Patent GB-899805-A (GB)
Title: Halogen-containing polyurethane foams and method of preparation
IPC: C08G18/56
Filed: 1960-06-14
Abstract: 899,805. Polyurethanes containing halogen. HOOKER CHEMICAL CORPORATION. June 14, 1960 [June 22, 1959; Nov. 18, 1959], No. 20861/60. Class 2(5) [Also in Group V] A process for preparing a liquid resinous reaction product comprises reacting (1) one mole of the dicarboxylic acid adduct of hexahalocyclopentadiene and a dicarboxylic compound containing aliphatic carbon to carbon unsaturation wherein the halogen is chlorine, bromine, fluorine or mixtures thereof, and (2) at least four moles of an organic polyisocyanate. A fire resistant polyurethane foam is obtained by reacting the liquid resinous product with a hydroxyl containing polymeric material having a hydroxyl number between 30 and 650 which is (A) a polyester comprising the reaction product of a polyhydric alcohol and a polycarboxylic compound, (B) a polyether comprising the reaction product of a monomeric 1:2-epoxide and a polyhydric alcohol or polycarboxylic acid, or (C) mixtures thereof; and (3) a foaming agent. Maleic, fumaric, itaconic and citraconic acids are specified for the preparation of the adducts. The preferred adduct is 1,4,5,6,7,7-hexachloro-(2.2.1)-5-heptene- 2,3-dicarboxylic acid; others are listed. In preparing the liquid resinous product the particle size of the adduct is preferably 1À68 mm. or smaller. Catalysts for the foamforming reaction are triethylamine, N-methyl morpholine, triethanolamine, antimony caprylate or naphthenate, antimonous chloride, dibutyl-tin dilaurate, tri-n-octyl tin oxide, hexabutyl di-tin, tributyl tin phosphate, or stannic chloride. Foaming agents are fluorochlorocarbons of b.p. 20‹ to 50‹C., water, a tertiary alcohol and concentrated acid, polymethylol phenols, dimethylol ureas, polycarboxylic acids and formic acid. For the preparation of the polyester there are specified aliphatic, cycloaliphatic, heterocyclic and aromatic alcohols containing 2 to 6 hydroxyl groups and optionally ester or halogen substituents and oxygen + sulphur atoms between carbons, and polycarboxylic acids which may be aliphatic, cycloaliphatic, aromatic or heterocyclic and saturated or unsaturated. Part or all of the acid and alcohol may be an adduct of hexahalocyclopentadiene. The polyethers employed are those obtained from polyhydric alcohols or polycarboxylic acids and such epoxides as alkylene oxides, epichlorhydrin, epibromohydrin, styrene oxide, glycidol, decylene oxide, triphenyl glycidyl silane, allyl glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl sulphide, glycidyl methyl sulphone, glycidyl acrylate, methacrylate, benzoate, acetate, octanoate, sorbate or allyl phthalate, phenyl-(p-octadecyloxybenzoyl) ethylene oxide and compounds of the formulae: glycidyl and (C 12 H 25 ) NH glycidyl. A polyhydric alcohol may be added to the reaction mixture. Monomeric 1,2-epoxide may be added to the isocyanate before the reaction. Examples employ such acids as 1,4,5,6,7,7-hexachloro - 2 - methylbicyclo - (2.2.1) - 5 - heptene- 2,3-dicarboxylic acid; 1,4,5,6,-tetrachloro-7,7-difluorobicyclo - (2.2.1) - 5 - heptene- 2, 3 - dicarboxylic acid and 1,4,5,6,7,7-hexecahlorobicyclo -(2.2.1)-5- heptene -2- acetic -2- carboxylic acid for the liquid resin preparation. The hydroxymaterial comprises poly-esters or alkylene oxide reaction products of similar acids.