Patent GB-630370-A (GB)
Title: The production of polymerisable organic materials
IPC: C08F22/10
Filed: 1946-12-30
Abstract: The polymerization is described of organic materials containing two unconjugated CH2=C groups per molecule, which are prepared by reacting one or more dihydric alcohols, the hydroxyl groups of which are separated by x atoms, under conditions which result in the esterification of their hydroxyl groups, with acrylic, methacrylic and/or an alpha haloacrylic acid and one or more dicarboxylic acids, the carboxyl groups of which are separated by y atoms, x plus y being 3 or more, and/or ester forming derivatives of these acids, e.g. the acid chlorides, anhydrides, or methyl, ethyl, propyl or butyl esters thereof, in proportions such that there are substantially equal numbers of hydroxyl and carboxyl radicals, and/or ester-forming derivatives thereof, present, and between 0.00147 and 0.0147 gram-molecules by weight of acrylic, methacrylic and/or alpha-haloacrylic acid, or ester forming derivative thereof, for every gram of dihydric alcohol plus dicarboxylic acid or equivalent weight of ester forming derivatives thereof.  Dicarboxylic acids specified are maleic, adipic, sebacic, phthalic, terephthalic, and diglycollic, and dihydric alcohols are ethylene, trimethylene, pentamethylene, hexamethylene and diethylene glycols.  In the preparation of the dihydric polyesters, and in their reaction with the acrylic acid or derivative, water or alcohols produced may be removed by azeotropic distillation, using, e.g. benzene or trichlorethylene, and a combined catalyst and polymerization inhibitor such as hydroquinone disulphonic acid (see Specification 606,685, [Group IV (b)],) may be used, together with a stream of air. A polymerization inhibitor such as hydroquinone may be present when solvent is distilled off from the reaction product.  The reactions are 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 copolymerize or polymerize simultaneously, e.g. di-(allyl glycollyl)succinate, glycol dimethacrylate, methyl methacrylate, butyl methacrylate, vinyl chloride, vinyl acetate, or 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 bond fibrous materials by polymerization, e.g. in producing laminated products.  Examples describe the reaction of various proportions within the prescribed limits of (1) ethylene glycol, phthalic anhydride, and methacrylic acid with or without sulphuric acid; (2) diethylene glycol, maleic anhydride, and methacrylic acid; (3) ethylene glycol, methacrylic acid and adipic or sebacic acid; (4) ethylene glycol, methacrylic acid, and maleic anhydride; (5) 1.5 pentane-diol, methacrylic acid, and maleic anhydride; (6) ethylene glycol, phthalic anhydride, and methyl methacrylate or -chloracrylate; trichlorethylene and hydroquinone disulphonic acid are present in all cases, and when methyl methacrylate is used in (6) above, they may be replaced by p-phenylene diamine and benzene. Further examples describe the copolymerization of the product of (1) with butyl methacrylate, using benzoyl peroxide, and also its polymerization alone.  Specification 607,888 also is referred to.ALSO:Polymerizable organic materials containing two unconjugated CH2=C< groups per molecule are prepared by reacting one or more dihydric alcohols, the hydroxyl groups of which are separated by x atoms, under conditions which result in the esterification of their hydroxyl groups, with acrylic, methacrylic and/or an alpha halo-acrylic acid and one or more dicarboxylic acids, the carboxyl groups of which are separated by y atoms, x plus y being 3 or more, and/or ester-forming derivatives of these acids, e.g. the acid chlorides, anhydrides, or methyl, ethyl, propyl or butyl esters thereof, in proportions such that there are substantially equal numbers of hydroxyl and carboxyl radicals, and/or ester-forming derivatives thereof, present, and between 0.00147 and 0.0147 gram-molecules by weight of acrylic, methacrylic and/or alpha-haloacrylic acid, or esterforming derivative thereof, for every gram of dihydric alcohol plus dicarboxylic acid or equivalent weight of ester-forming derivatives thereof. Dicarboxylic acids specified are maleic, adipic, sebacic, phthalic, terephthalic, and diglycollic, and dihydric alcohols are ethylene, trimethylene, pentamethylene, hexamethylene and diethylene glycols.  In the preparation of the dihydric polyesters, and in their reaction with the acrylic acid or derivative, water or alcohols produced may be removed by azeotropic distillation, using, e.g. benzene or trichlorethylene, and a combined catalyst and polymerization inhibitor such as hydroquinone disulphonic acid (see Specification 606,685) may be used, together with a stream of air.  A polymerization inhibitor such as hydroquinone may be present when solvent is distilled off from the reaction product.  The reactions are preferably carried out in glass or enamel-lined vessels.  The products may be polymerized (see Group IV (a)).  Examples describe the reaction of varying proportions within the prescribed limits of (1) ethylene glycol, phthalic anhydride, and methacrylic acid, with and without sulphuric acid; (2) diethylene glycol, maleic anhydride, and methacrylic acid; (3) ethylene glycol, methacrylic acid and adipic or sebacic acid; (4) ethylene glycol, methacrylic acid, and maleic anhydride; (5) 1.5-pentane-diol, methacrylic acid, and maleic anhydride; (6) ethylene glycol, phthalic anhydride, and methyl methacrylate or a -chloracrylate; trichlorethylene and hydroquinone disulphonic acid are present in all cases, and when methyl methacrylate is used in (6) above, they may be replaced by p-phenylene diamine and benzene. Specification 607,888 also is referred to.