Patent GB-890280-A (GB)
Title: Improvements in or relating to the manufacture of foamed polyurethanes
Inventor: STEPHENSON KENNETH
IPC: C08G18/22
Filed: 1959-02-25
Abstract: Foamed polyurethanes are made by reacting together an organic polyisocyanate and a hydroxyl-ended polymer in the presence of a co-ordination compound of titanium, zirconium, hafnium, thorium or manganese with a b -diketone, b -ketoester or b -hydroxyaldehyde, to give a reaction product containing free isocyanate groups which is then reacted with water.  Specified co-ordinating compounds are acetylacetone, benzoylacetone, 3-cyanoacetylacetone, dibenzoylacetone, propionylacetone, trifluoroacetylacetone, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate and salicylaldehyde.  Specified polyisocyanates include hexamethylene diisocyanate, tolylene diisocyanates, diphenyl methane-4:41-diisocyanate, 3-methyl diphenyl methane-4:41-diisocyanate, m- and p-phenylene diisocyanates, chlorophenylene-2:4-diisocyanate, dicyclohexyl methane diisocyanate, 2:4:6-triisocyanato toluene and 2:4:4-triisocyanatodiphenyl ether. Specified hydroxyl-ended polymers are polyesters, polyesteramides and polyethers of which many are listed.  The reaction may be continuous or discontinuous and may be effected in the presence of catalysts, non-ionic surfaceactive agents, salts of sulphuric acid derivatives of high molecular weight organic compounds, silicone oils, foam stabilizing agents, e.g. ethyl cellulose, certain polyhydroxy compounds, e.g. trimethylol propane, pigments, plasticizers, e.g. dinonyl phthalate and fire-proofing agents, e.g. tri-(b -chloroethyl) phosphate.  The stability of the intermediate reaction products may be improved by the addition thereto of acid-reacting substances, e.g. acetyl chloride.  In the Examples, mixed tolylene 2:4- and 2:6-diisocyanates are reacted with polypropylene glycol in the presence of:- (1) tris-(2:4-pentanediono) manganese III; (2) tetrakis-(2:4-pentanediono) zirconium IV; (3) a polyether derived from propylene oxide and 1:2:6-hexanetriol and tetrakis-(2:4-pentanediono) zirconium IV; (4) N:N-dimethylcyclohexylamine, tris-(2:4-pentanediono) manganese III and ethyl cellulose and (5) tetrakis-(2:4-pentanediono) thorium IV to form intermediates containing free isocyanate groups which are foamed by reaction with N:N-dimethylcyclohexylamine (except in Example 4) and water in the presence of an octyl phenolethylene oxide reaction product and the sodium salt of sulphated methyl oleate. Specification 869,988 is referred to.ALSO:Foamed polyurethanes are made by reacting together an organic polyisocyanate and a hydroxyl ended polymer in the presence of a co-ordination compound of titanium, zirconium, hafnium, thorium or manganese with a b -diketone, b -ketoester or b -hydroxyaldehyde to give a reaction product containing free isocyanate groups which is then reacted with water.  Specified co-ordinating compounds are acetylacetone, benzoylacetone, 3-cyanoacetylacetone, dibenzoylacetone, propionylacetone, trifluoroacetylacetone, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate and salicylaldehyde.  Specified polyisocyanates include hexamethylene diisocyanate, tolylene diisocyanates, diphenyl methane-4 : 41-diisocyanate, 3-methyl diphenyl methane-4 : 41-diisocyanate, m- and p-phenylene diisocyanates, chlorophenylene-2:4-diisocyanate, dicyclohexylmethane diisocyanate, 2: 4 : 6-triisocyanatotoluene and 2 : 4 : 4-triisocyanatodiphenyl ether.  Specified hydroxylended polymers are polyesters, polyesteramides and polyethers of which many are listed. The reaction may be continuous or discontinuous and may be effected in the presence of catalysts, non-ionic surface active agents, sodium salts of sulphuric acid derivatives of high molecular weight organic compounds, silicone oils, foam stabilising agents e.g. ethyl cellulose, certain polyhydroxy compounds e.g. trimethyl propane, plasticisers e.g. dinonyl phthalate and fire-proofing agents e.g. tri (b -chloroethyl) phosphate.  The stability of the intermediate reaction products may be improved by the addition thereto of acid-reacting substances e.g. acetyl chloride.  In the examples, mixed tolylene 2 : 4-and 2 : 6-diisocyanates are reacted with polypropylene glycol in the presence of: (1) tris-(2 : 4-pentanediono) manganese III; (2) tetrakis-(2 : 4-pentanediono) zirconium IV; (3) a polyether derived from propylene oxide and 1 : 2 : 6-hexane triol and tetrakis-(2 : 4- pentanediono) zirconium IV; (4) N : N-dimethyl cyclohexylamine, tris-(2 : 4-pentanediono) manganese III and ethyl cellulose and (5) tetrakis-(2 : 4-pentanediono) thorium IV which are foamed by reaction with N : N-dimethylcyclohexylamine (except in Example 4) and water in the presence of an octyl phenol-ethylene oxide reaction product and the sodium salt of sulphated methyl oleate.  Specification 869,988 is referred to.