随着高分子化学的进步,特别是可控自由基聚合反应的发现,不同拓扑结构聚合物的合成己获得了巨大的进展.为合成这些复杂结构的聚合物,人们成功地研究了不同的聚合方法.其中,不同功能团引发剂方法是较为方便和可行的方法之一,并且已广泛用于不同结构聚合物的合成.本文综述了用该方法合成不同拓扑结构聚合物,包括嵌段、杂臂星形、H-形、π-形、接枝和环状聚合物所取得的进展,特别强调的是这篇论文没有覆盖这方面的所有研究工作.这一合成方法的思路是基于将不同聚合反应,尤其是不同可控聚合反应相结合,或者将可控聚合与不同的偶合反应,例如与点击反应、Diel-Alder反应和活性酯反应等相结合.所讨论的多功能引发剂不仅包括小分子化合物,也包括带有两个和两个以上引发基团或链转移基团的聚合物.后者称为大分子多功能团引发剂,可以独立引发不同的聚合反应.
With the advances of polymerization chemistry,especially controlled radical polymerizations,big progress on the synthesis of various topological polymers has been achieved.Different synthetic strategies have been deve-loped,among them,the heterofunctional initiator method is a facile and feasible approach,and has been extensively applied.This review describes the research progress on the application of this synthetic strategy in the preparation of various topological polymers,including block copolymers,miktoarm stars,H-shaped copolymers,π-shaped copolymers,graft polymers and cyclic polymers,but this review does not cover all published papers on this aspect.This synthetic strategy is based on the combination of different polymerizations,especially controlled polymerizations,and the combination of different controlled polymerizations with coupling reactions,such as "click" reactions,Diels-Alder reaction and active ester reaction etc..The heterofunctional initiators discussed in this review include not only small organic molecules but also the polymers containing two or more initiation or chain transfer functional groups;the latter is also known as macro multifunctional initiators,which can initiate different polymerizations independently.