Patent GB-606717-A (GB)
Title: New polymerisable materials and polymers thereof
IPC: C08F20/20
Filed: 1946-01-02
Abstract: Polymerizable esters are made by reacting, under conditions which result in diacid ester formation, acrylic, methacrylic, or halo acrylic acid, or an ester-forming derivative thereof, with a dihydric mono- or polycarbonyl ester, a mixture of such esters, or a mixture of one or more of such ester and a dihydric alcohol, said ester or mixtures having between 5 and 25 per cent by weight hydroxyl groups, preferably 8-18 per cent.  Ester-forming derivatives specified are the acid chloride, anhydride, or methyl, ethyl, propyl, or butyl ester.  The dihydric mono- or polycarbonyl esters are prepared by reacting phosgene with more than an equimolecular proportion of a dihydric alcohol having at least 4 atoms between the hydroxyl groups in absence of a base at room temperature, followed by heating, or by reacting phosgene and a dihydric alcohol having at least 4 atoms between the hydroxyl groups to give a chloroformate, and reacting this with any dihydric alcohol, or by reacting a dichloroformate of any dihydric alcohol with any dihydric alcohol, the dichloroformate being added to the alcohol.  Dihydric alcohols specified are tetramethylene, pentamethylene, hexamethylene, di- and other polyethylene, and tri-methylene, glycols.  A polymerization inhibitor, e.g. hydroquinone disulphonic acid (see Specification 606,685, [Group IV (b)]), may be present during the reaction with acrylic acid, and may be removed by precipitation with sodium carbonate.  A solvent such as benzene or trichlorethylene may be present to remove water or alcohol by azeotropic distillation, and is subsequently removed by distillation at reduced pressure in presence of an inhibitor such as hydroquinone.  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, 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, 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. polymethyl methacrylate.  In examples, methacrylic acid is reacted with the product obtained from phosgene and (1) diethylene glycol; (2) pentane diol- .5; (3) diethylene glycol and pentane diol-1.5; (4) diethylene glycol and ethylene glycol; (5) ethylene glycol and ethylene glycol dichloroformate.  Also in examples: (6) the product of (1) is mixed with polymethylmethacrylate, benzoyl peroxide and butyl methacrylate, and the mixture is used to make laminated material with glass fibre cloth; (7) the product of (2) is used similarly, but with canvas; (8) the product of (2) is mixed with butyl methacrylate and benzoyl peroxide and used to make a laminated material with paper; (9) the product of (1) is mixed with polymethyl methacrylate and benzoyl peroxide and polymerized in a glass cell.ALSO:Polymerizable esters are made by reacting, under conditions which result in diacid ester formation, acrylic, methacrylic, or a -haloacrylic acid, or an ester-forming derivative thereof, with a dihydric mono- or poly-carbonyl ester, a mixture of such esters, or a mixture of one or more of such esters and a dihydric alcohol, said ester or mixtures having between 5 and 25 per cent by weight hydroxyl groups, preferably 8-18 per cent.  Ester-forming derivatives specified are the acid chloride, anhydride, or methyl, ethyl, propyl, or butyl ester.  The dihydric mono- or polycarbonyl esters are prepared by reacting phosgene with dihydric alcohol having at least 4 atoms between the hydroxyl groups in absence of a base at room temperature, followed by heating, or by reacting phosgene and a dihydric alcohol having at least 4 atoms between the hydroxyl groups to give a chloroformate, and reacting this with any dihydric alcohol, or by reacting a dichloroformate of any dihydric alcohol with any dihydric alcohol, the dichloroformate being added to the alcohol.  Dihydric alcohols specified are tetramethylene, pentamethylene, hexamethylene, di- and other polyethylene, and tri-methylene glycols.  A polymerization inhibitor, e.g. hydroquinone disulphonic acid (see Specification 606,685) may be present during the reaction with acrylic acid, and may be removed by precipitation with sodium carbonate.  A solvent such as benzene or tri-chlorethylene may be present to remove water or alcohol by azeotropic distillation, and is subsequently removed by distillation at reduced pressure in presence of an inhibitor such as hydroquinone.  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 co-polymerize or polymerize simultaneously, e.g. di-(allyl glycollyl) succinate, glycol dimethacrylate, methyl acrylate, 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, 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. polymethyl methacrylate.  In examples, methacrylic acid is reacted with the product obtained from phosgene and (1) diethylene glycol, (2) pentane diol-1.5, (3) diethylene glycol and pentane diol-1.5, (4) diethylene glycol and ethylene glycol, (5) ethylene glycol and ethylene glycol dichloroformate.  Also in examples: (6) the product of (1) is mixed with polymethylmethacrylate, benzoyl peroxide, and butyl methacrylate, and the mixture is used to make a laminated material with glass fibre cloth; (7) the product of (2) is used similarly but with canvas; (8) the product of (2) is mixed with butyl methacrylate and benzoyl peroxide and used to make a laminated material with paper; (9) the product of (1) is mixed with polymethyl methacrylate and benzoyl peroxide and polymerized in a glass cell.