多臂星形聚合物分子内末端基的偶联关环

来源 :中国化学会第29届学术年会 | 被引量 : 0次 | 上传用户：shinetos

【摘要】

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【作者】

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王双双陈永明

【机构】

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中国科学院化学研究所中山大学高分子与材料科学系

【出处】

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中国化学会第29届学术年会

【发表日期】

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2014年1期

【关键词】

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环形聚合物可控自由基聚合拓扑聚合物

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　　合成环形大分子的主要方式是通过大分子头尾端基的高效偶联反应实现的,原理上可以对多臂星形聚合物的末端进行偶联反应,以实现多环聚合物的合成.但是由于聚合物链构象的柔性和随意性,会产生各种随机的分子内不同端基的偶联反应,会带来多环聚合物结构的复杂性.本研究从形成双环聚合物的前驱体--四臂星形聚合物--研究这个问题.采用组成不对称的、含四个ATRP引发点的引发剂Br4,引发苯乙烯(St)聚合生成四臂星形聚苯乙烯(S)4.再将(S)4中四个-Br端基在极稀条件下进行分子内随机的原子转移自由基偶合反应生成双环聚合物c(S)4.由于(S)4四个臂与内核的键链方式是不同的,分子内-Br端基随机的偶合反应可形成含两种异构体混合的双环聚合物产物,两种异构体中环状单元的链接方式不同.通过断裂c(S)4分子中心的二硫键,可以直观的确定双环聚合物中两种异构体的结构为“8”形和“θ”形,并确定了各自的含量.分子内成环反应的效率及产物结构通过体积排除色谱、核磁氢谱、基质辅助激光解离飞行时间质谱及不同化学裂解等方法进行了表征.

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多臂星形聚合物分子内末端基的偶联关环

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