GB843841A - Polyurethane foams - Google Patents

Abstract

The invention comprises solutions in organic monomeric polyisocyanates of organic polymeric polyisocyanates which have at least one isocyanuric acid ring. It also comprises a process for the production of a polyurethane plastic by reacting an organic compound having at least two hydrogen atoms capable of reacting with a polyisocyanate with a solution in a monomeric organic polyisocyanate of an organic polymeric polyisocyanate which has at least one isocyanuric acid ring. The polyisocyanate polymer can be prepared by heating a monomeric organic polyisocyanate in the presence of a catalyst containing a tertiary amine and a carbamic acid ester mono-substituted on the nitrogen atom. The carbamic acid ester may be added as such or may be formed by adding to the reaction mixture for instance methanol, ethanol, butanol or benzyl alcohol. A mono-isocyanate may be included with the polyisocyanate in the polymerization mixture. provided the product has more than one NCO group per molecule. Before the polymerization the monomeric polyisocyanate may be reacted with compounds such as alcohols (saturated or unsaturated), phenols, glycols, polyfunctional alcohols, primary or secondary mono- or polyfunctional amines, amino-alcohols or aminophenols, provided that at least 25% unreacted-NCO groups are left. Polymerization can also be effected by the process of German Specification 951,168 or at elevated temperatures by the action of such compounds as tin tetrachloride, iron chloride and the copper or zinc complex of the Schiff's bases from stearylamine and salicyl aldehyde. Phenyl, tolyl, p-nitrophenyl, p-chlorophenyl, a -naphthyl, and benzyl isocyanates, tetra, hexa and decamethylene, m- and p-xylylene, 1- tertiary butyl -3, 5-xylylene, 4, 6-dimethyl -1, 3-xylylene, cyclohexyl-1, 4, dicyclohexyl methane- 4, 41, m- or p-phenylene, toluene, 2, 6- diethylbenzene-1, 4 diphenylmethane, diphenyldimethylmethane-4, 41, 3, 31-dimethoxydiphenylmethane and naphthalene -1, 5- diisocyanates, and 1- methyl benzene -2, 4, 6-, and triphenylmethane triisocyanates are suitable for polymerization. The polymer can be dissolved in 1-methyl -phenyl 2, 4-, 2, 6- or 3, 5- diisocyanate, tetra hexa or decamethylene diisocyanate, m- or p-xylylenediisocyanate or 2, 4, 41-diphenylether triisocyanate. In the preparation of polyurethanes the polyisocyanate solution can be reacted with polyesters polyamides, polyalkylene ether or thioether glycols, ethers from polyols and styrene oxide, epoxy resins, hydrogenation products of olefincarbon monoxide copolymers and phenolformaldehyde resins reacted with alkylene oxides. The polyesters may contain heterocyclic rings and double or triple bonds. In preparing foams a one or two stage process can be used. Fire proofing agents and plasticizers such as trichloralkyl phosphate, chlorinated paraffins and esters can be added. In an example (1) a mixture of an adipic acid/phthalic anhydride/hexanetriol polyester and an adipic acid/hexantriol/1, 3-butylene glycol polyester is mixed with adipic acid diethyl aminoethyl ester and aqueous sodium salt of castor oil sulphate and converted to a foam by adding polymerized toluylene -2, 4-diisocyanate dissolved in monomeric toluylene diisocyanate. The polymer is obtained by heating toluylene -2, 4- diisocyanate in the presence of ethanol and a reaction product of phenyl isocyanate and methyl diethanolamine. In other examples there are used polyesters prepared from reactants selected additionally from glycerine, diethylene glycol and oleic acid; a hydrogenated ethylenepropylenecarbon monooxide polymer; or a polypropylene ether glycol. Other polyisocyanates illustrated are obtained by heating in the presence of tertiary amine from methyl diethanolamine and phenyl isocyanate a reaction product still containing NCO groups of toluylene diisocyanate with (6) 2, 2, 4- trimethylpentenrediol (8) 4, 41-dihydroxy-diphenylmethane (9) 2, 2-diemethyl propanediol 1-, 3; (10) oleyl alcohol; (11) hydrogenated 4, 41- dioxydiphenyl dimethylmethane.ALSO:The invention comprises solutions in organic monomeric polyisocyanates of organic polymeric polyisocyanates which contain at least one isocyanueric acid ring. Such solutions are useful in the preparation of polyurethane plastics, particularly foamed products (see Groups IV(a) and V). The polyisocyanate polymer can be prepared by heating a monomeric polyisocyanate in the presence of a catalyst containing a tertiary amine and a carbamic acid ester mono - substituted on the nitrogen atom. The carbamic acid ester may be added as such or may be formed by adding to the reaction mixture for instance methanol, ethanol, butanol or benzyl alcohol. A monoisocyanate may be included with the polyisocyanate in the polymerisation mixture, provided that the product has more than one NCO group per molecule. Before the polymerisation the monomeric polyisocyanate may be reacted