GB927004A - Improvements in catalysts - Google Patents

Abstract

Catalyst compositions comprise a crystalline molecular sieve having sorbed therein an organic tin compound. The catalysts may be prepared by heating the molecular sieve to drive off substantially all the water of hydration and placing the activated molecular sieve and the organic tin compound in a vacuum desiccator. The tin compound may be a compound of formula R3SnX, R4Sn, R2SnX2, RSnX3, R2SnY, RSnOOR1, R(SnOOR1)2, <FORM:0927004/III/1> , or R2Sn(YRX)2 where R is a hydrocarbon or substituted hydrocarbon radical, R1 is a hydrocarbon or substituted hydrocarbon radical, hydrogen or metal, X is hydrogen, halogen, hydroxyl, amino, alkoxy, substituted alkoxy, acyloxy, substituted acyloxy, acyl or organic residues connected to tin through a sulphide link, and Y represents oxygen or sulphur; a stannous acylate; or a stannous alkoxide. Long lists of suitable tin compounds are given. The molecular sieve may be a synthesized zeolite of formula M 2/n O:Al2O3: wSiO2:yH2O where M is a cation of valence n, and w and y are the moles of silica and water, or a natural zeolite such as mordenite, gmelinite, clinoptilolite, chabazite, erionite, analcite and faujasite. Catalysts comprising dibutyl tin laurate, tributyl tin acetate, tetrabutyl tin and butyl tin trichloride sorbed on molecular sieves are described. The catalysts may be used in the reaction of compounds containing active hydrogen with organic isocyanates and thioisocyanates. Specifications 777,232, 777,233, 804,369, 868,846, 880,702, 882,451, 909,264, 909,265 and 909,266 are referred to.ALSO:Urethane resins, particularly cellular urethane resins, may be prepared by reacting polyisocyanates or polyisothiocyanates with active hydrogen containing compounds in the presence of a catalyst comprising a crystalline zeolite molecular sieve having sorbed therein an organic tin compound. The tin compound may be of formula R3SnX, R4Sn, R2SnX2, RSnX3, R2SnY, RSnOOR1, R(SnOOR1)2, <FORM:0927004/IV(a)/1> or R2Sn(YRX)2 where R is a hydrocarbon or substituted hydrocarbon radical, R1 is a hydrocarbon or substituted hydrocarbon radical, hydrogen or metal, X is hydrogen, halogen, hydroxyl, amino, alkoxy, substituted alkoxy, acyloxy, substituted acyloxy, acyl or organic residues connected to tin through a sulphide link, and Y is oxygen or sulphur; a stannous acylate; or a stannous alkoxide. Foams may be prepared by a one-step method involving simultaneous isocyanate extension of the active hydrogen compound, cross-linking and foam formation, or by a prepolymer technique involving partial extension of the active hydrogen compound with excess isocyanate and subsequent foaming and cross-linking by adding excess isocyanate, catalyst and water which may be absorbed on a molecular sieve. Alternatively foaming may be effected by means of blowing agents, e.g. trichloromonofluoromethane, dichlorodifluoromethane, dichlorofluoromethane, 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoro-2,2-dichloroethane, and 1,1,1-trifluoro, 2-chloro-2-fluoro, 3,3-difluoro, 4,4,4-trifluorobutane. Many suitable tin compounds, active hydrogen containing compounds and polyisocyanates are listed and examples describe the preparation of foams from a propylene oxide adduct of 1,1,3-tris(hydroxyphenyl) propane, a siloxane oxyalkylene copolymer surfactant and (1 and 7) dibutyl tin dilaurate loaded zeolite, water loaded zeolite and tolylene diisocyanate; (2 and 8) dibutyl tin dilaurate loaded zeolite, trichlorofluoromethane and tolylene diisocyanate; dibutyl tin dilaurate loaded zeolite, a prepolymer of a propylene oxide adduct of 1,1,3-tris(hydroxyphenyl) propane and diisocyanate and (4) water loaded zeolite and (5) trichlorofluoromethane; and (6) tolylene diisocyanate, trichlorofluoromethane and zeolite loaded with dibutyl tin dilaurate, tributyl tin acetate, tetrabutyl tin and butyl tin trichloride. Specification 777,232, 777,233, 804,369, 868,846, 880,702, 882,451, 909,264, 909,265 and 909,266 are referred to.ALSO:Urethane resin foams may be prepared by reacting polyisocyanates or polyisothiocyanates with active hydrogen containing compounds in the presence of a catalyst comprising a crystalline zoolite molecular sieve having sorbed therein an organic tin compound. The tin compound may be of formula R2SnX2, RSnX3, R2SnY, R3SnX, R4Sn, RSnOO R1, R(SnOOR1)2, <FORM:0927004/V/1> or R2 Sn(YRX)2 where R is a hydrocarbon or substituted hydrocarbon radical, R1 is a hydrocarbon or substituted hydrocarbon radical, hydrogen or metal, X is hydrogen, halogen, hydroxyl, amino, alkoxy, substituted alkoxy, acyloxy, substituted acyloxy, acyl or organic residues connected to tin through a sulphide link, and Y is oxygen or sulphur; a stannous acylate; or a stannous alkoxide. Foams may be prepared by a one-step method involving simultaneous isocyanate extension of the active hydrogen compound, cross-linking and foam formation, or by a prepolymer technique involving partial extension of the active hydrogen compound with excess isocyanate and subsequent foaming and cross-linking by adding excess isocyanate, catalyst and water, which may be absorbed on a molecular sieve. Alternatively foaming may be effected by means of a blowing agent, e.g. trichlorofluoromethane, dichlorodifluoromethane, dichlorofluoromethane, 1, 1- dichloro-1-fluoroethane, 1-chloro,- 1, 1- difluoro, 2, 2-dichloroethane, and 1, 1, 1- trifluoro,- 2-chloro-2-fluoro, 3, 3-difluoro, 4, 4, 4- trifluoro butane. Many suitable tin compounds, active hydrogen compounds and polyisocyanates are listed and examples describe the preparation of foams from a propylene oxide adduct of 1, 1, 3-tris (hydroxyphenyl) propane, a siloxane oxyalkylene copolymer surfactant and (1 and 7) dibutyl tin dilaurate loaded zeolite, water loaded zeolite and tolylene diisocyanate; (2 and 8) dibutyl tin dilaurate loaded zeolite, trichlorofluoro methane and tolylene diisocyanate; dibutyl tin dilaurate loaded zeolite, a prepolymer of a propylene oxide adduct of 1, 1, 3- tris (hydroxyphenyl) propane and diisocyanate and (4) water loaded zeolite and (5) trichlorofluoromethane; and (6) tolylene diisocyanate, trichlorofluoromethane and zeolite loaded with dibutyl tin dilaurate, tributyl tin acetate, tetrabutyl tin and butyl tin trichloride. Specifications 777,232, 777,233, 804,369, 868,846, 880,702, 882,451, 909,264, 909,265 and 909,266 are referred to.