Expanding the monomer scope of linear and branched vinyl polymerisations via copper-catalysed reversible-deactivation radical polymerisation of hydrophobic methacrylates using anhydrous alcohol solvents
Expanding the monomer scope of linear and branched vinyl polymerisations via copper-catalysed reversible-deactivation radical polymerisation of hydrophobic methacrylates using anhydrous alcohol solvents
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DOI：
10.1039/c9py00777f
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发表时间：
2019-10-07
影响因子：
4.6
通讯作者：
Rannard, Steve
中科院分区：
文献类型：
--
作者：
Flynn, Sean;Dwyer, Andrew B.;Rannard, Steve
cu催化的可逆失活自由基聚合疏水甲基丙烯酸酯单体在无水醇已经扩大到探索这种不寻常的选择溶剂的范围。在无水甲醇和异丙醇中相对容易地合成了一系列具有良好靶向分子量和低分散性（D = 1.12-1.53）的线性甲基丙烯酸均聚物。这些溶剂通常被认为是反溶剂，用于沉淀这种聚合物；因此，我们的研究评估了聚合反应混合物的均匀性和反应控制的程度。与双功能单体乙二醇二甲基丙烯酸酯（EGDMA）的统计共聚产生了支链统计共聚物，其平均分子量高达M-w = 1.76 x 10(6) g mol(-1)；随后的三检测尺寸排除色谱研究提供了深入了解单体结构对最终分离聚合物分支程度的影响。在这些条件下，通过改变EGDMA浓度来控制支链共聚物分子量的能力被认为高度依赖于甲基丙烯酸酯单体化学。讨论了在无水醇中疏水甲基丙烯酸酯聚合过程中可能影响分支反应的一些因素。
Cu-Catalysed reversible-deactivation radical polymerisation of hydrophobic methacrylate monomers in anhydrous alcohols has been expanded to explore the scope of this unusual choice of solvent. A range of linear methacrylic homopolymers with well-targeted molecular weight and low dispersity (D = 1.12-1.53) have been generated in anhydrous methanol and isopropanol with relative ease. These solvents are normally considered antisolvents and employed to precipitate such polymers; therefore, our studies have assessed the polymerisation reaction mixture homogeneity and extent of reaction control. Statistical copolymerisations with the bi-functional monomer, ethylene glycol di-methacrlylate (EGDMA), has led to branched statistical copolymers with weight average molecular weights up to M-w = 1.76 x 10(6) g mol(-1); subsequent triple-detection size exclusion chromatography studies have provided insight into the impact of monomer structure on the extent of branching within the final isolated polymers. The ability to control branched copolymer molecular weights under these conditions through variation of EGDMA concentrations was seen to be highly dependent on methacrylate monomer chemistry. A number of factors which are likely to effect branching reactions during the polymerisation of hydrophobic methacrylates in anhydrous alcohols are discussed.