Precisely controlled copper(0)‐catalyzed one‐pot reaction: Concurrent living radical polymerization and click chemistry
Precisely controlled copper(0)‐catalyzed one‐pot reaction: Concurrent living radical polymerization and click chemistry
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DOI：
10.1002/pola.26157
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发表时间：
2012-09
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通讯作者：
Weidong Zhang;Gaojian Chen;Zhijun Hu;Wei Zhang-;Zhengbiao Zhang;Xiu-lin Zhu
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作者：
Weidong Zhang;Gaojian Chen;Zhijun Hu;Wei Zhang-;Zhengbiao Zhang;Xiu-lin Zhu
研究了结合活性自由基聚合和“点击化学”的铜（0）催化一锅反应。通过精确调节反应时间，三种具有不同羧基取代度的新型明确聚合物：聚（甲基丙烯酸炔丙酯）（PPgMA）、聚（1-（4-羧基苯基）-[1,2,3]三唑-4-甲基丙烯酸甲酯）（PCTMMA）和聚（1-（4-羧基苯基）-[1,2,3]三唑-4-甲基丙烯酸甲酯-共-甲基丙烯酸炔丙酯） (PCTMMA-co-PPgMA)通过Cu(0)粉末/N,N,N',N",N"-五甲基二乙烯三胺(PMDETA)共催化LRP和点击化学选择性地获得。此外，凝胶渗透色谱和 1 H NMR 分析与 FTIR 光谱结合阐明，由于点击反应速率显着提高，一锅法经历了三个步骤：（1）生成新单体 1-（4-羧基苯基）-[1,2,3]三唑-4-甲基丙烯酸甲酯（CTMMA）； (2)两种单体(CTMMA和PgMA)的共聚； (3)构建均聚物PCTMMA。令人惊讶的是，与典型的 Cu(I) 催化的原子转移自由基聚合 (ATRP) 相比，铜(0) 催化的一锅反应表现出较高的羧酸基团耐受性。 © 2012 Wiley periodicals, Inc. J Polym Sci 第 A 部分：Polym Chem，2012
Copper(0)‐catalyzed one‐pot reaction combining living radical polymerization and “click chemistry” was investigated. By precisely tuning reaction time, three novel well‐defined polymers with different degree of carboxyl substitution, poly(propargyl methacrylate) (PPgMA), poly(1‐(4‐carboxyphenyl)‐[1,2,3]triazol‐4‐methyl methacrylate) (PCTMMA), and poly(1‐(4‐carboxyphenyl)‐[1,2,3]triazol‐4‐methyl methacrylate‐co‐propargyl methacrylate) (PCTMMA‐co‐PPgMA) were selectively obtained via Cu(0) powder/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) cocatalyzed LRP and click chemistry. In addition, gel permeation chromatography and1H NMR analysis in conjunction with FTIR spectroscopy elucidate that one‐pot process undergoes three steps due to a pronounced rate enhancement of click reaction: (1) generating new monomer, 1‐(4‐carboxyphenyl)‐[1,2,3]triazol‐4‐methyl methacrylate (CTMMA); (2) copolymerization of two monomers (CTMMA and PgMA); (3) building homopolymer PCTMMA. Surprisingly, in contrast to typical Cu(I)‐catalyzed atom transfer radical polymerization (ATRP), copper(0)‐catalyzed one‐pot reaction showed high carboxylic acid group tolerance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012