Polyacrylates Derived from Biobased Ethyl Lactate Solvent via SET-LRP
Polyacrylates Derived from Biobased Ethyl Lactate Solvent via SET-LRP
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DOI：
10.1021/acs.biomac.9b00435
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发表时间：
2019-05-01
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：
Bensabeh, Nabil;Moreno, Adrian;Percec, Virgil
本文首次报道了以乳酸烷基酯丙烯酸酯为原料的聚合物的精确合成。动力学实验证明了铜(0)线催化的单电子转移活性自由基生物基单体。这类被遗忘的聚合（SET-LRP）在25℃的醇中聚合（SET-LRP）的丙烯酸酯衍生物绿方法学提供了一个（EL）溶剂，具有甲基和正丁基酯的同源结构的聚合具有良好的分子量，分子量分布和链端官能性控制。常规醇类（如甲醇）的动力学图在单体上为一级，分子量随转化率线性增加。然而，发现水相EL混合物比纯EL更适合用于介导SET-LRP过程。近定量的单体转化率和高溴链端的功能，通过基质辅助激光解吸电离飞行时间分析证明，进一步允许制备含有橡胶聚乳酸丙烯酸乙酯聚（ELA）序列的创新生物基嵌段共聚物。例如，聚(ELA)-b-聚（甘油丙烯酸酯）嵌段共聚物在水中自组装形成稳定的胶束，手性乳酸衍生的嵌段形成胶束核，经芘探针荧光技术证实。动态光散射和透射电子显微镜测量揭示了这些生物基聚集体的纳米级球形形貌。
The precise synthesis of polymers derived from alkyl lactate ester acrylates is reported for the first time. Kinetic experiments were conducted to demonstrate that Cu(0) wire-catalyzed single electron transfer-living radical biobased monomers. The acrylic derivative of ethyl lactate green methodology for the LRP of this forgotten class of polymerization (SET-LRP) in alcohols at 25 degrees C provides a (EL) solvent and homologous structures with methyl and n-butyl ester were polymerized with excellent control over molecular weight, molecular weight distribution, and chain end functionality. Kinetics plots in conventional alcohols such as methanol were first order in the monomer, with molecular weight increasing linearly with conversion. However, aqueous EL mixtures were found to be more suitable than pure EL to mediate the SET-LRP process. The near-quantitative monomer conversion and high bromine chain-end functionality, demonstrated by matrix-assisted laser desorption ionization time-of-flight analysis, further allowed the preparation of innovative biobased block copolymers containing rubbery poly(ethyl lactate acrylate) poly(ELA) sequences. For instance, the poly(ELA)-b-poly(glycerol acrylate) block copolymer self-assembled in water to form stable micelles with chiral lactic acid-derived block forming micellar core as confirmed by the pyrene-probe-based fluorescence technique. Dynamic light scattering and transmission electron microscopy measurements revealed the nanosize spherical morphology for these biobased aggregates.