Patent GB-935615-A (GB)
Title: Cellular polyurethane plastics
IPC: C08G18/24
Filed: 1960-04-13
Abstract: In a process for the production of polyurethane foam materials by reacting a polyisocyanate with a polyhydroxy and/or a polycarboxyl compound together with, at least if no polycarboxyl group is present, a foaming agent which may be water, there is employed to catalyse the reaction and stabilize the foam a silicon compound containing siloxane groupings, -Si-O-Si- and tetravalent tin and in which each tin atom is attached to from 1 to 3 organic radicals by means of tin-carbon bonds.  The silicon compound may be one containing stannosiloxane (­Sn-O-Si­) or stannoxane (-Sn-O-Sn) groupings in the molecule.  Tertiary amines may be employed as catalysts and water-soluble or basic silicones as stabilizers, in addition to the silicon compound containing tetravalent tin.  Preferably the process is applied to the reaction of an organic polyisocyanate, water and an organic compound containing predominantly secondary hydroxyl groups. Halohydrocarbons such as dichlorodifluoromethane and trichlorofluoromethane can also be used as blowing agents.  As polyhydroxy compounds there are listed condensation products of alkylene oxides, and reaction products of alkylene oxides with polyhydric alcohols or phenols, aliphatic or aromatic amines, amino alcohols, castor oil, sugar.  Hydroxy polyesters containing secondary hydroxyl groups as well as compounds containing active hydrogen in amino, carboxyl, -SH, urethane, urea and amide groups, and also the conventional polyethers, polythioethers and polyacetals can be used. The catalyst-stabilizers can contain any organic radicals which may be aliphatic, aromatic or heterocyclic and may contain unsaturation or such substituents as halogeno, nitro, alkoxy, carbalkoxy, dialkylamino, mercapto, carbonyl, thiocarbonyl, hydroxy, phosphato or phosphoryl substituents.  The silicon compounds comprise units of the type p  <FORM:0935615/IV(a)/1> , <FORM:0935615/IV(a)/2> and R11 wherein m and n are each 0, 1, 2 or 3; R and R1 are monovalent organic radicals; R11 is a radical derived from a polyhydric alcohol and is joined to the other units by oxygen bridges.  They include compounds having the recurring group <FORM:0935615/IV(a)/3> where a, b and c are integers and b may be zero.  The silicon compounds can be prepared by transesterification of a silanol containing an ­Si-OH group with an alkoxy tin compound; by reacting a silanol salt, such as the sodium salt of trimethylsilanol with an organotin halide; by reacting an alkoxysilane with a tin halide or tin acylate; by reacting a halosilane or halosiloxane with an alkyltin acylate.  The siloxanes used in preparing the catalysts may contain ether oxygen atoms and/or terminal hydroxyl groups, resulting from the reaction of silanes and siloxanes with polyhydric alcohols or alkylene oxides. In Example (1) a foam is prepared by reacting a linear polypropylene glycol, toluene-2,4- and 2,6-diisocyanates and water in the presence of a siloxane-alkylene oxide copolymer, permethylated N-aminoethylpiperazine and a stannosiloxane prepared by the interesterification of tetraethoxy-1,3-diphenyl disiloxane and dibutyl-tin diacetate.  Catalysts used in other examples are reaction products of (2) tetramethyl-1,3-diethoxy-disiloxane, polyethylene glycol, dibutyl-tin-diacetate in the presence of acetyl chloride; (3) 1,3-diethoxy tetramethyl disiloxane, polyethylene glycol and dibutyldimethoxy-tin; (4) 1,17-diethoxy-methyl-nona-siloxane and dibutyltin diacetate; (5) an acetic ester formed from methyl triethoxysilane and 1,19-diethoxymethyldecasiloxane, and an anhydrous polyethylene glycol-propylene glycol monoalkyl ether; (6) 1,3-diethoxy-tetramethyl-disiloxane and dibutyltin diacetate; (7) a dibutyltin diacetate/polydimethylsiloxane reaction product and a polyether of OH number 66; (8) dioctyltin-diacetate and a ,o -diethoxypolydimethylsiloxane; (10) a methylethoxypolysiloxane, 1,19diethoxymethyldecasiloxane and dibutyltin diacetate; (12) pentaethoxy-1,3,5-triphenyl-trisiloxane, 1,19-diethoxymethyldecasiloxane, dibutyltin diacetate and a polyethylene glycolpolypropylene glycol monoether; (13) tetraethoxy-1, 3-diphenyl-disiloxane, 1,19-diethoxymethyldecasiloxane (added in two portions) and dibutyltin diacetate.  Specifications 769,682, 884,781, 930,635 are referred to.ALSO:In a process for the production of polyurethane foam materials by reacting a polyisocyanate with a polyhydroxy and/or a polycarboxyl compound together with, at least if no polycarboxyl group is present, a foaming agent which may be water, there is employed to catalyse the reaction and stabilize the foam a silicon compound containing siloxane groupings, -Si-O-Si- and tetravalent tin and in which each tin atom is attached to from 1 to 3 organic radicals by means of tin-carbon bonds.  The silicon compound may be one containing stannosiloxane (#X Sn-O-Si #X) or stannoxane (-Sn-O-Sn) groupings in the molecule.  Tertiary amines may be used as catalysts and water-soluble or basic silicones as stabilizers, in addition to the silicon compound containing tetravalent tin.  Preferably the process is applied to the reaction of an organic polyisocyanate, water and an organic compound containing predominantly secondary hydroxyl groups. Halohydrocarbons such as dichlorodifluoromethane and trichlorofluoromethane can also be used as blowing agents.  As polyhydroxy compounds there listed condensation products of alkylene oxides, and reaction products of alkylene oxides with polyhydric alcohols or phenols, aliphatic or aromatic amines, aminoalcohols, castor oil, sugar.  Hydroxypolyesters containing secondary hydroxyl groups as well as compounds containing active hydrogen in amino, carboxyl, -SH, urethane, urea and amide groups, and also the conventional polyethers, polythioethers and polyacetals can be used. The catalyst-stabilizers can contain any organic radicals which may be aliphatic, aromatic or heterocyclic and may contain unsaturation or such substituents as halogeno, nitro, alkoxy, carboxy, dialkylamino, mercapto, carbonyl, thiocarbonyl, hydroxy, phosphate or phosphoryl substituents.  The silicon compounds comprise units of the type <FORM:0935615/V/1> wherein m and n each are 0, 1, 2 or 3, R and R1 are monovalent organic radicals; R11 is a radical derived from a polyhydric alcohol and is joined to the other units by oxygen bridges.  They include compounds having the recurring group <FORM:0935615/V/2> where a, b and c are integers and b may also be zero.  The preparation of the silicon tin compounds is described (see Group IV(a)).  In Example (1) a foam is prepared by reacting a linear polypropylene glycol, toluene-2, 4 and 2, 6-diisocyanates and water in the presence of a siloxane-alkylene oxide copolymer, permethylated N-aminoethylpiperazine and a stanno-siloxane prepared by the interesterification of tetraethoxy-1, 3-diphenyldisiloxane and dibutyltin diacetate, Examples of the preparation of other catalysts and their use are also given. Specifications 769,682, 884,781, and 930,635 are referred to.