Structure Formation of Metallopolymer-Grafted Block Copolymers
Structure Formation of Metallopolymer-Grafted Block Copolymers
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DOI：
10.1021/acs.macromol.6b00577
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发表时间：
2016-05-10
期刊：
影响因子：
5.5
通讯作者：
Gallei, Markus
中科院分区：
文献类型：
--
作者：
Ruettiger, Christian;Appold, Michael;Gallei, Markus
微相分离驱动嵌段共聚物的结构形成。本文采用迭代阴离子接枝聚合方法合成了以聚苯乙烯-嵌段-聚异戊二烯(PS-b-PI)为主链的低摩尔质量聚二茂铁基二甲基硅烷(PFS)和聚乙烯基二茂铁(PVFC)为骨架的功能性金属聚合物接枝二嵌段共聚物。聚异戊二烯含量约为30%的PS-b-PI嵌段共聚物在铂催化的硅氢化反应中引入了氯硅烷基团。H-1核磁共振波谱和尺寸排阻色谱表明，硅氯部分与活性金属聚合物发生了有效的反应，得到了具有嵌段选择性的接枝共聚物，其中PVFC和PFS的体积分数分别为34%和43%。通过透射电子显微镜测量，证实了功能性金属聚醚接枝嵌段共聚物的微相分离，揭示了其迷人的形貌。通过小角X射线散射、广角X射线散射和原子力显微镜测量，更详细地研究了PVFC接枝嵌段共聚物的结构形成，证实了PVFC链段在聚异戊二烯片层内呈层状结构，其形态特征为球形亚结构。
Microphase separation drives the structure formation in block copolymers. Here, functional metallopolymer-grafted diblock copolymers consisting of polystyrene-block-polyisoprene (PS-b-PI) as polymer backbone featuring low molar mass polyferrocenyldimethylsilane (PFS) and polyvinylferrocene (PVFc) are synthesized via an iterative anionic grafting-to polymerization strategy. PS-b-PI block copolymers having about 30 mol % 1,2-polyisoprene moieties are subjected to platinum-catalyzed hydrosilylation reaction for the introductiorr of chlorosilane groups. The Si Cl moieties are shown to efficiently react with the active metallopolymers yielding :block-selective metallopolymer-grafted copolymers with 34 vol % PVFc and 43 vol % PFS as evidenced by H-1 NMR spectroscopy as well as size exclusion chromatography. The microphase separation of the functional metallopolyiner-grafted block copolymers is evidenced via TEM measurements revealing fascinating morphologies. The structure formation of the PVFc-grafted block copolymers is, studied in more detail by small-angle X-ray scattering, wide-angle X-ray scattering, and atomic force microscopy measurements evidencing a lamellar, morphology featuring a spherical substructure for the PVFc segments, inside the polyisoprene lamellae.