Patent GB-904700-A (GB)
Title: Halogen-containing polyurethane foams and method of preparation
IPC: C08G18/67
Filed: 1960-06-14
Abstract: A process for preparing a liquid resinous reaction product comprises reacting (1) one mole. of a halogen containing polyhydric alcohol which is the reaction product of (A) a hexahalocyclopentadiene and a dihydric alcohol containing aliphatic carbon to carbon unsaturation, wherein the halogen is chlorine, bromine or fluorine or a mixture thereof, or (B) decachlorotetrahydro-4,7-methanoindenone and a polyhydric alcohol containing at least three hydroxyl groups, and (2) at least four moles. of an organic polyisocyanate.  To prepare a foam the liquid resinous reaction product is reacted, together with a foaming agent, with a hydroxyl containing polymeric material having a hydroxyl number of between 30 and 650 which is either a polyester comprising the reaction product of a polyhydric alcohol and a polycarboxylic compound, or a polyether comprising the reaction product of a monomeric 1,2-epoxide and a polyhydric alcohol or polycarboxylic acid, or mixtures of the polyester and polyether.  The polyhydroxy compound may be the reaction product of an adduct of a hexahalocyclopentadiene and a polycarboxylic compound containing aliphatic carbon to carbon unsaturation with a polyhydric alcohol or with the 1,2-epoxide.  Foaming agents are low boiling solvents such as fluorochlorocarbons; water; a tertiary alcohol and concentrated acid; polymethylol phenols; dimethylol ureas, polycarboxylic compounds and formic acid. Catalysts for the foaming reaction are triethylamine, N-methylmorpholine, triethanolamine; antimony caprylate or naphthenate; antimonous chloride; dibutyl tin dilaurate, tri-n-octyl tin oxide hexabutyltin, tributyltin phosphate or stannic chloride.  Monomeric 1,2-epoxide may be added to the polyisocyanate prior to its reaction with the hexahalocyclopentadiene adduct. Antimony oxide, clay, calcium sulphate, ammonium phosphate, dyes, fibrous glass asbestos and synthetic fibres may be incorporated.  In typical Examples, (1) 1,4,5,6,7,7-hexachloro-2,3-bis-hydroxymethyl-bicyclo-(2.2.1) -5-heptane and 2,4-and 2,6-tolylene diisocyanates are reacted to give a liquid resin which (Example 3) is reacted with a mixture of polypropylene glycol, 1.2.6-hexanetriol, water, dibutyltin dilaurate and silicone oil to give a foamed product; (2) and (4) a foam is obtained by reacting the liquid resin from the butane triol adduct of decachloro-tetrahydro-4,7-methanoindenedione and toluene 2,4 and 2,6-diisocyanates with polypropylene glycol, silicone oil and water.ALSO:A process for preparing a liquid resinous reaction product comprises reacting (1) one mole of a halogen containing polyhydric alcohol which is the reaction product of (A) a hexahalocyclopentadiene and a dihydric alcohol containing aliphatic carbon to carbon unsaturation, wherein the halogen is chlorine, bromine or fluorine or a mixture thereof, or (B) decachlorotetrahydro -4, 7- methanoindenone and a polyhydric alcohol containing at least three hydroxyl groups, and (2) at least four moles of an organic polyisocyanate.  To prepare a foam the liquid resinous reaction product is reacted, together with a foaming agent, with a hydroxyl containing polymeric material having a hydroxyl number of between 30 and 650 which is either a polyester comprising the reaction product of a polyhydric alcohol and a polycarboxylic compound, or a polyether comprising the reaction product of a monomeric 1, 2- epoxide and a polyhydric alcohol or polycarboxylic acid, or mixtures of the polyester and polyether.  The polyhydroxy compound may be the reaction product of an adduct of a hexahalocyclopentadiene and a polycarboxylic compound containing aliphatic carbon to carbon unsaturation with a polyhydric alcohol or with the 1, 2- epoxide. Foaming agents are low boiling solvents such as fluorochloro carbons; water; a tertiary alcohol and concentrated acid; polymethylol phenols; dimethylol ureas, polycarboxylic compounds and formic acid. Catalysts for the foaming reaction are triethylamine, N-methylmorpholine, triethanolamine; antimony caprylate or naphthenate; antimonous chloride; dibutyl tin dilaurate, tri-n-octyl tin oxide, hexabutyl tin, tributyl tin phosphate or stannic chloride. Monomeric 1, 2- epoxide may be added to the polyisocyanate prior to its reaction with the hexahalocyclopentadiene adduct.  Antimony oxide, clay calcium sulphate, ammonium phosphate, dyes, fibrous glass, asbestos and synthetic fibres may be incorporated.  In typical examples (1) 1, 4, 5, 6, 7, 7- hexachloro -2, 3-bis-hydroxymethylbicyclo -(2.2.1) -5-heptene and 2, 4- and 2, 6- tolylene diisocyanates are reacted to give a liquid resin which (Example 3) is reacted with a mixture of polypropylene glycol, 1, 2, 6-hexanetriol water, dibutyltin dilaurate and silicone oil to give a foamed product; (2) and (4) a foam is obtained by reacting the liquid resin from the butane triol adduct of decachlorotetrahydro -4, 7- methano - indenedione and tolune 2, 4 and 2, 6- diisocyanates with polypropylene glycol, silicone oil and water.