Patent GB-898724-A (GB)
Title: Improvements in and relating to isocyanate or isothiocyanate reactions
IPC: C08G18/66
Filed: 1959-11-20
Abstract: A method for accelerating the reaction of an organic compound containing -NCY groups (in which Y is an oxygen or sulphur atom) with polyfunctional compounds such as polyethers, polyesters and polyesteramides containing active hydrogen atoms comprises conducting the reaction in the presence of a catalyst composition comprising an organic tin compound having at least one direct carbon to tin bond and a tertiary amine.  The products may be foamed or non-foamed polyurethanes.  The tin compounds specified are of the classes described in Specifications 892,136 and 892,137.  Specified amines which are unreactive with isocyanate groups are triethylamine, tributylamine, trioctylamine, N-methyl-, ethyl, octadecyl and cocomorpholines, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N1-bis-(21-hydroxypropyl) piperazine, N,N,N1,N1-tetramethyl-ethylene or 1,3-propanediamine, triethylene diamine, 1,4-bis(2-hydroxypropyl) methylpiperazine, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, bis(N,N-diethylaminoethyl) adipate, N-ethyl-hexamethylene diamine, N - ethylpiperidine, a  - methylbenzyldimethylamine, dimethylhexadecylamine, 3-methylisoquinoline, dimethylcetylamine and isocyanates and organometallic tin compounds containing tertiary nitrogen atoms.  Amines reactive with isocyanate groups are triethanolamine, triisoropanolamine, N-methyl- and -ethyl diethanolamines, polyoxyalkylene polymers and copolymers started with triethanolamine, triisopropanolamine, ethylenediamine, ethanolamine and diethylenetriamine, polyesters based on tertiary ethanolamines and polycarboxylic acids containing tertiary nitrogen atoms.  The polyethers can be linear or branched polymers or copolymers (including block copolymers).  They may be propylene oxide adduct of polyols (including novolaks, castor oil and alkyl glucosides), polyamines and amino-alcohols.  Lists of starting materials for suitable polyesters and polyesteramides are given. The organic polyisocyanates and isothiocyanates are those of the formula R(NCY)x in which x is 2 or more and R can be hydrocarbon or can be of the formula R-Z-R- where Z is -O-, -O-R-, -CO-, -CO2-, -S-, -SRS- or -SO2-.  Dimers and trimers of isocyanates and such compounds as ethylphosphonic diisocyanate, phenylphosphonous diisocyanate, compounds containing a =Si-NCY group, and isocyanates derived from sulphonamides [R(SO2NCO)2] can also be used.  In producing foamed polyurethanes the "prepolymer" and "semi or quasi prepolymer" techniques can be used.  In an example (1) a polyester prepared by reacting pentaerythritol, mixed methyl-epsilon-caprolactones and dibutyl tin oxide is reacted with 2,4-tolylene diisocyanate (containing ethoxylated cellulose), an emulsifier (comprising condensation product of a dimethyl polysiloxane and a butoxy end-blocked polyoxyalkylene glycol), and N-methylmorpholine. After reaction at room temperature a foam is produced by adding water to the product.ALSO:A method for accelerating the reaction of an organic compound containing an -NCY group in which Y is an oxygen or sulphur atom with a compound containing an active hydrogen atom as determined by the Zerewitinoff method comprises conducting the reaction in the presence of a catalyst composition comprising an organic tin compound having at least one direct carbon to tin bond and a tertiary amine. The tin compounds specified are of the classes described in Specifications 892,136 and 892,137.  Lists of suitable amines are given.  Reactions described are of phenyl isocyanate with (a) butanol, in the presence of dibutyl tin diacetate, dioctyl tin oxide tetrabutyl tin, and dibutyl tin dichloride, alone or in the presence of triethylamine, N-methyl morpholine or triethylene diamine; (b) water in the presence of dibutyltin diacetate alone or mixed with triethylamine; (c) diphenyl urea and the same catalysts as in (b). Other isocyanates mentioned are those of the formula R(NCY)x in which x is 2 or more and R can be hydrocarbon or can be of the formula -R-Z-R-where Z is -O-, -CO-, -CO2-, -S-, -SRS- or -SO2-.  Dimers and trimers of isocyanates and such compounds as ethylphosphonic diisocyanate, phenyl-phosphonous diisocyanate, compounds containing a=SiNCY group and isocyanates derived from sulphonamides, such as R(SO2NCO)2 can also be used.ALSO:A method for accelerating the reaction of an organic compound containing -NCY groups (in which Y is an oxygen or sulphur atom) with polyfunctional compounds such as polyethers, polyesters and polyesteramides, containing active hydrogen atoms comprises conducting the reaction in the presence of a catalyst composition comprising an organic tin compound having at least one direct carbon to tin bond and a tertiary amine.  The products may be foamed or non-foamed polyurethanes.  The tin compounds specified are of the classes described in Specifications 892,136 and 892,137.  Specified amines which are unreactive with isocyanate groups are triethylamine, tributylamine, trioctylamine, N-methyl-, ethyl, octadecyl and coco-morpholine, N-methyldiethanolamine, N, N1-bis-(2-hydroxypropyl) piperazine, N, N, N1N1-tetramethyl-ethylene or 1, 3-propane diamine, triethylene diamine, 1, 4-bis (2-hydroxy-propyl) methylpiperazine, N, N-dimethylbenzylamine, N, N-dimethyl-cyclohexylamine, bis(N, N-diethylaminoethyl) adipate, N-ethyl hexamethylene diamine, N-ethylpiperidine, a -methylbenzyldimethyl amine, dimethylhexadecylamine, 3-methylisoquinoline, dimethylcetylamine and isocyanates and organometallic tin compounds containing tertiary nitrogen atoms. Amines reactive with isocyanate groups are triethanolamine, triisopropanolamine, N-methyl and ethyl diethanolamines, polyoxyalkylene polymers and copolymers started with triethanolamine, triisopropanolamine, ethylene diamine, ethanolamine and diethylene triamine, polyesters based on tertiary ethanolamines and polycarboxylic acids containing tertiary nitrogen atoms.  The polyethers can be linear or branched polymers or copolymers (including block copolymers).  They may be propylene oxide adducts of polyols, (including novolaks, castor oil and alkyl glucosids), polyamines and amino-alcohols.  Lists of starting materials for suitable polyesters of and polyester-amides are given.  The organic polyisocyanates and isothiocyanates are those of the formula R(NCY)x in which x is 2 or more R can be hydrocarbon or can be of the formula R-Z-R where Z is -O-, -OR-, CO, -CO2-, -S-, -SRS- or -SO2-.  Dimers and trimers of isocyanates and such compounds as ethylphosphonic diisocyanate, phenyl-phosphonous diisocyanate, compounds containing a =Si-NCY group and isocyanates derived from sulphonamides can be used also.  In producing foamed polyurethanes the "prepolymer" and "semi or quasi prepolymer" techniques can be used.  In an Example (1) a polyester prepared by reacting pentaerythritol, mixed methyl-epsilon caprolactones and dibutyltin oxide is reacted with 2, 4-tolylene diisocyanate (containing ethoxylated cellulose) an emulsifier (comprising a polysiloxane and an end-blocked polyoxy-alkylene glycol) and N-methyl morpholine.  After reaction at room temperature a foam is produced by adding water to the product.