Self-accelerating click reaction for preparing cyclic polymers from unconjugated vinyl monomers
Self-accelerating click reaction for preparing cyclic polymers from unconjugated vinyl monomers
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非共轭乙烯基单体制备环状聚合物的自加速点击反应
DOI：
10.1016/j.polymer.2017.12.071
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发表时间：
2018-02
期刊：
影响因子：
4.6
通讯作者：
Zhang Ke
中科院分区：
文献类型：
--
作者：
Li Zi;Qu Lin;Zhu Wen;Liu Jian'an;Chen Ji-Qiang;Sun Peng;Wu Ying;Liu Zhengping;Zhang Ke
开发了一种高效的无金属双分子同双官能环闭合方法，专门用于从非共轭乙烯基单体制备定义明确的环状聚合物。在这种方法中，定义良好的同双官能线性聚合物与叠氮末端的制备通过使用可逆加成链转移聚合/大分子设计，通过交换的黄原酸酯（RAFT/MADIX）的非共轭的乙烯基单体的存在下的叠氮黄原酸酯链转移剂。采用自加速双应变促进叠氮-炔环加成（DSPAAC）反应，以对称二苯并-1，5-环辛-3，7-二炔（DBA）为小连接基，对线型聚合物前体进行闭环，得到相应的环状聚合物.该方法利用DSPAAC闭环反应的自加速性质，巧妙地消除了传统双分子闭环方法中对等摩尔量遥爪聚合物和小分子连接基团的要求。更重要的是，使用过量的DBA小连接基可以显著提高环状聚合物的制备效率。此外，由该新方法得到的环状聚合物可以通过环状聚合物主链内的S-C（S）键的温和氨解而方便地裂解回线性聚合物。
An efficient metal-free bimolecular homodifunctional ring-closure method was developed specifically for preparing well-defined cyclic polymers from unconjugated vinyl monomers. In this approach, well-defined homodifunctional linear polymers with azide terminals were prepared by using the reversible addition chain transfer polymerization/macromolecular design by interchange of xanthates (RAFT/MADIX) to polymerize unconjugated vinyl monomers in the presence of a diazide xanthate chain transfer agent. The self-accelerating double strain-promoted azide-alkyne cycloaddition (DSPAAC) reaction was then applied to ring-close the linear polymer precursors withsym-dibenzo-1,5-cyclooctadiene-3,7-diyne (DBA) as small linkers, leading to the formation of corresponding cyclic polymers. By virtue of the self-accelerating property of DSPAAC ring-closing reaction, this novel method smartly eliminated the requirement of equimolar amounts of the telechelic polymers and small linkers in the traditional bimolecular ring-closure methods for pure cyclic polymers. More importantly, the usage of excess DBA small linkers could significantly enhance the preparation efficiency of cyclic polymers. Moreover, the cyclic polymers resulted from this novel method could be conveniently cleaved back to linear polymers by a mild aminolysis of the S-C(S) bond within the cyclic polymer backbone.
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影响因子：
16.6
作者：
Qian, Ziqing;Xu, Xiaohua;Amacher, Jeanine F.;Madden, Dean R.;Cormet-Boyaka, Estelle;Pei, Dehua
通讯作者：
Pei, Dehua
影响因子：
4.6
作者：
Takuya Yamamoto;Y. Tezuka
通讯作者：
Takuya Yamamoto;Y. Tezuka
胶束介质中选择性点击反应高效制备大环二嵌段共聚物
影响因子：
15
作者：
Ge, Zhishen;Zhou, Yueming;Liu, Shiyong
通讯作者：
Liu, Shiyong
DOI：
10.1055/s-2002-32542
发表时间：
2002-06
期刊：
Synthesis
影响因子：
--
作者：
S. Chaffins;M. Brettreich;F. Wudl
通讯作者：
S. Chaffins;M. Brettreich;F. Wudl
非共轭乙烯基单体闭环制备环状聚合物的方法
影响因子：
4.6
作者：
Tang, Qingquan;Chen, Jiqiang;Zhao, Yang;Zhang, Ke
通讯作者：
Zhang, Ke