Cordella Daniela, Kermagoret Anthony, Debuigne Antoine, Riva Raphaël, German Ian, Isik Mehmet, Jérôme Christine, Mecerreyes David, Taton Daniel, Detrembleur Christophe
Center for Education and Research on Macromolecules (CERM), Chemistry Department, University of Liege (ULg), Sart-Tilman, B6a, 4000 Liege, Belgium.
Institute for Polymer Materials (POLYMAT), University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avda. Tolosa 72, 20018 Donostia-san Sebastian, Spain.
ACS Macro Lett. 2014 Dec 16;3(12):1276-1280. doi: 10.1021/mz500721r. Epub 2014 Dec 5.
The precision synthesis of poly(ionic liquid)s (PILs) in water is achieved for the first time by the cobalt-mediated radical polymerization (CMRP) of -vinyl-3-alkylimidazolium-type monomers following two distinct protocols. The first involves the CMRP of various 1-vinyl-3-alkylimidazolium bromides conducted in water in the presence of an alkyl-cobalt(III) complex acting as a monocomponent initiator and mediating agent. Excellent control over molar mass and dispersity is achieved at 30 °C. Polymerizations are complete in a few hours, and PIL chain-end fidelity is demonstrated up to high monomer conversions. The second route uses the commercially available bis(acetylacetonato)cobalt(II) (Co(acac)) in conjunction with a simple hydroperoxide initiator (-butyl hydroperoxide) at 30, 40, and 50 °C in water, facilitating the scaling-up of the technology. Both routes prove robust and straightforward, opening new perspectives onto the tailored synthesis of PILs under mild experimental conditions in water.
首次通过两种不同的方案，利用钴介导的自由基聚合（CMRP）实现了在水中对聚离子液体（PILs）的精确合成。这两种方案均涉及对1-乙烯基-3-烷基咪唑鎓型单体进行CMRP。第一种方案是在水中，以烷基钴（III）配合物作为单一组分引发剂和介导剂，对各种1-乙烯基-3-烷基咪唑鎓溴化物进行CMRP。在30℃时，可实现对摩尔质量和分散度的出色控制。聚合反应在数小时内完成，并且在高单体转化率下仍能证明PIL链端保真度。第二条路线是在30℃、40℃和50℃的水中，将市售的双（乙酰丙酮）钴（II）（Co(acac)）与一种简单的氢过氧化物引发剂（叔丁基氢过氧化物）结合使用，这有利于该技术的扩大规模。这两条路线都证明是稳健且直接的，为在水中温和的实验条件下对PILs进行定制合成开辟了新的前景。
