引用本文:
王家宝, 穆红亮, 李悦生. 吡啶亚胺(胺)钒烯烃聚合催化剂[J]. 应用化学,
2015, 32(5): 510-518.
doi:
10.11944/j.issn.1000-0518.2015.05.140315
Citation: WANG Jiabao, MU Hongliang, LI Yuesheng. Vanadium Complexes Containing Pyridylimine(amine) Ancillary Ligands for Olefin Polymerization[J]. Chinese Journal of Applied Chemistry, 2015, 32(5): 510-518. doi: 10.11944/j.issn.1000-0518.2015.05.140315
Citation: WANG Jiabao, MU Hongliang, LI Yuesheng. Vanadium Complexes Containing Pyridylimine(amine) Ancillary Ligands for Olefin Polymerization[J]. Chinese Journal of Applied Chemistry, 2015, 32(5): 510-518. doi: 10.11944/j.issn.1000-0518.2015.05.140315
吡啶亚胺(胺)钒烯烃聚合催化剂
摘要:
设计合成了一系列以吡啶二亚胺、吡啶胺-亚胺和吡啶二胺为螯合配体的三价钒配合物2a~2e,并通过红外和元素分析等技术手段对其进行了结构表征。在助催化剂和再生活化剂的存在下,这些催化剂展示出了高活性和良好的高温稳定性。得到高相对分子质量、单峰分布聚乙烯表明聚合体系为单活性中心。以吡啶二胺为螯合配体的配合物2e(2,6-bis[2,6-(iPr)2PhNC(Me)]2(C5H3N)VCl)在50℃下显示出的活性高达6.96 kg PE/mmolV·h,且在70℃时仍保持高的催化活性,这表明双阴离子吡啶二胺能更好的保护催化活性中心。此外,这类三价钒催化剂能高活性催化乙烯-降冰片烯及乙烯-己烯共聚,在温和条件下即可得到较高单体插入率(降冰片烯37.3%,己烯4.8%)的共聚物。
English
Vanadium Complexes Containing Pyridylimine(amine) Ancillary Ligands for Olefin Polymerization
Abstract:
A series of vanadium(Ⅲ) complexes 2a~2e bearing pyridyldiimine,pyridyl-imineamine and pyridyldiamine ligands was designed,synthesized,and characterized by IR and elemental analysis.Upon treatment with Et2 AlC l and CCl3COOEt(ETA),these catalysts displayed high catalytic activity towards ethylene polymerization even at elevated reaction temperature,affording polymers with high relative molecular mass and unimodal relative molecular mass distributions,indicating the formation of a single active site during the polymerization.It was found that ligands structures exerted great influence on the polymerization behavior.Complex 2e (2,6-bis[2,6-(iPr)2PhNC(Me)]2(C5H3N)VCl) supported by dianionic pyridyldiamine showed an activity of 6.96 kg PE/(mmolV·h) at 50℃ and the activity was well kept at the elevated temperature(70℃).Efficient copolymerization of ethylene with NBE or 1-hexene was also observed.Poly(ethylene-co-NBE) with the NBE content up to 37.7% was obtained by complex 2e under mild condition,and the incorporation of 4.8% 1-hexene was observed in poly(ethylene-co-1-hexene) by complex 2d.
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