Cis-1,4-specific polymerization of 1,3-conjugated dienes with bis(benzimidazole)NiCl2 catalyst system

IF 4.1 2区化学 Q2 POLYMER SCIENCE Polymer Pub Date : 2024-11-09 DOI:10.1016/j.polymer.2024.127806

Yasuyuki Ueda , Kakeru Tsukahara , Masahito Hasumi , Kohei Uyama , Hiroshi Yukawa , Takehito Kato , Tomoyuki Toda , Shun Ohta , Kei Nishii

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Abstract

We report herein that the catalytic system composed of a bis(benzimidazole)NiCl₂ complex (1, bis(benzimidazole) = phenylbis(benzimidazol-2-yl)methane), Al(C₈H₁₇)₃ (AlOct₃), and [Ph₃C][B(C₆F₅)₄] mediates highly cis-1,4-specific (up to 95 %) polymerization of isoprene (IP). This is the first nickel complex-based catalyst system that achieved the cis-1,4-specific IP polymerization with a selectivity of more than 90 %. The effects of AlR₃ (R = ⁱBu, Et, Me), AlEt₂Cl and activator ([PhNMe₂H][B(C₆F₅)₄], B(C₆F₅)₃, MAO) on the polymerization behavior were also investigated. The 1/AlOct₃/[Ph₃C][B(C₆F₅)₄] system also catalyzed the cis-1,4-specific polymerization of other 1,3-conjugated dienes such as 1,3-butadiene (BD), (E)-1,3-pentadiene (EPD) and β-myrcene (MY) (up to 92 % for BD, 84 % for EPD and 72 % for MY).

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双(苯并咪唑)NiCl2 催化剂体系对 1,3-共轭二烯的顺式-1,4-特异性聚合反应

我们在此报告了由双(苯并咪唑)NiCl2 复合物（1，双(苯并咪唑)=苯基双(苯并咪唑-2-基)甲烷）、Al(C8H17)3 (AlOct3) 和 [Ph3C][B(C6F5)4] 组成的催化体系介导了异戊二烯（IP）的高度顺式-1,4-特异性聚合（高达 95%）。这是首个基于镍络合物的催化剂体系，它实现了选择性超过 90% 的顺式-1,4-特异性 IP 聚合。此外，还研究了 AlR3（R = iBu、Et、Me）、AlEt2Cl 和活化剂（[PhNMe2H][B(C6F5)4]、B(C6F5)3、MAO）对聚合行为的影响。1/AlOct3/[Ph3C][B(C6F5)4] 系统还催化了其他 1,3-共轭二烯（如 1,3-丁二烯 (BD)、(E)-1,3-戊二烯 (EPD) 和 β-月桂烯 (MY)）的顺式-1,4-特异性聚合（BD 达 92%，EPD 达 84%，MY 达 72%）。

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来源期刊

Polymer 化学-高分子科学

CiteScore

7.90

自引率

8.70%

发文量

959

审稿时长

32 days

期刊介绍： Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics. The main scope is covered but not limited to the following core areas: Polymer Materials Nanocomposites and hybrid nanomaterials Polymer blends, films, fibres, networks and porous materials Physical Characterization Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films Polymer Engineering Advanced multiscale processing methods Polymer Synthesis, Modification and Self-assembly Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization Technological Applications Polymers for energy generation and storage Polymer membranes for separation technology Polymers for opto- and microelectronics.