Synthesis of Stereoregular Reactive Polymers and Sequence-controlled Click Reaction Thereof

以阴离子法制备的正规整聚甲基丙烯酸丙酯为原料，采用Cu(I)介导的炔与叠氮化物咔嗒反应合成了正规整聚合物衍生物。通过对部分改性聚合物的H-1 NMR分析，发现沿聚合物侧基的咔嗒反应受添加胺的类型的强烈影响；强配位的三胺促进了三唑基的随机引入，弱配位的单胺则通过侧基中预先形成的三唑基的邻位辅助作用（邻位效应）形成块状序列，有效激活Cu(I)。这种差异也影响了click接枝反应、click星形聚合物形成和click交联反应，揭示了添加胺在聚合物可控click反应中的效用。

Cu(I)-mediated click reaction of alkyne and azide was applied for the synthesis of stereoregular polymer derivatives from anionically prepared stereoregular poly(propargyl methacrylate). From H-1 NMR analysis of the partially modified polymers, the click reaction along the polymer side groups was found to be strongly affected by the type of added amines ; strongly coordinative triamines promotes random introduction of the triazole units, while weakly coordinating monoamines formed blocky sequence due to the Anchimeric assistance effect(neighboring effect) by the preformed triazole units in the side groups which efficiently activate Cu(I) species. This difference also affects the click grafting reaction, click star polymer formation, and click crosslinking reaction, revealing the utility of added amine in the controlled click reaction of polymers.