Patent GB-606716-A (GB)
Title: New polymerisable materials and polymers thereof
IPC: C08F22/10
Filed: 1946-01-02
Abstract: Polymerizable esters of the formula (CH2 = CX.CO.O.R.O.CO.O)2Z (where Z and R are divalent organic radicals and X is hydrogen, halogen, or methyl, and the embodiments of R and X may differ in the groups substituent to Z) (see Group IV (b)) may be polymerized in presence of a polymerization catalyst, and for this purpose they may be mixed with other unsaturated substances which copolymerize or polymerize simultaneously, e.g. di-(allyl glycollyl) succinate, glycol dimethacrylate, methyl or butyl methacrylate, vinyl chloride, vinyl acetate, styrene, maleic anhydride, or polyesters of maleic or fumaric acid and dihydric alcohols.  Dyes, pigments, fillers, reinforcing materials and thermoplastic polymers may also be incorporated when the products are polymerized.  The products may be used to bind fibrous materials by polymerization, as in producing laminated products, or they may be polymerized in casting cells, and for these purposes they may be mixed with polymeric substances, e.g. polymethylmethacrylate.  Examples describe the reaction of methacryloxy ethyl chloroformate in presence of trichlorethylene and ammonia with (1) ethylene glycol, (2) diethylene glycol, and (3) pentane diol.  In further examples, (4) the product of (1) is mixed with butyl methacrylate and benzoyl peroxide and used to bind sheets of canvas; (6) the product of (2) is mixed with benzoyl peroxide and polymerized in a glass cell; (7) the product of example (3) is mixed with benzoyl peroxide and used to bind sheets of kraft paper.ALSO:Polymerizable esters of the formula (CH2 = CX.CO.O.R.O.CO.O)2Z (where Z and R are divalent organic radicals and X is hydrogen, halogen, or methyl, and the embodiments of R and X may differ in the groups substituent to Z) are made by reacting a dihydric alcohol with one or more chloroformates of half esters of dihydric alcohols and acrylic, methacrylic, or alpha-haloacrylic acid.  The half-esters referred to are prepared from the acrylic acid or its chloride, anhydride or ester, and a dihydric alcohol, or from a salt and a chlorhydrin, in presence of a polymerisation inhibitor such as hydroquinone disulphonic acid (see Specification 606,685); an equimolecular proportion of acrylic acid or derivative is added portion-wise when the ester is prepared from a dihydric alcohol, the water being removed as formed by azeotropic distillation using, e.g., benzene or trichlorethylene.  The chloroformates are made from these half-esters by reaction with phosgene.  The final reaction is carried out in presence of a liquid or gaseous base, e.g., ammonia or pyridine, at room temperature; a polymerization inhibitor may be present.  The use of a solid base, e.g. sodium carbonate or lime, makes necessary higher temperatures.  Solvent is removed by distillation under reduced pressure, and the reaction is preferably carried out in glass or enamel-lined vessels.  The products may be polymerized in presence of a polymerization catalyst, and for this purpose they may be mixed with other unsaturated substances which co-polymerize or polymerize simultaneously, e.g. di-(allyl glycollyl)succinate, glycol dimethacrylate, methyl or butyl methacrylate, vinyl chloride, vinyl acetate, styrene, maleic anhydride, or polyesters of maleic or fumaric acid and dihydric alcohols.  Dyes, pigments, fillers, reinforcing materials and thermoplastic polymers may also be incorporated when the products are polymerized.  The products may be used to bind fibrous materials by polymerization, as in producing laminated products, or they may be polymerised in casting cells, and for these purposes they may be mixed with polymeric substances, e.g. polymethylmethacrylate. Examples describe the reaction of methacryloxy ethyl chloroformate in presence of trichlorethylene and ammonia with (1) ethylene glycol, (2) diethylene glycol, and (3) pentane diol.  In further examples: (4) the product of (1) is mixed with benzoyl peroxide and butyl methacrylate and used to bind sheets of glass fibre cloth; (5) the product of (1) is mixed with butyl methacrylate and benzoyl peroxide and used to bind sheets of canvas; (6) the product of (2) is mixed with benzoyl peroxide and polymerized in a glass cell; (7) the product of example (3) is mixed with benzoyl peroxide and used to bind sheets of kraft paper.