Patent GB-889048-A (GB)
Title: Improvements in or relating to the manufacture of polyurethanes
Inventor: TWITCHETT HARRY JAMES
IPC: C08G18/20
Filed: 1959-05-13
Abstract: Polyurethanes are made by reacting an organic polyisocyanate and an hydroxyl-containing material in the presence of a catalyst comprising a polyheterocyclic amine containing only one nitrogen atom that forms part of the ring structure of either two or three saturated rings; said rings each having as a ring member said nitrogen atom, and wherein one ring contains not more than six carbon atoms and the other ring or rings each contain not more than five carbon atoms. Specified catalysts are 1-azabicyclo [5.4.0]-undecane, 1-azabicyclo [3.2.2.] nonane, conidine, pyrrolizidine, octahydropyrrocoline, 1-azabicyclo [5.3.0] decane, 1-azabicycle [2.2.1] heptane, 1-azabicyclo [3.2.1] octane, 1-azabicyclo [3.3.1] nonane, 1-aza-adamantane, quinuclidine, 3-methylconidine, 8-methylpyrrolizidine, 2:6.dimethylpyrrolizidine, 2:6:8-trimethylpyrrolizidine, 3-ethylquinuclidine, 3-ethyloctahydropyridocoline, 1:2-trimethylenedecahydroisoquinoline, hexahydrolilolidine and hexahydrojulodidine.  Specified polyisocyanates are hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane-4,41-diisocyanate, 3-methyldiphenylmethane-4:41-diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene-2:41-diisocyanate, dicyclohexylmethane diisocyanate, 2:4:6-triisocyanatotoluene and 2:4:41-triisocyanatodiphenyl ether.  Specified hydroxyl-containing materials are polyesters, polyethers and polyesteramides, many being exemplified.  Modifying catalysts, e.g. dimethylcyclohexylamine, potassium carbonate, potassium acetate, potassium naphthenate, manganous and manganic acetyl acetonates and dialkyl tin compounds; silicone oils; foam stabilizing agents; colouring matters; plasticizers and fire-proofing agents may be present in the reaction mixture.  In the Examples:- (1) a polyester derived from adipic acid, ethylene glycol and glycerol is reacted with 2:4-tolylene diisocyanate in the presence of cyclohexanone, methylethyl ketone and pyrrolizidine to make a lacquer; (2) and (3) a polyether derived from propylene oxide and glycerol is reacted with a mixture of 2:4- and 2:6-tolylene diisocyanate in the presence of ethyl cellulose, acetone, water, an octyl phenol-ethylene oxide reaction product and (2) pyrrolizidine, (3) quinuclidine to form foams; (4) and (5) a polyether made by oxypropylation of a trihydric alcohol is reacted with 4:41-diisocyanatodiphenylmethane in the presence of a polysiloxaneoxyalkylene block copolymer, trichlorofluoromethane and (4) pyrrolizidine, (5) 8-methylpyrrolizidine to form foams.ALSO:Polyurethanes are made by reacting an organic polyisocyanate and an hydroxyl-containing material in the presence of a catalyst comprising a polyheterocyclic amine containing only one nitrogen atom that forms part of the ring structure of either two or three saturated rings; said rings each having as a ring member said nitrogen atom, and wherein one ring contains not more than six carbon atoms and the other ring or rings each contain nor more than five carbon atoms.  Specified catalysts are 1-azabicycle [5.4.0]- undecane, 1-azabicyclo [3.2.2] nonane, conidine, pyrrolizidine, octahydropyrrocoline, 1-azabicyclo [5.3.0] decane, 1-azabicylo [2.2.1 heptane, 1-azabicyclo [3.2.1] octane, 1-azabicyclo [3.3.1] nonane, 1-azaadamantane, quinuclidine, 3-methylconidine, 8-methylpyrrolizidine, 2 : 6.dimethylpyrrolizidine, 2 : 6 : 8-trimethylpyrrolizidine, 3-ethylquinuclidine, 3-ethyloctahydropyridocoline, 1:2-trimethylenedecahydroisoquinoline, hexahydrolilolidine and hexahydrojulolidine.  Specified polyisocyanates are hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane-4,41-diisocyanate, 3-methyldiphenylmethane-4 : 41-diisocyanate, m- and p-phenylene diisocyanate, chlorophenylene-2 : 41-diisocyanate, dicylochexylmethane diisocyanate, 2 : 4 : 6-triisocyanatotoluene and 2 - 4 : 41-triisocyanatodiphenyl ether.  Specified hydroxyl-containing materials are polyesters, polyethers and polyesteramides, many being exemplified.  Modifying catalysts e.g. dimethylcyclohexylamine, potassium carbonate, potassium acetate, potassium naphthenate, manganouse and manganic acetyl acetonates and dialkyl tin compounds; silicone oils; foam stabilising agents; colouring matters; plasticisers and fire-proofing agents may be present in the reaction mixture.  In the examples:- (1) a polyester derived from adipic acid, ethylene glycol and glycerol is reacted with 2 : 4-tolylene diisocyanate in the presence of cyclohexanone, methylethyl ketone and pyrrolizidine to make a lacquer; (2) and (3) a polyether derived from propylene oxide and glycerol is reacted with a mixture of 2 : 4-and 2 : 6-tolylene diisocyanate in the presence of ethyl celluslose, acetone, water, an octyl phenol ethylene oxide reaction product and (2) pyrrolizidine, (3) quinuclidine to form foams; (4) and (5) a polyether made by oxypropylation of a trihydric alcohol is reacted with 4 : 41-diisocyanatodiphenylmethane in the presence of a polysiloxane oxyalkylene block copolymer, trichlorofluoromethane and (4) pyrrolizidine, (5) 8-methylpyrrolizidine to form foams.