Patent GB-1019778-A (GB)
Title: A process for the production of flame-resistant synthetic resins containing repeating urethane groups
IPC: C08G18/38
Filed: 1964-02-12
Abstract: Flame-resistant polyurethanes are prepared by reacting an organic polyisocyanate with an amino alcohol containing one or more halogeno aryl groups and having at least two reactive hydrogen atoms.  A polyhydroxy compound e.g. polyester, polyether, polythioether or polyacetal may be included in the reaction. The amino alcohol may be the condensation product of a halogeno aralkyl halide which contains at least one chlorine and/or bromine atom in the nucleus and at least one side chain containing a halogen atom (none of said side chains containing more than one halogen atom) with ammonia, hydrazine or a polyamine where condensation product has been further reacted with an alkylene oxide.  Alternatively the amino alcohol may be the reaction product of said halogeno or alkyl halide with an amino alcohol which contains at least two hydroxyl groups and at least one primary or secondary amino group in the molecule.  Suitable polyisocyanates are specified including phosphorus, halogen and sulphur containing isocyanates and masked isocyanates.  Foams may be produced by incorporating water, azo compounds, low boiling hydrocarbons or halogenated hydrocarbons or halogenated hydrocarbons e.g. vinylidene chloride as a blowing agent. Catalysts specified are triethylamine, dimethylbenzylamine, 1 - dimethylamino - 3 - ethoxypropane, tin acylates or molybdenum glycollate. Emulsifiers may also be included. In typical examples: (1) an amino alcohol derived from ethylene diamine, trichlorobenzyl chloride and propylene oxide was mixed with propoxylated trimethylolpropane, permethylated aminoethylpiperazine and polysiloxane surfactant and foamed with diphenylmethane 4:41 diisocyanate and Cl3 FC (15). An aminoalcohol derived from hydrazine hydrate, trichlorobenzylchloride and 1-butene oxide was mixed with a polyester of adipic acid, phthalic anhydride, oleic acid and trimethylol propane and foam with diphenylmethane 4:41-diisocyanate, siloxane and sodium castor oil sulphate.ALSO:Aminoalcohols may be prepared by reacting the condensation product of a halogenoaralkyl halide which contains at least one chlorine and/or bromine atom in the nucleus and at least one side chain containing a halogen atom (none of said side chains containing more than one halogen atom) and ammonia, hydrazine or a polyamine with an alkylene oxide. Alternatively the aminoalcohol may be the reaction product of the said halogenoaralkyl halide with an aminoalcohol which contains at least two hydroxyl groups and at least one primary or secondary amino group in the molecule.  Halogenoaralkyl halides specified are: 2-, 3- or 4-chlorobenzyl chloride, 2 : 6- or 3 : 4-dichlorobenzyl chloride, commercial trichlorobenzychlorides, tetra- and pentachlorobenzyl chlorides, 2-bromobenzyl bromide, tribromobenzyl chlorides, nitrochlorobenzyl chlorides, o  : o 1 - dichloro - tetrachloroxylenes, a - and b -halogenphenyl-ethyl chlorides and halogenated tricresyl phosphates.  Many suitable polyamines are listed, e.g. ethylene diamine, N-alkylethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, 1 : 2- and 1 : 3 - diamino - propane, 1 : 4 - diaminobutane, 1 : 6 - diaminohexane, diamines of higher dicarboxylic acids, e.g. dimerized fatty acids, adducts of acrylonitrile to polyhydric alcohols and phenols followed by hydrogenation, xylylene-, phenylene- and naphthylene-diamines, piperazines and substituted aromatic polyamines. The reactions may be illustrated by the following equations: <FORM:1019778/C2/1> <FORM:1019778/C2/2> <FORM:1019778/C2/3> In typical examples: (A1) trichlorobenzyl chloride was reacted with ethylene diamine and the product reacted with 1 : 2-propylene oxide; (G1) diethanolamine was reacted with trichlorobenzyl chloride; (T) 1 : 2-propylene oxide was reacted with ethylene diamine followed by trichlorobenzyl chloride.