Design of AB divinyl "template monomers'' toward alternating sequence control in metal-catalyzed living radical polymerization
Design of AB divinyl "template monomers'' toward alternating sequence control in metal-catalyzed living radical polymerization
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DOI：
10.1039/c0py00252f
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发表时间：
2011-01-01
影响因子：
4.6
通讯作者：
Sawamoto, Mitsuo
中科院分区：
文献类型：
--
作者：
Hibi, Yusuke;Tokuoka, Shinsuke;Sawamoto, Mitsuo
对于通过活性自由基聚合的交替重复单元序列，设计并聚合了“模板单体”，其中两个可聚合的烯烃（乙烯基）官能团[例如，甲基丙烯酸酯（M）和丙烯酸酯（A）]并排放置在刚性萘支架上的1,8位。即使对于这样的二乙烯基单体，也可以通过金属催化的活性自由基聚合系统实现高度选择性的分子内自由基传播，从而得到线性控制的聚合物，而无需萘模板通过水解从所得聚合物中裂解，随后进行甲基化以进行序列表征，表明该聚合物由高度交替的序列（A-M-A：> 80%）组成，几乎不含同源三联体序列（M-M-M）。
For alternating repeat-unit sequence via living radical polymerization, "template monomers'' were designed and polymerized, where two polymerizable alkene (vinyl) functions [e.g., methacrylate (M) and acrylate (A)] were placed side by side at the 1,8-positions on a rigid naphthalene scaffold. Even for such a divinyl monomer, highly selective intramolecular radical propagation was achieved with metal-catalyzed living radical polymerization systems, to give linear controlled polymers without cross-linking. The naphthalene template was cleaved via hydrolysis from the resultant polymer, and subsequently methylated for sequence characterization. H-1 NMR analysis demonstrated that the polymers consisted of highly alternating sequences (A-M-A: >80%), practically free from homo triad sequences (M-M-M).