Patent GB-901056-A (GB)
Title: Improvements in or relating to the manufacture of polyurethanes
Inventor: MAGSON MAURICE SUGDEN
IPC: C08G18/26
Filed: 1960-03-23
Abstract: Polyurethanes are made by reacting organic polyisocyanates with hydroxyl group-containing polymers containing at least two isocyanate-reactive groups per molecule in the presence of a lead (II) salt of a carboxylic acid.  Specified lead (II) salts include the acetate, glycollate, thioglycollate, dithioglycollate, isobutyrate, propionate, pivalate, 2-ethyl hexoate, laurate, palmitate, oleate, ricinoleate, sulphated ricinoleate, basic acetate, dimethylglycinate, 6-dimethylaminocaproate, benzoate, phenylacetate, phenylglycinate, cinnamate, anthranilate and naphthenate.  The lead salts may be dissolved, suspended or dispersed in any of the reaction components.  Specified hydroxyl group-containing polymers are polyesters, polyesteramides and polyethers, many starting materials for their preparation being specified.  Specified polyisocyanates include hexamethylene, tolylene-2:4- and -2:6-, diphenylmethane-4:41, 3-methyl diphenylmethane-4:41, m- and p-phenylene, chlorophenylene-2:4-, naphthalene-1:5- and diphenyl - 4:41 - diisocyanate, 4:41 - diisocyanato-3:31-dimethyl diphenyl, diphenyl ether diisocyanate, dicyclohexylmethane diisocyanate, 2:4:6-triisocyanato toluene and 2:4:41-triisocyanato diphenyl ether. Foamed, cellular polyurethanes may be produced by effecting the reaction in the presence of water or fluorinated alkanes such as monofluorotrichloromethane, dibromodifluoromethane and 1:1:2-trichloro-1:2:2-trifluoroethane.  Basic catalysts, e.g. t-amines of which many are specified may be included in the reaction mixture.  In the examples, foamed polyurethanes are made by reacting in the presence of an alkyl-silane polyoxyalkylene copolymer:- (1) to (5) polyoxypropylene triol, water and a mixture of tolylene-2:4- and -2:6-diisocyanate in the presence of:- (1) basic lead acetate and dimethylcyclohexylamine, (2) and (5) the lead salt of a dicarboxylic acid obtained by reacting succinic anhydride with a linear polyproplylene glycol and dimethylcyclohexylamine, (3) the lead salt as in (2) and 4-dimethylaminopyridine and (4) the lead salt as in (2) and dimethylallyla nine; (6) and (7) a polyoxypropylene glycol, a polyoxypropylene triol, water and a mixture of tolylene-2:4- and -2:6-diisocyanate in the presence of dimethylbenzylamine, 4-dimethylaminopyridine and (6) lead octoate and (7) lead acetate trihydrate; (8) polyoxypropylene glycol, water and a mixture of tolylene-2:4- and -2:6-diisocyanate in the presence of lead acetate trihydrate and dimethylbenzylamine; (9) the oxypropylation product of tolylene diamine, diphenylmethane diisocyanate and monofluorotrichloromethane in the presence of b -trichloroethyl phosphate and lead 2-ethyl hexoate; (10) the oxypropylation product of tolylene diamine, 4:41-diisocyanatodiphenylmethane and monofluorotrichloromethane in the presence of b -trichloroethylphosphate and lead 2-ethylhexoate; (12) an oxypropylated trihydric alcohol, 4:41-diisocyanatodiphenylmethane and monofluorotrichloromethane in the presence of lead 2-ethylhexoate and dimethylcyclohexylamine; (13) and (14) polyoxypropylene glycol and a mixture of tolylene-2:4- and -2:6-diisocyanate in the presence of lead acetate trihydrate, 4-dimethylaminopyridine and in (13) oleic acid and dimethylbenzylamine; (15) a polyoxypropylene glycol, a polyoxypropylene triol, a mixture of tolylene-2:4- and -2:6-diisocyanate and water in the presence of lead acetate trihydrate and dimethylaminopyridine.  