| 摘要 |
The invention comprises a polymercaptan, liquid at room temperature, composed of linear polyester condensation polymer chains, the ends of said chains being connected with aliphatic mercapto radicals through links selected from thiourethane and urea links. Such a product (which is curable by oxidation) is prepared by reacting a hydroxy-terminated polyester condensation polymer with an amount of an organic diisocyanate such that the number of isocyanate groups exceeds the number of hydroxy groups in the reaction mixture, whereby isocyanate terminals are formed on the polymer and then reacting the resulting isocyanate terminated polymer with an amount of an organic mercaptan selected from dimercaptans and mercaptoamines such that the number of mercapto groups in the dimercaptan or of mercapto and amino groups in the mercapto-amine exceeds the number of isocyanate groups in the reaction mixture. (The amino group of the mercaptoamine or one of the sulphydryl groups of the dimercaptan reacts with the terminal isocyanate groups to give a urea or thiouretane linkage through which the sulphydryl group is connected to the chain.) When a mercaptoamine is used the polyester is preferably prepared from reactants that include a trihydric alcohol. For the preparation of the polyester glycol, diethylene glycol, glycerol, sorbitol, pentaerythritol, trimethylol-propane or ethane; amino alcohols; and oxalic, adipic, sebacic, 6-aminocaproic, phthalic, isophthalic, terephthalic, malonic, succinic, maleic, fumaric, dimer and itaconic acids are specified. Arylene, alkylene and cyclohexylene diisocyanates are listed. Ethane dithiol, bis-beta-mercapto-ethyl sulphide or the polythio-mercaptan polymers (m.wt. 500-1500) disclosed in U.S.A. Specification 2,466,963 are suitable dimercaptans. Mercapto-ethylamine, propylamines and butylamine are the preferred mercaptoamines. In typical Examples: (1) a mixture of polyesters from triethylene glycol and ethylene glycol, respectively, and adipic acid is reacted with excess 2,4-toluene diisocyanate and the NCO-containing product is reacted with excess ethanedithiol in the presence of 2-methylpyrrolidone as catalyst. Samples of the mercapto-terminated product are cured in admixture with (a) magnesium oxide, stearic acid and tertiary butyl hydroperoxide; (b) carbon black and tertiary butyl peroxide; (7) a mercapto-terminated polymer is obtained in a similar manner from diethylene glycol/trimethylol propane/adipic acid polyester, 2,4-toluene diisocyanate and mercapto-ethylamine.
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