重氮化合物在高分子合成化学中的应用进展

Recent Advance of Diazo Compounds in Polymer Synthesis

重氮化合物的转化反应在有机合成中已经得到深入的发展,人们基于此希望将其应用范围进一步延伸至高分子合成化学.将重氮化合物的高效有机反应发展成高分子聚合方法,对于实现结构新颖且具有应用价值的聚合物的合成具有重要的意义.目前,这一领域仍存在较大的发展空间,本综述将对近年来重氮化合物在高分子合成化学中应用进行总结,包括链式聚合、逐步聚合、聚合物末端官能化和聚合物后修饰等四个方面,最后对重氮化合物在高分子合成领域所存在的挑战进行展望.

Based on the well development of diazo compound transformations in organic synthesis,it is expected to extend its applications to the field of polymer synthesis.It is of vital importance to transform efficient organic reactions of diazo compounds into new polymerization methodology in order to afford polymers with new structures and functions.Currently,there is still great development potential in the application of diazo compounds in polymer synthesis.This review highlights the recent advancements of polymer synthesis chemistry with diazo compounds,including chain-growth polymerization,step-growth polymerization,end-group functionalization and post-polymerization modification.Transition-metal-catalyzed chain-growth polymerization of diazoacetates constructs C-C main chain from one carbon unit.Through the development of catalytic diazoacetate polymerization,the synthesis of high molecular weight polymers,stereocontrol polymerization and living/controlled polymerization can be realized successively.The stepwise polymerization of diazo compounds originated from their efficient organic conversions.The insertion reaction of diazo compounds into O-H and N-H bonds can be extended to stepwise polymerization to afford polyethers,polyesters and polyamines that are not easily accessible through other synthetic methods,while cross-coupling polymerization of diazo compounds via metal carbene insertion-migration mechanism can realize the synthesis of polymers with novel structures.Diazoacetates and diazomalonates can be employed to regulate the terminal structures of polymers synthesized through metal-catalyzed vinyl addition polymerization or ring-opening metathesis polymerization of olefins,and successively end-capped by metal carbene.The post-polymerization modifications based on diazo compounds can be applied to the introduction of polar functional groups into polyolefin.Compared to the copolymerization of polar olefins,the post-polymerization functionalization strategy avoids the depressed reactivity of varied monomers,and can be applicable to a broad scope of functional groups.The thermal and mechanical properties of polymers can be improved by this method.Finally,the future challenges in expanding the approaches on polymer chemistry of diazo compounds are prospected in this review.