Fast Access to Amphiphilic Multiblock Architectures by the Anionic Copolymerization of Aziridines and Ethylene Oxide
Fast Access to Amphiphilic Multiblock Architectures by the Anionic Copolymerization of Aziridines and Ethylene Oxide
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DOI：
10.1021/jacs.8b08054
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发表时间：
2018-10-17
影响因子：
15
通讯作者：
Wurm, Frederik R.
中科院分区：
文献类型：
--
作者：
Gleede, Tassilo;Rieger, Elisabeth;Wurm, Frederik R.
对于刺激响应性和两亲性（嵌段）聚合物而言，一个理想的体系是氮丙啶与环氧化物的共聚。然而，到目前为止，这两种高度张力的三元杂环的共聚尚未实现。在此，我们报道了环氧乙烷（EO）的活性氧阴离子和氮杂阴离子开环聚合以及磺酰胺活化的氮丙啶的结合。通过一步法一锅共聚，可得到定义明确的两亲性嵌段聚合物。实时¹H - NMR光谱显示，这是阴离子共聚中所报道的反应性比率差异最大的情况（对于2 - 甲基 - N - 对甲苯磺酰基氮丙啶/EO，r₁ = 265，r₂ = 0.004；对于2 - 甲基 - N - 甲磺酰基氮丙啶/EO，r₁ = 151，r₂ = 0.013），从而形成了具有单峰且分子量分布适中的嵌段聚合物（Mw/Mn大多……）
An ideal system for stimuli-responsive and amphiphilic (block) polymers would be the copolymerization of aziridines with epoxides. However, to date, no copolymerization of these two highly strained three-membered heterocycles had been achieved. Herein, we report the combination of the living oxy- and azaanionic ring-opening polymerization of ethylene oxide (EO) and sulfonamide-activated aziridines. In a single step, well-defined amphiphilic block copolymers are obtained by a one-pot copolymerization. Real-time H-1 NMR spectroscopy revealed the highest difference in reactivity ratios ever reported for an anionic copolymerization (with r(1) = 265 and r(2) = 0.004 for 2-methyl-N-tosylaziridine/EO and r(1) = 151 and r(2) = 0.013 for 2-methyl-N-mesylaziridine/EO), leading to the formation of block copolymers with monomodal and moderate molecular weight distributions (M-w/M-n mostly