| 摘要 |
A polyurethane rubber is obtained by reacting a polyalkylene ether thioether of molecular weight at least 732, in which there are preferably from one to fifteen ether links per thioether link and in which the terminal groups are hydroxyl, with an excess of a diisocyanate, and reacting the intermediate with a chain extender, e.g. water, glycol, diamine, dicarboxylic acid or other compound having two groups containing hydrogen reactive with isocyanate groups, to give a product which can be cured by heat and pressure, if necessary after incorporating additional diisocyanate. In a modification the polyether, diisocyanate and chain extender are reacted simultaneously. The intermediate may be stablized by incorporating a nitrogen base as described in Specification 791,853, or by ensuring that no free isocyanate groups remain. With increased sulphur content the polymers tend to be more plastic, with decreased sulphur, more rubbery. The alkylene groups in the polyether/thioether may contain up to 10 carbon atoms and need not all be the same. Ten examples are given, using polyethers of various sulphur contents and a molar excess of diisocyanate from 7 to 1 to 1.7 to 1. Water and tolylene diamine are used as chain-extending agents and pyridine as catalyst in the chain-extending reaction. The additional diisocyanate used for curing, when necessary, was N,N1-bis-(3-isocynato-4-methyl-phenyl) urea. Piperidine was used as stabilizer for certain intermediates. The molecular weights of the polyethers ranged from 1500 to 5200. Figures are given for various physical properties including water and liquid hydrocarbon absorption. Certain of the polymers remained rubbery down to - 20 DEG F. The polyalkylene ether-thioether glycol starting compounds may be prepared by azeotropic distillation of water from a suitable glycol or glycol mixture using e.g. p-toluene sulphonic acid as catalyst or by reacting bis-halogenothioethers with alkali salts of glycols. In examples: (1) thiodiglycol and paraformaldehyde were condensed to give a polyetherthioether of M.W. 1500; (2) thiodiglycol was self-condensed to a polymer of M.W. 3360; (3) thiodiglycol and ethylene glycol were condensed to a polymer of M.W. 5200; (4) thiodiglycol and diethylene glycol were condensed to a polymer of M.W. 3300; (5) thiodiglycol and triethylene glycol were condensed to a polymer of M.W. 3400; (6) thiodiglycol and 1.4 butane diol were condensed to a polymer of M.W. 2600; (7) as in (4) but yielding a polymer of M.W. 2490; (9) as in (6) but yielding a polymer of M.W. 1735. In the condensation reactions toluene or benzene was present and the water removed azeotropically, the polymer finally being purified and dried.
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