Banerjee Sanjib, Domenichelli Ilaria, Ameduri Bruno
Ingénierie et Architectures Macromoléculaires, Institut Charles Gerhardt, UMR 5253 CNRS, UM, ENSCM, Place Eugéne Bataillon, 34095 Montpellier Cedex 5, France.
Isituto di Chimica dei Composti Organometallici (ICCOM), Consiglio Nazionale delle Ricerche, SS Pisa, Via G. Moruzzi 1, 56124 Pisa, Italy.
ACS Macro Lett. 2016 Nov 15;5(11):1232-1236. doi: 10.1021/acsmacrolett.6b00707. Epub 2016 Oct 24.
Unique alternating copolymers based on vinyl acetate (VAc) and -butyl-2-trifluoromethacrylate (MAF-TBE, a nonhomopolymerizable monomer under radical conditions) have been synthesized by nitroxide-mediated polymerization (NMP) using a SG1-based BlocBuilder alkoxyamine (MAMA-SG1) at moderate temperature (at 40 °C) in dimethyl sulfoxide. First-order kinetics and linear evolutions of the molecular weight (up to 17100 g mol), maintaining low dispersity values ( ≤ 1.33), confirmed the controlled nature of the copolymerization. Interestingly, none of the starting monomers could undergo homopolymerization under the NMP condition initiated by MAMA-SG1. The resulting alternating copolymers were characterized by H, C, F, and P NMR spectroscopies and size exclusion chromatography (SEC). The poly(VAc--MAF-TBE) copolymer is amorphous and exhibited a single glass transition temperature of 59 °C. This is the first report of nitroxide-mediated (co)polymerization of VAc leading to well-defined copolymers with satisfactory yields. The results presented in this study established a new route via NMP toward the synthesis of strictly 1:1 alternating fluorocopolymers that can display diverse functionalities.
基于醋酸乙烯酯（VAc）和2-三氟甲基丙烯酸丁酯（MAF-TBE，一种在自由基条件下不可均聚的单体）的独特交替共聚物，已通过使用基于SG1的嵌段构建体烷氧基胺（MAMA-SG1）在二甲基亚砜中于适中温度（40°C）下进行的氮氧自由基介导聚合（NMP）合成。一级动力学以及分子量的线性增长（高达17100 g/mol），同时保持低分散度值（≤1.33），证实了共聚反应的可控性质。有趣的是，在由MAMA-SG1引发的NMP条件下，起始单体均不能发生均聚反应。所得的交替共聚物通过氢谱、碳谱、氟谱和磷谱核磁共振光谱以及尺寸排阻色谱（SEC）进行表征。聚（VAc-MAF-TBE）共聚物为无定形，且表现出单一玻璃化转变温度为59°C。这是关于氮氧自由基介导的VAc（共）聚合反应生成具有良好产率的明确共聚物的首次报道。本研究中呈现的结果通过NMP建立了一条新途径，用于合成可展现多种功能的严格1:1交替含氟共聚物。
