Development of New Synthetic Method for Block Copolymers of Controlled Molecular Weights.

本研究旨在开发一种合成新型可控分子量定制嵌段共聚物的新方法。研究结果包括：(1)通过甲基丙烯酸酯与环氧化物和内酯在铝卟啉引发剂作用下的连续活性聚合，合成了分子量分布较窄的聚甲基丙烯酸酯聚醚和聚酯嵌段共聚物；(2)环硫醚和环氧化物与锌取代的卟啉的光驱动活性聚合合成了聚醚和聚硫醚嵌段共聚物；(3)在大块的Lewis酸(如甲基2，6-二取代酚酸)的辅助下，甲基丙烯酸酯与铝卟啉的高速活性聚合(4)通过在周围苯基的邻位上引入氯基和甲氧基等极性取代基来设计高活性四苯基铝卟啉引发剂。

The present research is to develop a novel method for the synthesis of novel tailored block copolymers of controlled molecular weights.The results include the (1) synthesis of block copolymers of poly (methacrylic esters) polyethers and - polyesters of narrow molecular weight distributions, by the sequential living polymerizations of methacrylic esters and epoxides and lactones, respectively, with aluminum porphyrin initiators, (2) synthesis of block copolymers consisting polyethers and polythioethers by the photo-driven living polymerization of episulfides and epoxides with zinc N-substituted porphyrins, (3) development of high-speed living polymerization of methacrylic esters with aluminum porphyrins assisted by bulky Lewis acids such as methylaluminum 2, 6-disubstituted phenolates, (4) molecular design of highly active aluminum tetraphenylporphyrin initiators by introducing polar substituents such as chlorine and methoxy groups into all the ortho positions of the peripheral phenyl groups.