| 摘要 |
A method for accelerating the reaction of an organic compound containing a reactive -NCY radical (in which Y is oxygen or sulphur), such as polyisocyanates or polyisothiocyanates, with a compound containing reactive hydrogen (such as polymers having at least two end groups containing reactive hydrogen) comprises conducting the reaction in the presence of an organic tin compound having at least one direct carbon to tin bond. Reaction in the presence of water gives a foamed product. The polymers may, for example, be polyoxyalkylene polyols, polyesters and lactone polymers. The types of tin compounds which are suitable are (A) tin compounds having four carbon to tin bonds, such as those containing hydrocarbon or substituted-hydrocarbon radicals and also addition products of alkyl, aryl, aralkyl tin hydrides with unsaturated organic compounds; (B) tin compounds having n carbon to tin bonds and 4-n bonds from tin to halogen or hydrogen atoms or hydroxyl groups; (C) tin compounds having two carbon to tin bonds and a double bond from tin to oxygen or sulphur; (D) tin compounds having n carbon to tin bonds and 4-n bonds from tin to oxygen, sulphur, nitrogen or phosphorus linking organic radicals; (E) polystannic compounds having carbon to tin bonds and preferably also bonds from tin to halogen, hydrogen, oxygen, sulphur, nitrogen or phosphorus. Lists of compounds in each class are given. In Examples (1) a lactone-ethylene oxide copolymer (prepared by reacting epsilon-caprolactone, ethylene oxide and ethylene glycol in the presence of boron trifluoride-diethyl etherate) is mixed with 2,4- and 2,6-tolylene diisocyanates. To the mixture are added, respectively, dibutyltin oxide, dioctyltin oxide and (for comparison) N-methyl morpholine, and the gelling times are determined; (2) m-xylylene diisocyanate is added to a mixture of an adipic acid-diethylene glycol polyester, water emulsifying agent and a benzene solution of dioctyltin oxide. The components react to give a foamed product; (3) in a similar process to (2) the starting material is a reaction product of epsilon-caprolactone, ethylene oxide and trimethylolpropane. Other examples of preparing foams, in a generally similar manner, are varied by employing (4) an epsilon-caprolactoneethylene oxide-glycol copolymer and dibutyltin diacetate; (5) dioctyltin oxide; (6) adipic acid-diethylene glycol polester, dibutyltin diacetate and 2,4- and 2,6-tolylene diisocyanates; (7) a polyester from adipic acid and 1,2,6-hexanetriol and dibutyltin dilaurate; (8) a prepolymer from polypropylene glycol and 2,4- and 2,6-tolylene diisocyanates, 1,2,6-hexanetriol, water, silicone oil and dibutyltin diacetate or dibutyltin dilaurate. In further Examples (9) 2,4- and 2,6-tolylene diisocyanates are added to a mixture of polypropylene glycol, ethanolamine and dibutyltin laurate. The paste obtained is heated at 70 DEG C. and then milled on a rubber mill to form an elastomer; (10) a prepolymer from castor oil and 2,4- and 2,6-tolylene diisocyanates is mixed in toluene with ethylene glycol and dioctyltin oxide and applied on a glass plate as a film and allowed to dry. Other polyisocyanates and polyisothiocyanates can be of the formula R(NCY)x in which x is 2 or more and R represents hydrocarbon radicals or radicals of the type -R-Z-R-where Z may be -O-, -O-R-O-, -CO-, -CO2-, -S-, -SRS- or -SO2-. Dimers or trimers and such compounds as ethylphosphonic diisocyanate, phenylphosphonous diisocyanate, isocyanates from sulphonamides and compounds containing a SiNCY group are also included. Other specified materials containing active-hydrogen are glycol, diethylene glycol, hexamethylene glycol, glycerol, hexanetriol, sorbitol, dextrin, starch, cellulose, polyvinyl alcohol, cellulose acetate, shellac, castor oil, polyvinyl acetals or ketals, polyacrylic acids, ethylene diamine, hexamethylene diamine, ethanolamines, polyesteramides, poly (hexamethylene adipamide), wool, proteins and materials such as glass and metal that have films of moisture on their surfaces. Specification 892,136 is referred to.ALSO:A method for accelerating the reaction of an organic compound containing a reactive -NCY radical in which Y is oxygen or sulphur with a compound containing reactive hydrogen comprises conducting the reaction in the presence of an organic tin compound having at least one direct carbon to tin bond. The types of tin compound which are suitable are (A) tin compounds having four carbon to tin bonds, such as those containing hydrocarbon or substituted hydrocarbon radicals and also addition products of alkyl, aryl