Jia Mingchen, Hadjichristidis Nikos, Gnanou Yves, Feng Xiaoshuang
Physical Sciences and Engineering Division and KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955, Saudi Arabia.
Angew Chem Int Ed Engl. 2021 Jan 18;60(3):1593-1598. doi: 10.1002/anie.202011902. Epub 2020 Nov 17.
The direct copolymerization of p-tosyl isocyanate (TSI) with epoxides, initiated by onium salts in the presence of trialkylborane, to produce polyurethanes is reported. The rate of copolymerization and the (regio)selectivity were investigated in relation to the trialkylborane and the initiator used. Under optimized conditions such copolymerizations have been successfully performed for a wide range of epoxides, including ethylene oxide, propylene oxide, 1-octene oxide, cyclohexene oxide, and allyl glycidyl ether. These copolymerizations afford a new category of polyurethanes, clear of side products such as cyclic oxazolidinone, isocyanurate, and poly(isocyanate) linkages. The experimental conditions used in this work are compatible with those for the organocatalytic (co)polymerization of other oxygenated monomers and CO , holding the potential for their terpolymerization with p-tosyl isocyanate and the development of new materials with unprecedented properties.
据报道，在三烷基硼存在下，由鎓盐引发对甲苯磺酰异氰酸酯（TSI）与环氧化物直接共聚以制备聚氨酯。研究了共聚速率和（区域）选择性与所用三烷基硼和引发剂的关系。在优化条件下，已成功地对多种环氧化物进行了此类共聚，包括环氧乙烷、环氧丙烷、1-辛烯氧化物、氧化环己烯和烯丙基缩水甘油醚。这些共聚反应提供了一类新型聚氨酯，不含环状恶唑烷酮、异氰脲酸酯和聚（异氰酸酯）键等副产物。本工作中使用的实验条件与其他含氧单体和CO的有机催化（共）聚合条件兼容，具有与对甲苯磺酰异氰酸酯进行三元共聚以及开发具有前所未有的性能的新材料的潜力。
