Patent GB-625877-A (GB)
Title: New polymerisable materials and polymers thereof
IPC: C08F299/04
Filed: 1947-02-19
Abstract: Polymerizable products are made by reacting one or more dihydroxy acrylic, including methacrylic and a -halo-acrylic esters whose hydroxyl groups are separated by a chain of S atoms, with one or more compounds containing two carboxyl groups or ester-forming derivatives thereof separated by a chain of T atoms, S+T being 3 or more.  One or more monohydroxy acrylic esters may also be included and conditions are such as to inhibit polymerization.  Suitable dicarboxylic acids are maleic, adipic, sebacic, phthalic, terephthalic, and diglycollic. Ester-forming derivatives are the acid chlorides, anhydrides, and lower esters such as methyl, ethyl, propyl, and butyl esters. Dihydroxy acrylic esters may be obtained by partial esterification of polyhydroxy alcohols such as glycerol, and erythritol with acrylic acid, anhydride or lower esters.  Preparation of the hydroxy acrylic esters and the reaction of the invention may be effected in the presence of catalysts, with removal of water or alcohol of reaction as an azeotrope, and in the presence of polymerization inhibitors, especially polyhydric phenol sulphonic acids, as described in Specification 606,685, [Group IV (b)], copper salts and metallic halides as described in Specification 456,147, all of which can be removed by precipitation or washing.  The products are X. (O.CO.Z.CO.O.R.(O.A)p)n O.CO.Z.CO.O.Y, where n and p are integers, Z is a radical comprising a chain of S atoms, R a radical comprising a chain of T atoms, S+T is 3 or more, A is an acrylic, as herein defined, group, X is - R(O.A)pOH or - R1(O.A)q, and Y is H or - R1(O.A)q, where q is an integer, and R1 is an organic radical, R and R1 preferably containing not more than 4 carbon atoms each.  They yield preferred types of polymers if the reactants have a content of acrylic groups such that the weight of hydroxyl groups equivalent thereto, acrylic groups in excess of two per molecule being counted twice, and based on the weight of the reactants minus their weight of acrylic groups and the weight of the by-products is less than 25, preferably less than 17 per cent, and, if the weight of hydroxy groups equivalent to the acrylic groups, groups in excess of one per molecule being counted twice, plus the weight of hydroxyl groups in the hydroxy esters in excess of one per molecule is less than 25, preferably less than 17, and greater than 2.5, preferably greater than 7 per cent.  Compounds containing more than 2 carboxyl or hydroxyl groups should not be present in substantial amount.  Glycols may be incorporated.  The products of molecular weight 250-500 are most useful and are obtained by incorporating lower molecular weight compounds such as butyl methacrylate and glycol dimethacrylate. Polymerization may be effected in stages and in the presence of other unsaturated compounds which interpolymerize therewith or polymerize simultaneously, e.g. di-(alkyl glycollyl)-succinate, methacrylates, vinyl compounds, maleic anhydride, and polyesters of maleic or fumaric acid.  Dyes, fillers, pigments, and reinforcing materials may be included.  In examples, glycerol, methacrylic acid, trichlorethylene, as azeotroping solvent, and hydroquinone disulphonic acid or antimony pentachloride with, in the latter case, sulphuric acid, are refluxed while bubbling air, the products cooled, maleic or phthalic anhydride and sulphuric acid added, and refluxing continued, or phthalyl chloride added followed by warming to room temperature to give the polymethacrylic esters of glycerol maleates or phthalates.  The maleate ester is mixed with benzoyl peroxide in butyl methacrylate and used for bonding glass fibre cloth to form laminated board.ALSO:Polymerizable products are made by reacting one or more dihydroxy acrylic, including methacrylic and a -halo-acrylic, esters, whose hydroxyl groups are separated by a chain of S atoms, with one or more compounds containing two carboxyl groups or ester-forming derivatives thereof separated by a chain of T atoms, S + T being 3 or more.  One or more monohydroxy acrylic esters may also be included and conditions are such as to inhibit polymerization. Suitable dicarboxylic acids are maleic, adipic, sebacic, phthalic, terephthalic, and diglycollic.  Ester-forming derivatives are the acid chlorides, anhydrides, and lower esters such as methyl, ethyl, propyl, and butyl esters.  Dihydroxy acrylic esters may be obtained by partial esterification of polyhydroxy alcohols such as glycerol, and erythritol with acrylic acid, anhydride or lower esters. Preparation of the hydroxy acrylic esters and the reaction of the invention may be effected in the presence of catalysts, with removal of water or alcohol of reaction as an azeotrope, and in the presence of polymerization inhibitors, especially polyhydric phenol sulphonic acids as described in Specification 606,685, copper salts and metallic halides, as described in Specification 456,147, all of which can be removed by precipitation or washing.  The products are compounds of the formula X.(O.CO.Z.CO.O.R.(O.A.)p)n.O.CO.Z.CO.O.Y, where n and p are integers, Z is a radical comprising a chain of S atoms, R a radical comprising a chain of T atoms, S + T is 3 or more, A is an acrylic, as herein defined, group, X is - R.(O.A)p.OH or - R1(O.A)q, and Y is H or - R1(O.A)q, where q is an integer, and R1 is an organic radical, R and R1 preferably containing not more than 4 carbon atoms each. They yield preferred types of polymers if the reactants have a content of acrylic groups such that the weight of hydroxyl groups equivalent thereto, acrylic groups in excess of two per molecule being counted twice, and based on the weight of the reactants minus their weight of acrylic groups and the weight of the bye-products, is less than 25, preferably less than 17 per cent, and if the weight of hydroxy groups equivalent to the acrylic groups, groups in excess of one per molecule being counted twice, plus the weight of hydroxyl groups in the hydroxy esters in excess of one per molecule is less than 25, preferably less than 17, and greater than 2.5, preferably greater than 7 per cent.  Compounds containing more than 2 carboxyl or hydroxyl groups should not be present in substantial amount.  Glycols may be incorporated.  The products of molecular weight 250-500 are most useful and are obtained by incorporating lower molecular weight compounds such as butyl methacrylate and glycol dimethacrylate.  Polymerization may be effected in stages and in the presence of other unsaturated compounds, which interpolymerize therewith or polymerize simultaneously, e.g. di-(allyl glycollyl)-succinate, methacrylates, vinyl compounds, maleic anhydride, and polyesters of maleic or fumaric acid.  Dyes, fillers, pigments, and reinforcing materials may be included.  In examples, glycerol, methacrylic acid, trichlorethylene, as azeotroping solvent, and hydroquinone disulphonic acid or antimony pentachloride with, in the latter case, sulphuric acid, are refluxed while bubbling air, the product cooled, maleic or phthalic anhydride and sulphuric acid added, and refluxing continued, or phthalyl chloride added followed by warming to room temperature to give the polymethacrylic esters of glycerol maleates or phthalates.  The maleate ester is mixed with benzoyl peroxide in butyl methacrylate and used for bonding glass fibre cloth to form laminated board.