Direct synthesis via RAFT of amphiphilic diblock polyelectrolytes facilitated by the use of a polymerizable ionic liquid as a monomer,Polymer Chemistry

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Direct synthesis via RAFT of amphiphilic diblock polyelectrolytes facilitated by the use of a polymerizable ionic liquid as a monomer
Polymer Chemistry ( IF 4.1 ) Pub Date : 2021-09-08 , DOI: 10.1039/d1py00801c
Aleksander Guzik _{1,

2} , Patrizio Raffa ₁

Affiliation

A new method for obtaining amphiphilic block polyelectrolytes with a strongly hydrophobic block under homogeneous conditions is described and demonstrated by synthesizing poly(2-acrylamido-2-methanepropanesulfonate-b-styrene) block copolymers using RAFT polymerization. The technique involves the transformation of the 2-acrylamido-2-methanepropanesulfonate (AMPS) monomer into a polymerizable ionic liquid (PIL) by neutralization with triethylamine, which renders the resulting P(Et₃N-AMPS) macroCTA soluble in DMF, DMSO, and ethanol. Consequently, straightforward homogeneous chain extension with a strongly hydrophobic monomer such as styrene is possible under homogeneous conditions. Homopolymerization of the PIL monomer is studied, revealing pseudo-1^st-order kinetics and polydispersities slightly higher than those for the Na-AMPS monomer. High end group fidelity is demonstrated by chain extension experiments. Amphiphilic diblock copolymers are synthesized in a range of targeted chain compositions, and their formation is confirmed by SEC and ¹H-DOSY, and by investigating self-assembled structures with DLS. The reverse approach based on styrene-first polymerization also proved successful, further expanding the scope of this work. We believe that this provides an interesting alternative to protection–deprotection methods and emulsion polymerization methods, when strongly anionic block copolymers are desired.

中文翻译：

通过使用可聚合离子液体作为单体促进两亲双嵌段聚电解质的 RAFT 直接合成

通过使用 RAFT 聚合合成聚（2-丙烯酰胺-2-甲丙磺酸盐-b-苯乙烯）嵌段共聚物，描述并证明了一种在均相条件下获得具有强疏水性嵌段的两亲性嵌段聚电解质的新方法。该技术涉及通过用三乙胺中和将 2-丙烯酰胺基-2-甲丙烷磺酸酯 (AMPS) 单体转化为可聚合离子液体 (PIL)，从而使所得的 P(Et ₃ N-AMPS) macroCTA 可溶于 DMF、DMSO、和乙醇。因此，在均相条件下，可以使用强疏水性单体（如苯乙烯）进行直接均相扩链。研究了 PIL 单体的均聚反应，揭示了伪 1 ^st级动力学和多分散性略高于 Na-AMPS 单体。链扩展实验证明了高端基团的保真度。两亲性二嵌段共聚物在一系列目标链组成中合成，它们的形成通过 SEC 和¹ H-DOSY 以及使用 DLS 研究自组装结构得到证实。基于苯乙烯优先聚合的反向方法也被证明是成功的，进一步扩大了这项工作的范围。我们相信，当需要强阴离子嵌段共聚物时，这为保护-脱保护方法和乳液聚合方法提供了一种有趣的替代方法。

更新日期：2021-09-15

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