Facile synthesis of graft copolymers containing rigid poly(dialkyl fumarate) branches by macromonomer method,Journal of Polymer Science Part A: Polymer Chemistry

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Facile synthesis of graft copolymers containing rigid poly(dialkyl fumarate) branches by macromonomer method
Journal of Polymer Science Part A: Polymer Chemistry Pub Date : 2019-09-13 , DOI: 10.1002/pola.29499
Eriko Sato ₁ , Noboru Tamari ₁ , Hideo Horibe ₁

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Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free-radical polymerization process. First, synthesis of PDiPF macromonomers by addition-fragmentation chain transfer (AFCT) was investigated. 2,2-Dimethyl-4-methylene-pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2-(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2474–2480

中文翻译：

大单体法简便合成含有刚性聚富马酸二烷基酯支链的接枝共聚物

接枝共聚物显示出如嵌段共聚物中所见的微相分离结构，并且由于支化结构而具有比嵌段共聚物低的特性粘度。因此，考虑到成型加工性能，特别是对于含有刚性链段的聚合物，接枝共聚物是有用的结构。在这项工作中，通过全自由基聚合工艺合成了含有刚性聚富马酸二异丙酯 (PDiPF) 支链的接枝共聚物。首先，研究了通过加成-断裂链转移（AFCT）合成PDiPF大分子单体。发现 2,2-二甲基-4-亚甲基-戊二酸二甲酯是富马酸二异丙酯 (DiPF) 聚合的有效 AFCT 剂，因为它抑制了不希望的初级自由基终止，这在普通 AFCT 剂时显着发生，使用2-(溴甲基)丙烯酸甲酯。PDiPF 大分子单体与丙烯酸乙酯的共聚产生了具有柔性聚（丙烯酸乙酯）主链和刚性 PDiPF 支链的接枝共聚物。该接枝共聚物显示出微相分离结构、高透明度和对PDiPF和聚丙烯酸乙酯的特征热性能。© 2019 Wiley Periodicals, Inc. J. Polym。科学，A 部分：Polym。化学。聚合物。化学。聚合物。化学。2019 , 57 , 2474–2480

更新日期：2019-09-13

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