Examples (11) and (16) describe the preparation of lacquers by reacting in the presence of methylketone and cyclohexane, polyesters derived from glycerol, adipic acid and ethylene glycol with:- (11) tolylene-2:4-diisocyanate in the presence of lead 2-ethylhexoate and mixtures thereof with 4-dimethylaminopyridine, dimethylcyclohexylamine or dimethylbenzylamine and (16) hexamethylene diisocyanate in the presence of lead 2-ethylhexoate or lead pivalate; Example (17) describes the preparation of a polyurethane rubber by reacting in the presence of a lead salt of a C9 to C16 fatty acid and partially hydrated silica, a polyester derived from diethylene glycol, pentaerythritol and adipic acid and a diisocyanate formed by phosgenation of a diamine obtained by the condensation of aniline, o-toluidine and formaldehyde.ALSO:Foamed polyurethanes are made by reacting in the presence of water or a fluorinated alkane and a lead (II) salt of a carboxylic acid an organic polyisocyanate and an hydroxyl group containing at least two isocyanate reactive groups. Specified fluorinated alkanes are monofluorotrichloromethane, dibromodifluoromethane and 1 : 1 : 2-trichloro- 1 : 2 : 2-trifluorethane.  Specified lead (II) salts include the acetate, glycollate, thioglycollate, thiodiglycollate, oleate, isobutyrate, propionate, pivalate, 2-ethylhexoate, laurate, palmitate, ricinoleate, sulphated ricinoleate, basic acetate, dimethylglycinate, 6-dimethylaminocaproate, benzoate, phenylacetate, phenylglycinate, cinnamate, anthranilate and naphthenate.  The lead salts may be dissolved, suspended or dispersed in any of the reaction components. Specified hydroxyl group-containing polymers are polyesters, polyesteramides and polyethers, many starting materials for their preparation being specified.  Specified polyisocyanates include hexamethylene, tolylene-2:4- and-2:6-diphenylmethane-4: 41-3-dimethyldiphenylmethane-4: 41-, m- and p-phenylene, chlorophenylene-2: 4, naphthalene-1: 5- and diphenyl-4: 41-diisocyanate, 4 : 41-diisocyanato-3: 3-dimethyldiphenyl, diphenyl ether diisocyanate, dicyclohexylmethane diisocyanate, 2 : 4 : 6- triisocyanatotoluene and 2:4:41: triisocyanato diphenylether.  Basic catalysts e.g. t-amines of which many are specified may be included in the reaction mixture.  In the examples, foamed polyurethanes are made by reacting in the presence of an alkyl-silane polyoxyalkylene copolymer:-(1) to (5) polyoxiypropylene triol, water and a mixture of tolylene-2 : 4-and -2:6- diisocyanate in the presence of:-(1) basic lead acetate and dimethylcyclohexylamine, (2) and (5) the lead salt of a dicarboxylic acid obtained by reacting succinic anhydride with a linear polypropylene glycol and dimethylcyclohexylamine, (3) the lead salt as in (2) and 4-dimethylaminopyridine and (4) the lead salt as in (2) and dimethylallyllamine; (6) and (7) polyoxypropylene glycol, polyoxypropylene triol, water and a mixture of tolylene-2 : 4- and 2 : 6- diisocyanate in the presence of dimethylbenzylamine, 4-dimethylaminopyridine and (6) lead octoate and (7) lead acetate trihydrate; (8) polyoxypropylene glycol, water and a mixture of tolylene-2 : 4- and-2: 6- diisocyanate in the presence of lead acetate trihydrate and dimethylbenzylamine; (9) the oxypropylation product of tolylene diamine, diphenylmethane diisocyanate and monofluorotrichloromethane in the presence of b -trichloroethyl phosphate and lead 2-ethylhexoate; (10) the oxypropylation product of tolylene diamine, 4: 41- diisocyanato-diphenylmethane and monofluorotrichloromethane in the presence of b -trichloroethylphosphate and lead 2-ethylhexoate; (12) an oxypropylated trihydric alcohol, 4 : 41 diisocyanatodiphenylmethane and monofluorotrichloromethane in the presence lead 2-ethylhexoate and dimethylcyclohexylamine; (13) and (14) polyoxypropylene glycol and a mixture of tolylene-2 : 4-and 2:6-diisocyanate in the presence of lead acetate trihydrate, 4-dimethylaminopyridine and in (13) oleic acid and dimethylbenzylamine; (15) polyoxypropylene glycol, polyoxypropylene triol, a mixture of tolylene-2:4-and-2: 6-diisocyanate and water in the presence of lead acetate trihydrate and dimethylaminopyridine.