Patent GB-629015-A (GB)
Title: New polymerisable materials and polymers thereof
IPC: C08F20/62
Filed: 1947-02-14
Abstract: Polymerizable products are obtained by reacting under conditions such that polymerization is inhibited, one or more mono- and/or di-hydroxy acrylic, including methacrylic and a -haloacrylic, esters with one or more compounds containing 2 only methylol or alkoxymethyl groups attached ortho and/or para to a hydroxy and/or amino-substituted aromatic ring or to a nitrogen atom attached to a >CO, >CS or >C=N- group or an aromatic nucleus or containing 2 only isocyanate and/or isothiocyanate groups attached to alkyl groups.  Suitable dimethylol compounds include dimethylol urea, phenols, cresols, N,N-dimethylol succinamide and adipamide, and their methyl to buty ethers. hexamethylene di-isocyanate is also specified.  The hydroxy acrylic esters may be prepared as described in Specification 628,150. Polymerization inhibitors used in their preparation and in the preparation of the products of the invention may be those described in the said Specification. Preferred polymers are obtained from the products if, based on the weight of reactants less their weight of acrylic groups and the weight of by-products, the weight of hydroxyl groups equivalent to the acrylic groups, is less than 25, preferably less than 17 per cent, and the weight of hydroxyl groups equivalent to the acrylic groups, acrylic groups in excess of one per molecule being counted twice, plus the weight of hydroxyl groups 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.  The products have general formul ;- <FORM:0629015/IV (a)/1> where p, q, n are integers, R, R1 are organic radicals, A is an acrylic group, X is an aryl group with hydroxyl and/or amino substituents or is a divalent radical having terminal nitrogen atoms each attached to a >CO, >CS, >C=N-or an aromatic nucleus, Y is alkyl, Z is oxygen or sulphur, K is hydrogen, alkyl or -R1 (O.A)q, L is -R1 (O.A)q or -R (O.A)p.OH, M is -NCZ or NH.CZ.O.R1 (O.A)q, and Q is -NH.CZ.O.R1 (O.A)q or -NH.CZ.O.R (O.A)p. OH.  Polymerization is effected as in Specification 628,150, optionally with the additions therein specified.  In examples, glycerol, methacrylic acid, trichlorethylene which removes water as an azeotrope, and hydroquinone disulphonic acid are refluxed while bubbling air, the product neutralized, refluzed with copper sulphate and dimethylol urea, and the solvent distilled off after adding hydroquinone. The product is mixed with benzoyl peroxide in butyl methacrylate and used for bonding degreased glass fibre cloth into laminated material.  Hexamethylene di-isocyanate is added to copper acetate in b -hydroxyethylmethacrylate at 90 DEG  C.  This product gives a hard resin on heating with benzoyl peroxide in methyl methacrylate.  Specifications 456,147, 565,777 and 606,685, [Group IV (b)], also are referred to.ALSO:Polymerizable products are obtained by reacting, under conditions such that polymerization is inhibited, one or more mono-and/or di-hydroxy acrylic, including methacrylic and a -haloacrylic, esters with one or more compounds containing 2 only methylol or alkoxymethyl groups attached ortho and/or para to a hydroxy and/or amino-substituted aromatic ring or to a nitrogen atom attached to a >CO, >CS or >C=N-group or an aromatic nucleus or containing 2 only isocyanate and/or isothiocyanate groups attached to alkyl groups.  Suitable dimethylol compounds include di-methylol urea, phenols, cresols, N,N-dimethylol succinamide and adipamide, and their methyl to butyl ethers.  Hexamethylene di-isocyanate is also specified.  The hydroxy acrylic esters may be prepared as described in Specification 628,150.  Polymerization inhibitors used in their preparation and in the preparation of the products of the invention may be those described in the same Specification.  Preferred polymers are obtained from the products if, based on the weight of reactants less their weight of acrylic groups and the weight of by-products, the weight of hydroxyl groups equivalent to the acrylic groups is less than 25, preferably less than 17 per cent, and the weight of hydroxyl groups equivalent to the acrylic groups, acrylic groups in excess of one per molecule being counted twice, plus the weight of hydroxyl groups 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.  The products have general formul : (A.O)qR1.O.CH2.X.CH2.OR1(O.A)q K.O.CH2.X.CH2.O (R.(O.A)p.O.CH2.X.CH2.O)nL, (A.O)qR1.O.CZ.NH.Y.NH.CZ.O.R1(O.A)q, and M.Y.NH.CZ.O.(R.(O.A)p.O.CZ.NH.Y.NH.CZ.O)n.Q where p, q, n are integers, R, R1 are organic radicals, A is an acrylic group, X is an aryl group with hydroxyl and/or amino substituents or is a divalent radical having terminal nitrogen atoms, each attached to a >CO, >CS, >C=N-or an aromatic nucleus, Y is alkyl, Z is oxygen or sulphur, K is hydrogen, alkyl or -R1(O.A)q, L is -R1(O.A)q or -R(O.A)p.OH, M is -NCZ or -NH.CZ.O.R1(O.A)q, and Q is -NH.CZ.O. R1(O.A)q or -NH.CZ.O.R(O.A)p.OH.  Polymerization is effected as in Specification 628,150 optionally with the additions therein specified.  In examples, glycerol, methacrylic acid, trichlorethylene which removes water as an azeotrope, and hydroquinone disulphonic acid are refluxed while bubbling air, the product neutralized, refluxed with copper sulphate and dimethylol urea, and the solvent distilled off after adding hydroquinone. The product is mixed with benzoyl peroxide in butyl methacrylate and used for bonding degreased glass fibre cloth into laminated material.  Hexamethylene di-isocyanate is added to copper acetate in b -hydroxyethylmethacrylate at 90 DEG  C.  The product gives a hard resin on heating with benzoyl peroxide in methyl methacrylate. Specifications 456,147, 565,777, and 606,685 also are referred to.