Patent GB-807377-A (GB)
Title: Improvements in or relating to polyurethane resins
IPC: C08G18/10
Filed: 1956-05-17
Abstract: <PICT:0807377/III/1> A method of forming a polyurethane resin foam upon a solid surface by the reaction of a diisocyanate, a polyester of an alcohol containing at least two hydroxyl groups and a dicarboxylic acid, and water, comprises spraying from separate orifices (A) a liquid, anhydrous, sprayable, relatively stable prepolymer of a diisocyanate and such a polyester and (B) a liquid, water-containing dispersion of such a polyester, impinging the two sprays upon the said surface and effecting foaming and curing of the resultant mixture.  The prepolymer is prepared by preliminarily reacting about 30 to about 70 per cent, usually 50 per cent of the polyester with the diisocyanate.  By the term "relatively stable" is meant that the prepolymer is capable of storage for a period of one day.  The polyester components of the prepolymer and of the polyester mixture containing the water may be the same or different.  Such polyesters may be those prepared from phthalic, isophthalic, terephthalic, adipic, sebacic and azelaic acids, with dihydric alcohols such as propylene, dipropylene, ethylene, diethylene and polyethylene glycols, usually together with an alcohol containing at least 3 hydroxy groups selected from glycerol, pentaerythritol, trimethylol-ethane or propane and mannitol.  The diisocyanate may be of the formula OCN-R-NCO, where R is aromatic, heterocyclic, aliphatic or a mixed group comprising moieties from two or more of these, e.g. diphenyl, triphenyl, chlorophenyl, ethylene, 1,4-tetramethylene, p-phenylene, p-tolylene and hexamethylene diisocyanates.  In the preparation of the prepolymer there may be used as catalysts N-alkylmorpholine, trimethyl or triethylamine, dialkylamino-alcohols and tertiary amines in which the hydrocarbon chains contain 10 to 18 carbon atoms each, quaternary ammonium compounds which liberate amines in situ and salts of, e.g., N-methyl-morpholine, with acetic acid.  Excess N-methyl-morpholine may be used to reduce the viscosity of the prepolymer.  Component (B) may contain also a catalyst and emulsifying agents, e.g. a blend of a polycarboxylic acid compound and a sulphonated fatty oil acid, a reaction product of ethylene oxide and sorbitan monopalmitate or monostearate or an ethylene oxide/alkylphenol reaction product.  In place of water a hydrated salt may be used. In preliminary examples for the preparation of polyesters suitable for use in components A and B there are reacted (A) adipic acid, diethylene glycol and glycerol; (B) phthalic anhydride, adipic acid and trimethylol propane; (C) and (D) adipic acid, phthalic anhydride and glycerol; (E) adipic acid, phthalic acid, oleic acid and glycerol; (F) adipic acid, phthalic anhydride, diethylene glycol and pentaerythritol; (G) phthalic anhydride, adipic acid and trimethylol propane.  In examples of the process of the invention: (1) there are employed as component A:-a prepolymer from polyester of example A, tolylene diisocyanate, N-methylmorpholine and emulsifier, and as component B:-polyester of Example A, N-methylmorpholine, emulsifier and water; (2) a phenol-formaldehyde resin is incorporated with a polyester such as that of Example A (either by mixing or by adding to the polyester-forming reactants) for use in a process such as that described in Example (1).  This reduces the tendency of the foamable mixture to form large bubbles between the resin and the supporting surface.  In one embodiment (Fig. 1) prepolymer and a dispersion of polyester in pressure pots 50 and 51 (which are connected by lines 54 and 56 to a source 59 of gas under pressure) pass through pumps 63 and 64, heat-exchangers 68 and 69, and hose connections 73 and 74 to spray gun tubes 86 and 87.  The motors of the pumps are controlled by a pressure-operated switch 65 which is opened when the line-pressure rises due to stopping of the spray-gun.  The heat-exchangers and the jackets 76 and 77 of the hose connections 73 and 74 are supplied with heat-transfer medium, e.g. at 160 DEG  F.  