High-Molecular-Weight Polyampholytes Synthesized via Daylight-Induced, Initiator-Free Radical Polymerization of Renewable Itaconic Acid.,Macromolecular Rapid Communications

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High-Molecular-Weight Polyampholytes Synthesized via Daylight-Induced, Initiator-Free Radical Polymerization of Renewable Itaconic Acid.
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2020-01-20 , DOI: 10.1002/marc.201900611
Kacper Mielczarek ₁ , Maria Łabanowska ₂ , Magdalena Kurdziel ₂ , Rafał Konefał ₃ , Hynek Beneš ₃ , Sonia Bujok ₃ , Grzegorz Kowalski ₄ , Szczepan Bednarz ₁

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Herein, it is reported for the first time that when mixed with choline chloride, itaconic acid (IA), normally a low-reactive vinyl monomer, undergoes initiator-free radical polymerization under normal daylight. Furthermore, the process results in the formation of abnormally high-molecular-weight poly(itaconic acid) derivatives with Mw greater than ≈800 000 g mol-1 . Detailed 1D/2D NMR studies indicate that the polymers have two types of ionizable moieties, that is, anionic carboxylic and cationic choline ester groups in an average molar ratio of 12:1. Potentiometric titration shows polyampholyte behavior of the polymers. Tentative mechanistic studies reveal that the daylight-induced polymerization is initiated by species generated via interactions of near UV light with IA. However, EPR findings show that choline also participates in secondary radical reactions. The obtained polyampholytes are useful bio-based materials for fast and straightforward fabrication of polymer-clay nanocomposite hydrogels with excellent mechanical properties.

中文翻译：

通过可诱导的衣康酸的日光诱导，无引发剂自由基聚合反应合成高分子量的两性电解质。

在此，首次报道了通常为低反应性乙烯基单体的衣康酸（IA）与氯化胆碱混合时，在通常的日光下发生引发剂-自由基聚合。此外，该过程导致形成了Mw大于约800000 g mol-1的异常高分子量聚衣康酸衍生物。详细的1D / 2D NMR研究表明，聚合物具有两种类型的可电离部分，即平均摩尔比为12：1的阴离子羧酸和阳离子胆碱酯基。电位滴定显示了聚合物的两性电解质行为。初步的机理研究表明，日光诱导的聚合反应是由近紫外光与IA相互作用产生的物种引发的。然而，EPR的发现表明胆碱也参与了次级自由基反应。所获得的两性电解质是有用的生物基材料，用于快速而直接地制备具有优异机械性能的聚合物粘土纳米复合水凝胶。

更新日期：2020-01-21

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