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首页> 美国卫生研究院文献>Polymers >Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers
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Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

机译：聚苯乙烯-聚烯烃-聚苯乙烯嵌段共聚物的二端官能聚烯烃的聚苯乙烯链增长

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摘要

Triblock copolymers of polystyrene (PS) and a polyolefin (PO), e.g., PS-block-poly(ethylene-co-1-butene)-block-PS (SEBS), are attractive materials for use as thermoplastic elastomers and are produced commercially by a two-step process that involves the costly hydrogenation of PS-block-polybutadiene-block-PS. We herein report a one-pot strategy for attaching PS chains to both ends of PO chains to construct PS-block-PO-block-PS directly from olefin and styrene monomers. Dialkylzinc compound containing styrene moieties ((CH2=CHC6H4CH2CH2)2Zn) was prepared, from which poly(ethylene-co-propylene) chains were grown via “coordinative chain transfer polymerization” using the pyridylaminohafnium catalyst to afford di-end functional PO chains functionalized with styrene and Zn moieties. Subsequently, PS chains were attached at both ends of the PO chains by introduction of styrene monomers in addition to the anionic initiator Me3SiCH2Li·(pmdeta) (pmdeta = pentamethyldiethylenetriamine). We found that the fraction of the extracted PS homopolymer was low (~20%) and that molecular weights were evidently increased after the styrene polymerization (ΔMn = 27–54 kDa). Transmission electron microscopy showed spherical and wormlike PS domains measuring several tens of nm segregated within the PO matrix. Optimal tensile properties were observed for the sample containing a propylene mole fraction of 0.25 and a styrene content of 33%. Finally, in the cyclic tensile test, the prepared copolymers exhibited thermoplastic elastomeric properties with no breakage up over 10 cycles, which is comparable to the behavior of commercial-grade SEBS.
机译：聚苯乙烯（PS）和聚烯烃（PO）的三嵌段共聚物，例如PS-嵌段-聚（乙烯-co-1-丁烯）-嵌段-PS（SEBS），是用作热塑性弹性体的有吸引力的材料，并且可以商业生产通过分两步的方法进行，涉及到PS嵌段聚丁二烯嵌段PS的昂贵氢化。我们在此报告一种一锅法，用于将PS链连接到PO链的两端，以直接从烯烃和苯乙烯单体构建PS-嵌段-PO-嵌段-PS。制备了含苯乙烯基团的二烷基锌化合物（（CH2 = CHC6H4CH2CH2）2Zn），使用吡啶基氨基ha催化剂通过“配位链转移聚合”从其中生长了聚（乙烯-共-丙烯）链，从而提供了被二官能的PO官能化的PO苯乙烯和锌部分。随后，通过引入苯乙烯单体以及阴离子引发剂Me3SiCH2Li·（pmdeta）（pmdeta =五甲基二亚乙基三胺），将PS链连接到PO链的两端。我们发现，提取的PS均聚物的比例很低（〜20％），并且苯乙烯聚合后分子量明显增加（ΔMn= 27-54 kDa）。透射电子显微镜显示球形和蠕虫状的PS域，在PS基质中分离出几十个nm。对于含有0.25的丙烯摩尔分数和33％的苯乙烯含量的样品，观察到最佳的拉伸性能。最后，在循环拉伸试验中，制得的共聚物表现出热塑性弹性体性能，在10个循环内没有破坏，这可与商业级SEBS的性能相媲美。

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