glycidyl methacrylate, acrylic acid and vinylpyridine; (B)2 as (B)1 except that methyl methacrylate is replaced by butyl methacrylate; and (B)3 as (B)1 except that methyl methacrylate is replaced by a mixture of methyl methacrylate, styrene and acrylonitrile. In Example 7 copolymers (A)1 to (B)3 are mixed in pairs (A : B) and cast from methylene chloride solution to form films. In Examples 8, 14 to 16 and 18 to 24 the film is prepared by process (b) above, and the copolymers are obtained by polymerizing; 8(A) methyl acrylate, acrylic acid and butanediol dimethacrylate and (B) methyl methacrylate glycidyl methacrylate, acrylic acid, maleic anhydride and vinylpyridine ; 14(A) methyl acrylate, acrylonitrile, acrylic acid and butanediol dimethacrylate and (B) methyl methacrylate, acrylonitrile, glycidyl acrylate and acrylic acid; 15(A) n-butyl acrylate and acrylic acid and (B) n-butyl methacrylate, glycidyl acrylate and acrylic acid; 16(A) n-butylacrylate and acrylic acid and (B) methyl methacrylate, glycidyl acrylate and acrylic acid; 18(A) ethylacrylate, acrylic acid, acrylonitrile and butanedioldimethacrylate; and (B) ethyl methacrylate, acrylonitrile, glycidyl methacrylate and acrylic acid; 19(A) n-butyl acrylate and acrylic acid and (B) styrene, glycidyl acrylate and maleic anhydride; 20(A) as 19(A) and 20(B) styrene, glycidyl acrylate and acrylic acid; 21(A) methyl acrylate and acrylic acid (0À7 part) and (B) methyl methacrylate, styrene, glycidyl acrylate and maleic anhydride; 22(A) as 15(A), and 22(B) butyl methacrylate, styrene, glycidyl acrylate and maleic anhydride; 23(A) n-butyl acrylate, acrylic acid and ethylene glycol dimethacrylate, and (B) methyl methacrylate, styrene, acrylonitrile, glycidyl methacrylate and acrylic acid; and 24(A) as 23(A), and 24(B) methyl methacrylate, acrylic acid and glycidyl methacrylate. In Examples 9 to 13 copolymer A is obtained from methyl acrylate and acrylic acid and copolymer B is obtained from methyl methacrylate, acrylic acid and glycidyl methacrylate. In comparative Example 17 a copolymer is prepared by polymerizing the monomers used in Example 16 (both A and B) in one stage.