with compounds such as alcohols (saturated or unsaturated), phenols, glycols, polyfunctional alcohols, primary or secondary mono- or polyfunctional amines, aminoalcohols or aminophenols, provided that at least 25% free NCO groups are left. Polymerisation can also be effected by the process of German Specification 951,168 or by the action at elevated temperatures of such compounds as tin tetrachloride, iron chloride and the copper or zinc complex of the Schiff's base from stearylamine and salicylaldehyde. Phenyl, tolyl, p-nitrophenyl, p-chlorophenyl, a -naphthyl and benzyl isocyanates, tetra, hexa and decamethylene, m and p-xylylene, 1-tertiary butyl-3, 5-xylylene, 4,6-dimethyl- 1,3-xylylene, cyclohexyl-1,4, dicyclohexylmethane -4,41, m or p-phenylene, tolylene, 2.6-diethylbenzene - 1,4-, diphenylmethane, or diphenyldimethylmethane -4,41, 3,31-dimethoxydiphenylmethane and naphthalene-1,5-diisocyanates and 1-methylbenzene-2,4,6 and triphenylmethane triisocyanate are suitable for polymerizations. The polymer can be dissolved in 1-methyl-phenyl-2,4, 2,6 or 3,5-diisocyanate tetra, hexa or decamethylene diisocyanate, m- or p-xylylene diisocyanate or 2,3,41 - diphenylether triisocyanate. In example (1) polyisocyanates are prepared by heating tolylene-2,4-diisocyanate in the presence of ethanol and a reaction product of phenyl isocyanate and methyl diethanolamine. Other polymeric polyisocyanates are prepared by heating in the presence of a tertiary amine from methyl diethanolamine a phenyl isocyanate a reaction product still containing NCO groups of toylene diisocyanate with (6) 2,2,4-trimethylpentenediol; (8) 4,41-dihydroxydiphenylmethane; (9) 2,2-dimethylpropanediol-1,3; (10) oleyl alcohol; (11) hydrogenated 4,41-dioxydiphenyl dimethylmethane.ALSO:A process for the production of a polyurethane plastic comprises reacting an organic compound having at least two hydrogen atoms capable of reacting with a polyisocyanate with a solution in a monomeric organic polyisocyanate of an organic polymeric polyisocyanate which has at least one isocyanuric acid ring. The process is of advantage in the production of foamed products. The polyisocyanate polymer can be prepared by heating a monomeric organic polyisocyanate in the presence of a catalyst containing a tertiary amine and a carbamic acid ester mono-substituted on the nitrogen atom (see Group IV(b)). A monoisocyanate may be included with the polyisocyanate in the polymerisation mixture. Before the polymerisation the monomeric polyisocyanate may be reacted with compounds such as alcohols, primary or secondary amines, amino-alcohols, or amino-phenols provided that at least 25% unreacted NCO groups are left. Phenyl, tolyl, p-nitrophenyl, p-chlorophenyl, a -naphthyl, and benzyl isocyanates, tetra, hexa, and decamethylene, m- and p-xylylene, 1-tertiary butyl-3, 5-xylylene, 4,6-dimethyl-1, 3-xylylene, cyclohexyl-1,4, dicyclohexylmethane-4, 41, m- or p-phenylene, tolylene, 2, 6-diethylenbenzene1, 4-, diphenylmethane, diphenyldmethylmethane-4, 41, 3, 31-dimethoxydiphenylmethane and naphthalene-1, 5- diisocyanates and 1-methylbenzene-2, 4, 6,- and triphenylmethane triisocyanate are suitable for polymerisation. The polymer can be dissolved in 1-methylphenyl- 2, 4, 2, 6-, or 3, 5- diisocyanate, tetra orhexa ordecamethylene diisocyanate, m- or p-xylylenediisocyanate or 2, 4, 41-diphenyl-ether triisocyanate. In the preparation of polyurethanes the polyisocyanate solution can be reacted with ethers from polyols and styrene oxide, polyesters, polyamides, polyalkylene ether or thioether glycols, epoxy resins, hydrogenated products of olefin-carbon monoxide copolymers and phenolformaldehyde resins reacted with alkylene oxides. The polyesters may contain heterocyclic rings or double or triple bonds. In preparing foams a one or two stage process can be used. Fire-proofing agents and plasticisers such as trichloroalkyl phosphate, chlorinated paraffins and esters can be added. In an example (1) a mixture of an adipic acid/phthalic anhydride/hexanetriol/polyester and an adipic acid/hexanetriol/1, 3-butylene glycol polyester is mixed with adipic acid diethylaminoethyl ester and aqueous sodium salt of castor sulphate and converted to a foam by adding polymerised toluylene -2, 4-diisocyanate dissolved in monomeric toluylene diisocyanate. The polymer is obtained by heating toluylene-2, 4-diisocyanate in the presence of ethanol and a reaction product of phenyl isocyanate and methyl diethanolamine. In other examples there are used polyesters prepared from reactants selected additionally from glycerine diethylene glycol andolein acid; a hydrogenated ethylene-propylene-carbon monoxide polymer; or a polypropylene ether glycol. Other polyisocyanates are obtained by heating in the presence of a tertiary amine from methyl diethanolamine and phenyl isocyanate a reaction product still containing NCO groups of toluylene diisocyanate with (6) 2, 2, 4-trimethylpentenediol; (8) 4, 41-