三苯甲基取代的<italic style="font-style: italic">α</italic>-二亚胺镍催化乙烯聚合制备聚烯烃弹性体

许浒; 张自强; 陈昶乐; 王福周

doi:10.11777/J.issn1000-3304.2025.25059

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三苯甲基取代的α-二亚胺镍催化乙烯聚合制备聚烯烃弹性体

研究论文 | 更新时间：2025-05-22

- 三苯甲基取代的α-二亚胺镍催化乙烯聚合制备聚烯烃弹性体
- Preparation of Polyolefin Elastomers Using Triphenylyl-substituted α-diimide Nickel-catalysed Ethylene Polymerisation
- 高分子学报 2025年页码：1-12
- 作者机构：
  
  1.安徽大学物质科学与信息技术研究院合肥 230601
  2.中国科学技术大学高分子科学与工程系合肥 230026
- 作者简介：
  
  E-mail: changle@ustc.edu.cn
  wangfuzhou@ahu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣52025031);22261142664┫;中国科学院稳定支持基础研究领域青年团队计划(YSBR-094)
- DOI：10.11777/J.issn1000-3304.2025.25059
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7398
- 收稿日期：2025-03-03，
  
  录用日期：2025-04-10，
  
  网络出版日期：2025-05-22，
- 稿件说明：
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许浒, 张自强, 陈昶乐, 王福周. 三苯甲基取代的α-二亚胺镍催化乙烯聚合制备聚烯烃弹性体. 高分子学报, doi: 10.11777/J.issn1000-3304.2025.25059

Xu, H.; Zhang, Z. Q.; Chen, C. L.; Wang, F. Z. Preparation of polyolefin elastomers using triphenylyl-substituted ‍α‍-diimide nickel-catalysed ethylene polymerisation. Acta Polymerica Sinica, doi: 10.11777/J.issn1000-3304.2025.25059
许浒, 张自强, 陈昶乐, 王福周. 三苯甲基取代的α-二亚胺镍催化乙烯聚合制备聚烯烃弹性体. 高分子学报, doi: 10.11777/J.issn1000-3304.2025.25059 DOI： CSTR： 32057.14.GFZXB.2025.7398.

Xu, H.; Zhang, Z. Q.; Chen, C. L.; Wang, F. Z. Preparation of polyolefin elastomers using triphenylyl-substituted ‍α‍-diimide nickel-catalysed ethylene polymerisation. Acta Polymerica Sinica, doi: 10.11777/J.issn1000-3304.2025.25059 DOI： CSTR： 32057.14.GFZXB.2025.7398.

摘要

在聚烯烃金属催化剂的修饰过程中，远程大位阻基团对取代位点进行修饰的策略具有潜在的能力来调节催化行为，然而这种策略在配位插入烯烃聚合反应中常常被忽略. 本研究合成并表征了一系列

-二亚胺镍催化剂

Ni1

Ni5

，这些催化剂具有不同位阻且对位被三苯甲基修饰. 在氯化二乙基铝(Et

AlCl)的活化作用下，使用这些镍催化剂进行了乙烯链行走聚合反应，同时探讨了空间位阻效应所产生的影响. 研究表明，在对位引入三苯基甲基基团能够形成远端刚性位阻，从而显著提高镍催化剂的热稳定性，并且使镍催化剂展现出更高的催化活性. 催化剂的空间位阻效应以及聚合条件的变化对乙烯聚合活性、所制备的聚乙烯分子量、支化度、热力学性能以及力学性能均具有显著影响. 尤其是异丙基取代的

Ni3

Ni5

展现出极高的催化活性，高达1.26×10

g‧mol

-1

‧h

-1

，能够生成高分子量的支链聚乙烯，并使其保持优良的力学性能和弹性性能. 值得注意的是，在120 ℃高温聚合条件下，不对称结构的

Ni5

仍然保持了较高的活性(8.10×10

g‧mol

-1

‧h

-1

Abstract

The strategy of remote bulky group substitution in modifying polyolefin catalysts has the potential to modulate catalytic behavior

a facet often overlooked in coordination insertion olefin polymerization reactions. In this study

a series of

para-

trityl substituted

α‍

-diimine nickel catalysts

Ni1

Ni5

with different steric hindrances were synthesized and characterized. Upon activation with diethylaluminum chloride (Et

AlCl)

all Ni(II) catalysts were employed for ethylene chain-walking polymerization and the effects of spatial steric hindrance were investigated. The research indicates that the introduction of trityl groups at the

para-

position can form remote rigid steric hindrance

thereby significantly enhancing the thermal stability of the nickel catalysts and exhibiting outstanding catalytic performance. The spatial steric effects of the catalysts

as well as changes in polymerization conditions

have a significant impact on ethylene polymerization activity

the molecular weight of the resulting polyethylene

branching degree

thermodynamic properties

and mechanical properties. The isopropyl-substituted

Ni3

Ni5

exhibited extremely high catalytic activities of up to 1.26×10

g·mol

-1

·h

-1

toward ethylene polymerization producing high molecular weight branched polyethylene

while maintaining excellent mechanical and elastic properties. Notably

even at a higher polymerization temperature of 120 ℃

the asymmetric structure of

Ni5

still maintained high activity of up to 8.10×10

g‧mol

-1

‧h

-1

关键词

Keywords

references

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芘环基二亚胺镍催化剂的合成及其乙烯聚合/共聚的性能研究

三苯甲基取代的α-二亚胺镍催化乙烯聚合制备聚烯烃弹性体

Preparation of Polyolefin Elastomers Using Triphenylyl-substituted α-diimide Nickel-catalysed Ethylene Polymerisation

DOI：10.11777/J.issn1000-3304.2025.25059

摘要

Abstract

关键词

Keywords

references