Hyperbranched Polyethylene Ionomers Containing Cationic Tetralkylammonium Ions Synthesized by Pd–Diimine-Catalyzed Direct Ethylene Copolymerization with Ionic Liquid Comonomers,Macromolecules

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Hyperbranched Polyethylene Ionomers Containing Cationic Tetralkylammonium Ions Synthesized by Pd–Diimine-Catalyzed Direct Ethylene Copolymerization with Ionic Liquid Comonomers
Macromolecules ( IF 5.1 ) Pub Date : 2015-08-21 00:00:00 , DOI: 10.1021/acs.macromol.5b01224
Peng Xiang ₁ , Zhibin Ye ₁

Affiliation

Synthesis of polyolefin-based ionomers through direct catalytic copolymerization of olefin with ionic comonomers has been challenging with no prior reports. We demonstrate in this article the first direct synthesis of a class of hyperbranched polyethylene ionomers containing positively charged tetralkylammonium ions and different counteranions (tetrafluoroborate, hexafluorophosphate, bis(trifluoromethane)sulfonimide, or hexafluoroantimonate) by copolymerization of ethylene with tetralkylammonium-containing acrylate-type ionic liquid comonomers (3–5, 7). The use of a Pd–diimine catalyst (1), which shows excellent stability toward the highly polar ionic group, is key to the direct synthesis. A detailed study on the catalytic copolymerization and the effects of the polymerization condition on the macromolecular chain parameters of the resulting ionomers has been performed. A range of ionomers differing in ion content and counteranion has been synthesized and characterized. Meanwhile, systematic studies on the structural, thermal, and melt rheological properties of the ionomers have been undertaken. The dramatic effects of ion incorporation on these properties, particularly on the rheological properties, are demonstrated.

中文翻译：

Pd-二胺催化的乙烯与离子液体共聚单体直接乙烯合成的含阳离子四烷基铵离子的超支化聚乙烯离聚物

通过烯烃与离子共聚单体的直接催化共聚来合成基于聚烯烃的离聚物一直是具有挑战性的，没有先前的报道。我们在本文中证明了通过乙烯与含四烷基铵的丙烯酸酯型离子共聚反应，可以直接合成一类含正电荷的四烷基铵离子和不同抗衡离子（四氟硼酸根，六氟磷酸根，双（三氟甲烷）磺酰亚胺或六氟锑酸根）的超支化聚乙烯离聚物。液态共聚单体（3 – 5、7）。使用Pd-二亚胺催化剂（1）（对高极性离子基团表现出优异的稳定性）是直接合成的关键。已经进行了催化共聚和聚合条件对所得离聚物的大分子链参数的影响的详细研究。已经合成并表征了一系列离子含量和抗衡阴离子不同的离聚物。同时，已经对离聚物的结构，热和熔体流变性质进行了系统研究。证明了离子掺入对这些性质，特别是对流变性质的巨大影响。

更新日期：2015-08-21

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