and aralkyl tin hydrides with unsaturated organic compounds; (B) tin compounds having n carbon to tin bonds and 4-n bonds from tin to hydrogen or halogen atoms or hydroxyl groups; (C) tin compounds having two carbon to tin bonds and a double bond from tin to oxygen or sulphur; (D) tin compounds having n carbon to tin bonds and 4-n bonds from tin to oxygen, sulphur, nitrogen or phosphorus linking organic radicals; (E) polystannic compounds having carbon to tin bonds and preferably also bonds from tin to halogen, hydrogen, oxygen, sulphur, nitrogen or phosphorus. Lists of compounds in each class are given. Illustrated are catalysed reactions of phenyl isocyanate and methanol (in the presence of about 40 different tin compounds and also, for comparison, of p-toluene sulphonic acid, acetic acid, N-methyl morpholine, triethylamine, cobalt naphthenate sodium methoxide and ferric chloride); phenyl isocyanate and water; N,N1-diphenylurea and phenyl isocyanate; methanol, butanol and water, respectively with octadecyl isocyanate; 1-octyl isocyanate, 2-methylheptyl isocyanate and 1,1-dimethyl-hexyl isocyanate, respectively, with butanol; phenylisothiocyanate and butanol; 2,4-tolylene, hexamethyene and m-xylene diisocyanates and butanol. Also mentioned are isocyanates containing -O-, -O-R-O-, -CO-, -CO2-, -S-, -S-R-S-, or -SO2- linkages where R is a hydrocarbon radical, compounds containing a SiNCY group, and also ethyl phosphonic diisocyanate, phenylphosphonous diisocyanate, cyanic acid, thiocyanic acid, tributyl tin isocyanate and isocyanates derived from sulphonamides. Lists of other active hydrogen-compounds given include those having oxygen-hydrogen bonds; nitrogenhydrogen bonds; mercaptans; halogen acids; compounds containing active methylene groups; acetylenic compounds and dialkyl phosphonates. Tributyltin phosphorus dibutoxide is prepared by reacting in the presence of ammonia dibutoxy phosphorus chloride and the compound (C4H9)3SuNa (obtained by reacting tributyltin chloride with sodium). Specification 892,136 is referred to.ALSO:In the preparation of polyurethane foams by the reaction of polyisocyanates or polyisothiocyanates with a compound containing reactive hydrogen, such as polymers having at least 2 end groups containing reactive hydrogen, in the presence of water, the reaction is accelerated by the use of an organic tin compound having at least one direct carbon to tin bond as catalyst. The types of tin compounds which are suitable are (A) those having four carbon to tin bonds, such as those containing hydrocarbon or substituted hydrocarbon radicals and also addition products of alkyl, aryl or aralkyl tin hydrides with unsaturated organic compounds; (B) tin compounds having n carbon to tin bonds and 4-n bonds from tin to halogen or hydrogen atoms or hydroxyl groups; (C) tin compounds having 2 carbon to tin bonds and a double bond from tin to oxygen or sulphur; (D) tin compounds having n carbon to tin bonds and 4-n bonds form tin to oxygen, sulphur nitrogen or phosphorus linking organic radicals; (E) polystannic compounds having carbon to tin bonds and preferably also bonds from tin to halogen, hydrogen, oxygen, sulphur, nitrogen or phorphorus. Lists of compounds in each class are given. In Examples (2) m-xylylene diisocyanate is added to a mixture of an adipic acid-diethylene glycol polyester, water, emulsifying agent and benzene solution of dioctyltin oxide. The components react to give a foamed product; (3) in a similar process the starting material is a reaction product of epsilon-caprolactone, ethylene oxide and trimethylolpropane. Other examples of preparing foams, in a generally similar manner are varied by employing (4) an epsilon-caprolactone-ethylene oxide-glycol copolymer and dibutyltin diacetate; (5) dioctyltin oxide; (6) adipic acid-diethylene glycol polyester, dibutyltin discetate and 2,4- and 2,6-tolylene diisocyanates; (7) a polyester from adipic acid and 1,2,6,-hexanetriol and dibutyltin dilaurate; (8) a prepolymer from polypropylene glycol and 2,4- and 2,6-tolylene diisocyanates, 1,2,6-hexanetriol, water, silicone oil and dibutyltin diacetate or dibutiltin dilaurate. Other suitable reactants are of the formula R(NCY)x in which x is 2 or more and R represents hydrocarbon radicals or radicals of the type R-Z-R where Z may be -O-, -O-R-O-, -CO-, -CO2-, -S-, -SRS-, or SO2. Dimers or trimers and such compounds as ethylphosphonic diisocyanate, phenyl-phosphonous diisocyanate, isocyanates from sulphonamides and compounds containing a /snSiNCY group are also included. Specification 892,136 is referred to. |