The spray-gun comprises a pair of convergent nozzle tubes attached to a single handle and supplied through tube 88 with gas under pressure.ALSO:A method of forming a polyurethane resin foam upon a solid surface by the reaction of a diisocyanate, a polyester of an alcohol containing at least two hydroxyl groups and a dicarboxylic acid, and water, comprises spraying from separate orifices (A) a liquid, anhydrous, sprayable, relatively stable prepolymer of a diisocyanate and such a polyster and (B) a liquid, water-containing dispersion of such a polyester, impinging the two sprays upon the said surface and effecting foaming and curing of the resultant mixture.  The prepolymer is prepared by preliminarily reacting about 30 to about 70 per cent, usually approximately 50 per cent, of the polyester with the diisocyanate. By the term "relatively stable" is meant that the prepolymer is capable of storage for a period of one day.  The polyester components of the prepolymer and of the polyester mixture containing the water may be the same or different.  Such polyesters may be those prepared from phthalic, isophthalic, terephthalic, succinic, adipic, sebacic and azelaic acids, with dihydric alcohols such as propylene, dipropylene, ethylene, diethylene and polyethylene glycols, usually together with an alcohol containing at least 3 hydroxy groups selected from glycerol, pentaerythritol, trimethylol-ethane or -propane and mannitol.  The diisocyanate may be of the formula OCN-R-NCO where R is aromatic, heterocyclic, aliphatic or a mixed group comprising moieties from two or more of these, e.g. diphenyl, triphenyl, chlorophenyl, ethylene, 1,4-tetramethylene, p-phenylene, p-tolylene, and hexamethylene diisocyanates.  In the preparation of the prepolymer there may be used as catalysts N-alkyl-morpholine, trimethyl or triethylamine, dialkylamino-alcohols and tertiary amines in which the hydrocarbon chains contain 10 to 18 carbon atoms each, quaternary ammonium compounds which liberate amines in situ, and salts of, e.g., N-methyl morpholine with acetic acid.  Excess N-methyl morpholine may be used in reducing the viscosity of the prepolymer. Component (B) may contain also a catalyst and emulsifying agents (e.g. a blend of a polycarboxylic acid compound and a sulphonated fatty oil acid, a reaction product of ethylene oxide and sorbitan monopalmitate or monostearate or an ethylene oxide/alkyl phenol condensation product.  In place of water an hydrated salt may be used.  In preliminary examples for the preparation of polyesters suitable for use in components A and B there are reacted (A) adipic acid, diethylene glycol and glycerol; (B) phthalic anhydride, adipic acid and trimethylol propane; (C) and (D) adipic acid, phthalic anhydride and glycerol; (E) adipic acid, phthalic anhydride, oleic acid and glycerol; (F) adipic acid, phthalic anhydride, diethylene glycol and pentaerythritol; (G) phthalic anhydride, adipic acid and trimethylol propane.  In examples of the process of the invention (1) there are employed as component A:-a prepolymer from polyester of Example A, tolylene diisocyanate, N-methylmorpholine and emulsifier, and as component B:-polyester of Example A, N-methyl morpholine, emulsifier and water; (2) a phenolformaldehyde resin is incorporated with a polyester such as that of Example A (either by mixing or by adding to the polyester-forming reactants) for use in a process such as described in Example (1).  This reduces the tendency of the foamable mixture to form large bubbles between the resin and the supporting surface. Illustrative embodiments of apparatus for applying foams are described.  In one a spray apparatus is depicted comprising a pair of convergent nozzle tubes to which components A and B, respectively, are supplied by variable delivery pumps.  Droplets of spray from each nozzle intermingle completely or partly on the way to the surface sprayed.  Radiant may be applied to accelerate the curing.  A second diagram shows a flow sheet of a system for supplying the spray with the components A and B, and includes a pressure-operated switch connected to the fluid lines arranged to switch off the current to the motor pumps when the pressure rises due to the stopping of the spraygun.