SET-LRP of Bio- and Petroleum-Sourced Methacrylates in Aqueous Alcoholic Mixtures
SET-LRP of Bio- and Petroleum-Sourced Methacrylates in Aqueous Alcoholic Mixtures
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DOI：
10.1021/acs.biomac.9b00257
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发表时间：
2019-04-01
影响因子：
6.2
通讯作者：
Percec, Virgil
中科院分区：
文献类型：
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作者：
Moreno, Adrian;Bensabeh, Nabil;Percec, Virgil
单电子转移-活性自由基聚合（SET-LRP）在“程序化”有机水双相体系中消除了对溶剂的明智选择，也提供了加速的反应速率。在这里，我们报告努力扩大这些系统的单体范围，以甲基丙烯酸单体和聚合物为目标。各种环保型水性酒精混合物与铜(0)丝催化剂、三（2-二甲氨基乙基）胺（Me-6-TREN）配体和对甲苯磺酰氯（Ts-CI）引发剂结合使用，以提供由甲基丙烯酸甲酯、甲基丙烯酸丁酯和其他来自生物质原料的单体（如乳酸、异山梨酯、糠醛和月桂酸）制成的明确定义的聚甲基丙烯酸酯。讨论了水对SET-LRP过程中反应混合物性质、反应速率和聚合控制的影响。通过在高转化率下“原位”扩链合成不同目标摩尔质量的聚合物和准嵌段AB共聚物，证明了在报告条件下保留的控制。这些结果突出了SET-LRP提供基于可再生资源的可持续解决方案的能力。
Single-electron transfer-living radical polymerization (SET-LRP) in "programmed" aqueous organic biphasic systems eliminates the judicious choice of solvent and also provides accelerated reaction rates. Herein, we report efforts to expand the monomer scope for these systems by targeting methacrylic monomers and polymers. Various environmentally friendly aqueous alcoholic mixtures were used in combination with Cu(0) wire catalyst, tris(2-dimethylaminoethyl) amine (Me-6-TREN) ligand, and p-toluenesulfonyl chloride (Ts-CI) initiator to deliver well-defined polymethacrylates from methyl methacrylate, butyl methacrylate, and other monomers derived from biomass feedstock (e.g., lactic acid, isosorbide, furfural, and lauric acid). The effect of water on the nature of the reaction mixture during the SET-LRP process, reaction rate, and control of the polymerization is discussed. The control retained under the reported conditions is demonstrated by synthesizing polymers of different targeted molar mass as well as quasi-block AB copolymers by "in situ" chain extension at high conversion. These results highlight the capabilities of SET-LRP to provide sustainable solutions based on renewable resources.