可控活性聚合多乙烯基单体制备新型单链超内环化聚合物的研究历史及进展

Controlled/living polymerization of multivinyl monomers:toward novel single chain cyclized polymers

多乙烯基单体因其方便易得、固有的反应多活性位点而一直是合成多种复杂拓扑结构聚合物的理想单体;然而Flory-Stockmayer(F-S)均相场理论及广泛的前期尝试已证实多乙烯基单体的聚合会在极低转化率(<10%)下形成凝胶,而无法进行可控聚合.近年来,可控活性聚合方法的发展为动力学控制下的多乙烯基单体聚合奠定了基础,并成功合成多种具有不同复杂结构的聚合物.特别地,合成了具有新颖拓扑结构的单链超内环化聚合物.本文综述了近年来多乙烯基单体聚合的历史,动力学控制下的可控活性聚合机理以及单链超内环化聚合物的聚合过程、结构特征、应用等,展望了该新颖结构聚合物的应用前景,并对多乙烯基单体的可控活性聚合领域的未来发展提出了建议.

Polymerization of multivinyl monomers （MVMs） can produce polymers with novel topological structure and different functionalities due to their inherent multiple reactive sites. However, the polymerization of MVMs would inevitably lead to a polymeric cross-linked network （gel） even at extremely low conversion rates （typically under 10%） according to the Flory-Stockmayer mean-field theory （F-S theory）. Recently, the development of controlled/living radical polymerization （CRP） paved the way towards kinetically-controlled polymerization of MVMs allowing the synthesis of novel macromolecular architectures. In particular, a novel knotted polymeric structure was obtained. This review summarizes the kinetically-controlled mechanism of CRP as the recent, major development in the field of polymerization of MVMs. The synthesis methods, novel structures and applications of knotted/cyclized polymers are also included. Moreover, the prospects for the application of polymers with novel structures and the future development of CRP of MVMs are proposed.