Banerjee Sanjib, Ladmiral Vincent, Debuigne Antoine, Detrembleur Christophe, Rahaman S M Wahidur, Poli Rinaldo, Ameduri Bruno
Ingénierie et Architectures Macromoléculaires, Institut Charles Gerhardt, UMR 5253 CNRS, UM, ENSCM, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France.
Center for Education and Research on Macromolecules (CERM), University of Liege, CESAM Research Unit, Sart-Tilman B6a, 4000, Liege, Belgium.
Macromol Rapid Commun. 2017 Aug;38(15). doi: 10.1002/marc.201700203. Epub 2017 May 31.
Organometallic-mediated radical polymerization (OMRP) has given access to well-defined poly(vinyl acetate-alt-tert-butyl-2-trifluoromethacrylate)-b-poly(vinyl acetate) and poly(VAc-alt-MAF-TBE) copolymers composed of two electronically distinct monomers: vinyl acetate (VAc, donor, D) and tert-butyl-2-trifluoromethacrylate (MAF-TBE, acceptor, A), with low dispersity (≤1.24) and molar masses up to 57 000 g mol . These copolymers have a precise 1:1 alternating structure over a wide range of comonomer feed compositions. The reactivity ratios are determined as r = 0.01 ± 0.01 and r = 0 at 40 °C. Remarkably, from a feed containing >50% molar VAc content, poly(VAc-alt-MAF-TBE)-b-PVAc block copolymers are produced via a one-pot synthesis. Such diblock copolymers exhibit two glass transition temperatures attributed to the alternating and homopolymer sequences. The OMRP of this fluorine-containing alternating monomer system may provide access to a wide range of new polymer materials.
有机金属介导的自由基聚合（OMRP）已成功合成了结构明确的聚（醋酸乙烯酯-alt-叔丁基-2-三氟甲基丙烯酸酯）-b-聚（醋酸乙烯酯）和聚（醋酸乙烯酯-alt-MAF-TBE）共聚物，这些共聚物由两种电子性质不同的单体组成：醋酸乙烯酯（VAc，给体，D）和叔丁基-2-三氟甲基丙烯酸酯（MAF-TBE，受体，A），具有低分散度（≤1.24）且摩尔质量高达57000 g/mol。这些共聚物在很宽的共聚单体进料组成范围内具有精确的1:1交替结构。在40℃下测定的竞聚率为r₁ = 0.01 ± 0.01和r₂ = 0。值得注意的是，从摩尔VAc含量>50%的进料中，通过一锅法合成制备了聚（醋酸乙烯酯-alt-MAF-TBE）-b-PVAc嵌段共聚物。这种二嵌段共聚物表现出两个归因于交替序列和均聚物序列的玻璃化转变温度。这种含氟交替单体体系的OMRP可能为制备多种新型聚合物材料提供途径。
