Patent GB-964151-A (GB)
Title: Process for the production of polyurethane foam materials
IPC: C08G18/67
Filed: 1962-04-26
Abstract: In a process for the production of foam materials comprising urethane groups from polyhydroxyl compounds and polyisocyanates in the presence of water and/or other blowing agents, the polyhydroxyl compounds are addition products of dienophilic unsaturated monocarboxylic and/or polycarboxylic acids or monohydric or polyhydric alcohols with colophony resins, which addition products are, if desired, also esterified with excess of polyhydric alcohols. Such esterification can take place successively or also simultaneously with the Diels-Alder addition. As the colophony resin there can be used resinic acid, consisting of abietic acid with smaller proportions of canalagous and isomeric acid, or pure abietic acid or its esters.  Specified unsaturated acids are acrylic, methacrylic, crotonic, maleic, fumaric, itaconic, aconitic, sorbic and chloromaleic acids and their anhydrides, esters and acid chlorides, and linoleic, linolenic ricinoleic acids, linseed and tall oil fatty acids.  1, 4-Butene diol is a suitable dienophilic alcohol. Polyhydric alcohols for the esterification may be aliphatic, cycloaliphatic, aromatic or heterocyclic, a list being given.  Also specified are degraded starches, aminoalcohols (including oxyalkylated ethylene or phenylene diamines), castor oil, polyesters, polyalkylene glycol ethers, polythioethers and polyacetals. Concurrently there can be reacted polycarboxylic acids such as phthalic, adipic, sebacic, dimerised and trimerised fatty acids, succinic and terephthalic acids. The polyhydroxyl compounds or the adducts can be modified by halogenation or hydrogenation.  Suitable alkylene and arylene polyisocyanates, including phosphorus-containing and unsubstituted compounds are listed.  Water, azo compounds, low-boiling hydrocarbons, halogenated methanes or ethanes and vinylidene chloride are suitable blowing agents.  The reaction mixture may also contain catalysts (amine, tin acylates, acetylacetonates or molybdenum glycollate), emulsifiers, foam stabilizers, basic silicone oils, paraffins, dyestuffs, pigments and flame-proofing agents. In examples (1) colophony resin, triethylene glycol and maleic anhydride are reacted at 120 DEG C. The product is heated further in the presence of titanium tetrabutylate at 190 DEG C. to effect esterification. The compound obtained is mixed with propoxylated ethylene diamine, polysiloxane polyalkylene glycol ester, aqueous sodium castor oil sulphonate and crude 4, 41-diphenylmethane diisocyanate to give a foam; (2) a reaction product of colophony, maleic anhydride and hexane triol is mixed with a polyacetal (from cane sugar, formaldehyde and diethylene glycol), permethylated aminoethyl piperazine, siloxane, aqueous sodium castor oil sulphonate and 4, 41-diphenylmethane diisocyanate.  Hydroxy compounds used as starting materials in other examples are prepared from resin acids and (3) a cane-sugar-triethylene glycol reaction product, maleic anhydride and triethylene glycol; (4) maleic anhydride, triethylene glycol and trimethylol propane; (5) maleic anhydride and diethylene glycol; (7) diethylene glycol-cane sugar reaction product (in presence of HBF 4), maleic anhydride, diethylene glycol and adipic acid; (8) methyl maleinate and triethylene glycol; (9) triethylene glycol, and methyl methacrylate (in the presence of t-butyl pyrocatechol); (10) triethylene glycol and itaconic acid; (11) 2-butene-1, 4-diol and triethylene glycol; (14) a reaction product of cane sugar and tri-ethylene glycol further reacted with maleic anhydride; (18) maleic anhydride and polyethylene glycol; (19) maleic anhydride, polethylene glycol and diethylene glycol; (20) polyethylene glycol, tall oil fatty acid and maleic anhydride; (21) tall oil fatty acid and triethylene glycol. Other starting materials are prepared; (6) by bromination of the starting material used in (1) or by reaction of (12) a polyacetal from cane sugar, formaldehyde and diethylene glycol with an adduct of colophony and maleic anhydride; (13) triethylene glycol and a reaction product of methyl abietate and maleic anhydride; (15) maleic anhydride, cane sugar, diethylene glycol and rosin WW, the product being reacted with adipic and rape oil acids; (16) triethylene glycol/cane sugar reaction product, maleic anhydride, rosin WW and oleic acid.  In some examples the polyisocyanate used is a reaction product of toluene diisocyanate with methylal in the presence of BF 3 etherate. Specifications 867,156 and 909,604 are referred to.