Synthesis and Self-Assembly of Well-Defined Condensation Polymers from Chain-Growth Polycondensation

聚合物和可控建筑材料的合成是当前工业界和学术界的研究热点。然而，在缩聚反应中，由于缩聚反应是以逐级增长的方式进行的，所以没有合成具有限定的相对分子质量和窄的相对分子质量分布的聚合物。我们已经提出，在满足上述所有要求的情况下，控制缩聚反应的方法之一是使缩聚反应以类似活性聚合的引发剂以链增长的方式进行。本项目的目标是开发具有可控分子量和低多分散性的缩聚聚合物的链生长缩聚，并寻找含有这些定义良好的缩聚聚合物的新型自组装聚合物。(1)通过链式缩聚，实现了对芳香族聚醚、芳香族聚酯、聚醚砜S、聚噻吩类聚合物的相对分子质量和多分散性的控制。研究发现，在硅片上形成了结构清晰的芳香族聚醚超分子纳米结构。(2)合成了规整的芳香族聚酰胺嵌段共聚物和聚乙二醇、聚苯乙烯、聚四氢呋喃等普通聚合物。还制备了N-烷基和N-H芳香族聚酰胺的嵌段共聚物，发现它们可以自组装形成超分子微序束。(3)合成了接枝有规整的芳香族聚酰胺的新型聚苯乙烯。(4)合成了低分散度的星形聚合物和含芳香族聚酰胺的星形嵌段共聚物。

Synthesis of polymers and materials of controlled architectures is of current interest in both industrial and academic research. In polycondensation, however, polymers of having a defined molecular weight and a narrow molecular weight distribution have not been synthesized, because polycondensation proceeds in a step-growth reaction manner. We have proposed that one of approaches to controlled polycondensation with the formation of that fulfill all of the above-mentioned requirements is to make polycondensation proceed in a chain-growth reaction manner from an initiator like living polymerizations. The goal of this project is to develop chain-growth polycondensation for condensation polymers having controlled molecular weights and low polydispersities and to find novel self-assembly of polymers containing these well-defined condensation polymers.The summary of results is as follows. (1) Control over molecular weight and polydispersity have been achieved on aromatic polyethers, aromatic polyesters, poly (ether sulfone)s, polythiophenes by chain-growth polycondensation. Well-defined aromatic polyethers are find to be arranged to form supramolecular nanostructures on silicon wafer. (2) Block copolymers of well-defined aromatic polyamides and general polymers such as poly (ethylene glycol), polystyrene, and polyTHF have been synthesized. The block copolymers of N-alkyl and N-H aromatic polyamides have been also prepared and found to self-assemble to form supramolecular micro-order bundles. (3) Novel polystyrenes that well-defined aromatic polyamides are grafted on have been synthesized. (4) Star polymers and star block copolymers containing aromatic polyamides with low polydispersities have been synthesized.