Asadi Vahid, Li Xuecong, Ruggeri Francesco Simone, Zuilhof Han, van der Gucht Jasper, Kodger Thomas E
Physical Chemistry and Soft Matter, Wageningen University & Research Stippeneng 4 6708 WE Wageningen The Netherlands
Laboratory of Organic Chemistry, Wageningen University & Research Stippeneng 4 6708 WE Wageningen The Netherlands.
Polym Chem. 2022 Jul 20;13(32):4666-4674. doi: 10.1039/d2py00841f. eCollection 2022 Aug 16.
Linear-bottlebrush-linear (LBBL) triblock copolymers are emerging systems for topologically-tunable elastic materials. In this paper, a new synthetic methodology is presented to synthesize LBBL polystyrene--bottlebrushpolydimethylsiloxane--polystyrene (PS--bbPDMS--PS) triblock copolymer the "grafting onto" approach where the precursors are individually synthesized through living anionic polymerization and selective coupling reaction. In this two-step approach, polystyrene--polymethylvinylsiloxane (PS--PMVS) diblock copolymer with a low dispersity couples with another living PS block to form PS--PMVS--PS triblock copolymer. Secondly, this is followed by grafting of separately prepared monohydride-terminated PDMS chains with controllable grafting density through a hydrosilylation reaction. In addition to fully tunable architectural parameters, this approach permits a quantitative determination of the ratio of diblock and triblock bottlebrush copolymers and consistency between batches, highlighting the feasibility for scaled-up production. These LBBL triblock copolymers self-assemble into soft, low-modulus thermoplastic elastomers, and the precise knowledge of the composition is crucial for correlating microstructure to mechanical properties.
线性-刷状-线性（LBBL）三嵌段共聚物是用于拓扑可调弹性材料的新兴体系。本文提出了一种新的合成方法来合成LBBL聚苯乙烯-刷状聚二甲基硅氧烷-聚苯乙烯（PS-bbPDMS-PS）三嵌段共聚物，即“接枝到”方法，其中前体通过活性阴离子聚合和选择性偶联反应单独合成。在这个两步法中，低分散度的聚苯乙烯-聚甲基乙烯基硅氧烷（PS-PMVS）二嵌段共聚物与另一个活性PS嵌段偶联形成PS-PMVS-PS三嵌段共聚物。其次，通过硅氢加成反应，用可控接枝密度的单独制备的单氢封端的PDMS链进行接枝。除了完全可调的结构参数外，这种方法还允许定量测定二嵌段和三嵌段刷状共聚物的比例以及批次间的一致性，突出了放大生产的可行性。这些LBBL三嵌段共聚物自组装成柔软、低模量的热塑性弹性体，而组成的精确知识对于将微观结构与机械性能相关联至关重要。
