Patent GB-936395-A (GB)
Title: A process for the production of foamed polyurethanes
IPC: C08G18/42
Filed: 1960-01-15
Abstract: In a process for the production of a foamed polyurethane, a polyhydroxy compound (which may also contain carboxyl groups) is reacted with a polyisocyanate in the presence of a metal catalyst and the reaction mixture simultaneously or subsequently foamed, if necessary or if desired (the latter case being when carboxyl groups are also present) with water.  The metal catalyst is a salt, alcoholate or phenolate of tetravalent tin and a carboxylic acid, alcohol or phenol, each of which contains at least one basic tertiary nitrogen atom (which may be part of a heterocyclic ring) in the molecule, or is an organic chelate of tetravalent tin which contains at least one basic tertiary nitrogen atom (which may be part of a heterocyclic ring) in the molecule, each tin atom in the catalyst being attached to an organic radical by at least one carbon-tin bond. Specified polyhydroxy compounds are alkylene oxide polymers, dihydroxy naphthalenes, polyethers and addition products of alkylene oxides with dior polyhydric alcohols or phenols, aliphatic or aromatic mono- or polyamines or aminoalcohols containing at least two active hydrogen atoms and polyesters containing at least two hydroxyl groups.  Many polyisocyanates and tin compounds are specified. Reaction mixture additives, e.g. sulphonated castor oil, adducts of ethylene oxide with hydrophobic compounds containing one or more active hydrogen atoms, silicone-alkylene oxide copolymers, silicones containing basic nitrogen atoms, paraffin oils, silicone oils, dyestuffs, fillers, flame-proofing agents and plasticizers and accelerators, e.g. dimethylbenzylamine, 1-alkoxy-3-dialkylaminopropane, endoethylenepiperazine, permethylated-N-ethylaminopiperazine, dimethylalkylamines, alkali metal hydroxides, carbonates, phenolates and alcoholates may be present.  Many examples are given.  Specifications 769,680, 769,682, 843,841, 884,781, 892,137, U.S.A. Specification 2,727,917, and German Specifications 964,988 and 1,040,251 are referred to.ALSO:Organotin compounds containing tertiary nitrogen are made by reacting a salt, alcoholate, or phenolate of tetravalent tin and a carboxylic acid, alcohol or phenol containing at least one tertiar nitrogen atom (which may be part of a heterocyclic ring) or an inorganic chelate of tetravalent tin containing at least one tertiary nitrogen atom (which may be part of a heterocyclic ring), each tin atom being attached to at least one organic radical by a carbon-tin bond.  In the examples:- (6) CH3-O-[Sn(C4H9)O]29-nCH3 (where n = 1.5) is trans-esterified with a -(b -diethylaminoethyl)acetoacetic acid ethyl ester; (7) acetoacetic-(b -diethylaminoethyl) ester is trans-esterified with dibutyl dimethoxy tin; (8) a -(b -diethylaminoethyl)acetoacetic acid ethyl ester is trans-esterified with dibutyl dimethoxy tin; (10) dibutyl dimethoxy tin is trans-esterified with the trans-esterification product of ethyl acetoacetate with N-methyl-N-stearyl ethanolamine; (12) dibutyl tin-bis(o -dimethyl aminocaproate) is made by esterifying dibutyl tin oxide with the free acid; (14) dioctyl tin-bis(o -dimethyl amino caproate) is made by esterifying dioctyl dimethoxy tin with the free acid; (15) dibenzyl-tin-bis(o -dimethyl aminocaproate) is made by trans-esterifying the free acid with dibenzyl dimethoxy tin; (16) (CH3)2-N-CH2)5-COO-\sTSn(C4H9) \sV2-n-O-CO(CH2)5N-(CH3)2 (where n = 1.5) is made by trans-esterifying the corresponding dimethoxy stannoxane with dimethylaminocaproic acid; (17) a stannoxane compound