Baffie Florian, Patias Georgios, Shegiwal Ataulla, Brunel Fabrice, Monteil Vincent, Verrieux Ludmilla, Perrin Lionel, Haddleton David M, D'Agosto Franck
Université de Lyon, Université Lyon 1, CPE Lyon, CNRS UMR 5128, Laboratoire CP2M, Équipe PCM, 69616, Villeurbanne, CEDEX, France.
University of Warwick, Department of Chemistry, Gibbet Hill, CV4 7AL, Coventry, UK.
Angew Chem Int Ed Engl. 2021 Nov 22;60(48):25356-25364. doi: 10.1002/anie.202108996. Epub 2021 Oct 22.
Two scalable polymerisation methods are used in combination for the synthesis of ethylene and methacrylate block copolymers. ω-Unsaturated methacrylic oligomers (MMA ) produced by catalytic chain transfer (co)polymerisation (CCTP) of methyl methacrylate (MMA) and methacrylic acid (MAA) are used as reagents in the radical polymerisation of ethylene (E) in dimethyl carbonate solvent under relatively mild conditions (80 bar, 70 °C). Kinetic measurements and analyses of the produced copolymers by size exclusion chromatography (SEC) and a combination of nuclear magnetic resonance (NMR) techniques indicate that MMA is involved in a degradative chain transfer process resulting in the formation of (MMA) -b-PE block copolymers. Molecular modelling performed by DFT supports the overall reactivity scheme and observed selectivities. The effect of MMA molar mass and composition is also studied. The block copolymers were characterised by differential scanning calorimetry (DSC) and their bulk behaviour studied by SAXS/WAXS analysis.
两种可扩展的聚合方法联合用于合成乙烯和甲基丙烯酸酯嵌段共聚物。通过甲基丙烯酸甲酯（MMA）和甲基丙烯酸（MAA）的催化链转移（共）聚合（CCTP）制备的ω-不饱和甲基丙烯酸低聚物（MMA）在相对温和的条件下（80 巴，70 °C），于碳酸二甲酯溶剂中用作乙烯（E）自由基聚合的试剂。通过尺寸排阻色谱（SEC）以及核磁共振（NMR）技术组合对所得共聚物进行动力学测量和分析，结果表明MMA参与了降解链转移过程，从而形成了（MMA）-b-PE嵌段共聚物。由密度泛函理论（DFT）进行的分子建模支持了整体反应机理和观察到的选择性。还研究了MMA摩尔质量和组成的影响。通过差示扫描量热法（DSC）对嵌段共聚物进行表征，并通过小角X射线散射/广角X射线散射（SAXS/WAXS）分析研究其本体行为。
