Patent GB-940418-A (GB)
Title: Hot oil resistant polyurethane compositions
IPC: C08G18/86
Filed: 1959-11-10
Abstract: 940,418. Polyurethane compositions. GENERAL TIRE & RUBBER CO. Nov. 10, 1959 [Nov. 14, 1958], No. 38128/59. Headings C3B and C3R. A method of making a polyurethane composition comprises the steps of reacting a hydroxyl terminated polyol having only two hydroxyl groups in the molecule, a molecular weight of at least 500 and an acid number not greater than 2 with an organic diisocyanate to form a substantially linear long chain urethane polymer, controlling the amount of polyisocyanate used in said composition to 0À95 to 2 weight equivalents per weight equivalent of polyol, and mixing the urethane polymer with 0À25 to 20 parts by weight based on 100 parts by weight of the urethane polymer of an organic epoxy compound having at least one functional epoxy group. The composition is cured to give a hot oil-resistant product. In an alternative process the epoxy compound is mixed with the polyol before the reaction with the polyisocyanate is effected. Before the curing step the polymer may be mixed with an organic polyisocyanate, alone or together with a carboxylic acid, or with an organic peroxide. It is believed that the epoxy compound has a cross-linking action which offsets the apparent breakdown of the polyurethane chains at high temperatures. The preferred epoxide is the diglycidyl ether of bisphenol A. Other suitable diepoxides are reaction products of epichlorhydrin with such polyols as bisphenol C, glycerol or ethylene glycol. They can be used in monomeric form or as polymers of low molecular weight, e.g. 350 to 1,000. Others mentioned are epichlorhydrin reaction products of neopentyl glycol, pentylene-1,5-glycol, tetrabromobisphenol A; also, phenyl glycidyl ether, styrene oxide, and the reaction product of cardonol with epichlorhydrin. Flexible polyurethanes are preferred products, but rigid materials can be obtained, by using a cross-linking agent such as trimethylol propane or by using polyesters and polyesters of the cross-linking type. Curing can be effected by peroxides, or diperoxides together with excess polyisocyanate. Methylol ureas or phenol formaldehyde resins can replace the polyisocyanate. Acid anhydrides plus epoxy compounds also improve the hot oil resistance of the polyurethanes. The polyurethanes may be prepared from such polyols as polyethers or polyesters. In the reaction with the polyisocyanites suitable catalysts are iron ocetyl ocetonate, octylene glycol titanate, stearyl titanate, dicyclopentadrenyl iron and tertiary amines such as α-methyl-benzyl dimethylamine. The polyetherpolyurethanes before curing can be compounded with carbon black. In examples there is used a polyester-urethane gum prepared by reacting equal molar proportions of p,p <SP>1</SP>-diisocyanate diphenyl methane and a poly 60/40 (ethylene-butylene -1, 4) adipate of M.W. 2000. Portions of this is compounded with (2) stearic acid, carbon black, dicumyl peroxide, and bisphenol A diglycidyl ether; (3) the diglycidyl ether and also durene, paraffin wax or stearic acid, which are compounded by hot or cold milling. The mixtures are sheeted out and moulded. In Example (5) various amounts of diglycidyl ether are added to the polyester before reaction with the polyisocyanate and the product is then mixed with stearic acid, carbon black and dicumyl peroxide and the compositions are cured. In Example (6) a mixture of polyurethane gum, stearic acid, carbon black, glycidyl ether and polymethylene polyphenyl isocyanate is vulcanized. In other examples the mixtures cured comprise (7) polyurethane gum, mill lubricant, glycidyl ether of bisphenol A, blocked isocyanate, carbon black, dicumyl peroxide and nadick anhydride; (8) polether-polyurethane (from polytetra-methylene ether glycol and diisocyanate-diphenyl methane), carbon black, stearic acid, dicumyl peroxide and the diglycidyl ether of bisphenol C.