Expanding the Dimensionality of Polymers Populated with Organic Robust Radicals toward Flow Cell Application: Synthesis of TEMPO-Crowded Bottlebrush Polymers Using Anionic Polymerization and ROMP
Expanding the Dimensionality of Polymers Populated with Organic Robust Radicals toward Flow Cell Application: Synthesis of TEMPO-Crowded Bottlebrush Polymers Using Anionic Polymerization and ROMP
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DOI：
10.1021/ma501632t
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发表时间：
2014-12
期刊：
影响因子：
5.5
通讯作者：
T. Sukegawa;Issei Masuko;K. Oyaizu;H. Nishide
中科院分区：
文献类型：
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作者：
T. Sukegawa;Issei Masuko;K. Oyaizu;H. Nishide
聚聚苯乙烯（4-甲基丙烯酰氧基-2，2，6，6-四甲基哌啶-1-氧基）（PNB-g-PTMA）通过基于4-甲基丙烯酰氧基-2，2，6，6-四甲基哌啶-1-氧基的开环复分解聚合反应，得到经六亚甲基取代的二苯基己基锂的六亚甲基官能化的大分子单体（NB-PTMA），随后使用Grubbs第三-生成催化剂，其避免了涉及克里思部分的氮氧自由基的关键副反应。由于这些反应的官能团耐受性，阴离子聚合导致高产率（>94%）、窄的多分散性指数（98%）和高自由基浓度（0.95个自由基/单体单元）。用动态光散射和原子力显微镜（AFM）测量了PNB-g-PTMA的单分子尺寸，准确地反映了PNB-g-PTMA的瓶状结构。
Poly(norbornene)-g-poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl) (PNB-g-PTMA) was prepared by a grafting-through approach based on anionic polymerization of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl using a norbornene-substituted diphenylhexyllithium to yield a norbornene-functionalized macromonomer (NB-PTMA) and subsequent ring-opening metathesis polymerization of NB-PTMA using a Grubbs third-generation catalyst, which avoided critical side reactions involving the nitroxide radical of TEMPO moiety. The anionic polymerization resulted in high yields (>94%), narrow polydispersity indices ( 98%) and high radical concentrations (0.95 radicals per monomer unit), by virtue of the functional group tolerance of these reactions. Single molecular dimension of PNB-g-PTMA was measured by dynamic light scattering and by atomic force microscopy (AFM), which precisely reflected the bottl...