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基于二胺配体的钛配合物催化乙烯共聚合研究
Diamine-based Titanium Catalyzed Ethylene Copolymerization
- 高分子学报 2025年56卷第10期 页码：1791-1800
- 作者机构：
东华大学材料科学与工程学院 先进纤维材料全国重点实验室 上海 201620
- 作者简介：
E-mail: mingyuanli@dhu.edu.cn
caizg@dhu.edu.cn
- 基金信息：国家自然科学基金(52473002)
DOI：10.11777/j.issn1000-3304.2025.25069
中图分类号：- CSTR：32057.14.GFZXB.2025.7397
收稿：2025-03-12，
录用：2025-04-07，
网络出版：2025-06-24，
纸质出版：2025-10-20
- 稿件说明：
移动端阅览
杨明萱, 郭新星, 陈龙, 孙俊芬, 李明远, 蔡正国. 基于二胺配体的钛配合物催化乙烯共聚合研究. 高分子学报, 2025, 56(10), 1791-1800
Yang, M. X.; Guo, X. X.; Chen, L.; Sun, J. F.; Li, M. Y.; Cai, Z. G. Diamine-based titanium catalyzed ethylene copolymerization. Acta Polymerica Sinica, 2025, 56(10), 1791-1800
杨明萱, 郭新星, 陈龙, 孙俊芬, 李明远, 蔡正国. 基于二胺配体的钛配合物催化乙烯共聚合研究. 高分子学报, 2025, 56(10), 1791-1800 DOI： 10.11777/j.issn1000-3304.2025.25069. CSTR： 32057.14.GFZXB.2025.7397.
Yang, M. X.; Guo, X. X.; Chen, L.; Sun, J. F.; Li, M. Y.; Cai, Z. G. Diamine-based titanium catalyzed ethylene copolymerization. Acta Polymerica Sinica, 2025, 56(10), 1791-1800 DOI： 10.11777/j.issn1000-3304.2025.25069. CSTR： 32057.14.GFZXB.2025.7397.
摘要
合成了两种基于二胺配体的六元环非茂钛配合物[RN(CH
2
)
3
NR
]
TiMe
2
(
4a
: R = 2
6-Me
2
-C
6
H
3
4b
: R = 2
6-
i
Pr
2
-C
6
H
3
)并进行了结构表征，随后在改性甲基铝氧烷(MMAO)活化下，系统研究了其催化乙烯均聚及共聚行为. 实验结果表明，配体芳环上带有异丙基的配合物
4b
比带有甲基的配合物
4a
表现出更高的聚合活性. 在Al/Ti摩尔比为800、聚合温度为100 ℃、乙烯压力为2.0 MPa的条件下，
4b
催化乙烯均聚的活性高达1.68×10
6
g·mol
-1
·h
-1
并且在催化乙烯与1-癸烯共聚中表现出更高活性，达到4.08×10
6
g·mol
-1
·h
-1
. 该类催化体系在145 ℃的聚合温度下仍保持稳定的聚合活性，说明其具有优异的热稳定性. 本研究揭示了二胺类钛催化剂配体芳环上取代基的电子位阻效应对催化性能的影响机制，对设计开发兼具高活性、高耐温性及优异共聚能力的非茂钛催化剂体系具有重要意义.
Abstract
Two six-membered non-metallocene titanium complexes based on diphenylamine ligands
[RN(CH
2
)
3
NR
]
TiMe
2
(
4a
: R = 2
6-Me
2
-C
6
H
3
;
4b
: R = 2
6-
i
Pr
2
-C
6
H
3
) were synthesized. The titanium complexes were applied for ethylene homo- and copolymerization with
α
-olefin and norbornene in the presence of modified methylaluminoxane (MMAO) as a cocatalyst by adjusting polymerization conditions such as temperature
ethylene pressure
and the dosage of MMAO. The polymerization results demonstrated that the electronic and steric effects of the substituents on the aniline ligands significantly influenced the catalytic activity. The isopropyl-substituted complex
4b
exhibited an ethylene homopolymerization activity of 1.68×10
6
g·mol
-1
·h
-1
under the conditions of Al/Ti = 800 (molar ratio)
temperature of 100 ℃
and 2 MPa ethylene pressure. Moreover
its activity in ethylene/1-decene copolymerization further increased to 4.08×10
6
g·moll
-1
·h
-1
. Both homo- and copolymerization activities of complex
4b
were higher than those of methyl-substituted complex
4a
. Additionally
this catalyst system maintained stable polymerization activity even at 145 ℃
demonstrating the excellent thermal stab
ility of this diamine-based titanium catalyst. This study elucidated the mechanistic role of the electronic and steric effects of the substituents
providing valuable insights for the design and development of non-metallocene catalysts to achieve high catalyst activity
thermal stability
and excellent copolymerization ability.
关键词
Keywords
references
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