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[摘要]：A systematic survey of basic/nucleophilic organocatalysts for the polyaddition in bulk of polyols, PEG-600, and PTMO-650, to isophorone diisocyanate (IPDI) has been performed. Guanidines were shown to be very efficient catalysts for the urethane linkage formation. Bicyclic penta-alkylated guanidines such as MTBD led to polyurethane molecular weight and dispersity that are in the range of those observed with tin-based catalysts such as DBTDL. Tetra-alkylated guanidine such as TBD was shown to be a weaker catalyst as compared to pentaalkylated guanidines, as a result of its high reactivity toward isocyanate, resulting in the formation of a less nucleophilic urea. Although the mechanism has not yet been firmly established, these experiments suggest that a nucleophilic-catalysis mechanism, involving the attack of one of the nitrogen of the guanidine onto the unsaturated system of the isocyanate, should not be totally ruled out with such strong Bronsted base catalysts. |
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