of the formula <FORM:0936395/IV(a)/1> is made by esterifying dibutyl tin oxide with o -dimethylamino caproic acid; (18) a basic tin compound of the formula <FORM:0936395/IV(a)/2> is made by esterifying the corresponding acid with dibutyl tin oxide; (19) trimethyl tin-o -dimethylaminocaproat is made by trans-esterifying o -dimethylamino caproic acid with triethyl methoxy tin; (21) dibutyl dimethoxy tin is trans-esterified with 8-oxy-quinoline; (22) a basic tin phenolate is made from 2 : 4 : 6-bis(dimethylaminomethyl) phenol and dibutyl dimethoxy tin; (23) a basic tin phenolate is made from dibutyl dimethoxy tin and dimethylaminomethyl phenol; (24) <FORM:0936395/IV(a)/3> is made by reacting dibutyl dimethoxy tin with N-methyl diethanolamine; (25) dioctyl-tin-bis-(5-diethylamino pentylate-2) is made by reacting dioctyl dimethoxy tin with 1-diethylaminopentanol-4; (26) a basic dibenzyl tin phenolate is made by reacting dibenzyl tin dichloride with the sodium salt of 2 : 4 : 6-tris-(dimethylamino methyl) phenol; (27) a basic triethyl teriphenolate is made by reacting triethyl methoxy tin with 2 : 4 : 6-tris-(dimethylaminomethyl)-phenol; (30) a dioctyl tin compound is made by trans-esterification of acetoacetic acid ester, N-methyl-N-stearyl ethanolamine and dioctyl dimethoxy tin and (31) a dibenzyl tin complex is made by trans-esterification of N-methyl-N-stearyl-ethanolamine with acetoacetic acid ester and dibenzyl dimethoxy tin.  Specifications 769,680, 769,681, 769,682, 838,841, 884,781, 892,137, U.S.A.  Specification 2,727,917, and German Specifications 964,988 and 1,040,251 are referred to.ALSO:In a process for the production of a foamed polyurethane, a polyhydroxy compound (which may also contain carboxyl groups) is reacted with a polyisocyanate in the presence of a metal catalyst and the reaction mixture simultaneously or subsequently foamed, if necessary or if desired (the latter case being when carboxyl groups are also present) with water.  The metal catalyst is a salt, alcoholate or phenolate of tetravalent tin and a carboxylic acid, alcohol or phenol, each of which contains at least one basic tertiary nitrogen atom (which may be part of a heterocyclic ring) in the molecule, or is an organic chelate of tetravalent tin which contains at least one basic tertiary nitrogen atom (which may be part of a heterocyclic ring) in the molecule, each tin atom in the catalyst being attached to an organic radical by at least one carbon-tin bond.  Specified polyhydroxy compounds are alkylene oxide polymers, dihydroxy naphthalenes, polyethers and addition products of alkylene oxides with di- or polyhydric alcohols or phenols, aliphatic or aromatic mono- or polyamines or amino alcohols containing at least two active hydrogen atoms and polyesters containing at least two hydroxyl groups.  Many polyisocyanates and tin compounds are specified.  Reaction mixture additives e.g. sulphonated castor oil, adducts of ethylene oxide with hydrophobic compounds containing one or more active hydrogen atoms, siliconealkylene oxide copolymers, silicones containing basic nitrogen atoms, paraffin oils, silicone oils, dyestuffs, filters, flame-proofing agents and plasticisers and accelerators e.g. dimethyl benzylamine, 1-alkoxy-3-dialkylamino-propane, endoethylene piperazine, per methylated-N-ethylaminopiperazine, dimethyl alkyamines, alkali metal hydroxides, carbonates, phenolates and alcoholates may be present.  Many examples are given.  Specifications 769,680, 769,681, 769,682, 838,841, 884,781, 892,137, U.S.A. Specification 2,727,917 and German Specifications 964,988 and 1,040,251 are referred to.