邻位大位阻取代基胺双酚钛(Ⅳ)配合物的合成、表征和催化乙烯(共)聚合研究

李丰; 何江浩; 母瀛

doi:10.14028/j.cnki.1003-3726.2021.06.009

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邻位大位阻取代基胺双酚钛(Ⅳ)配合物的合成、表征和催化乙烯(共)聚合研究

庆祝胡友良研究员80华诞专辑 | 更新时间：2022-08-30

- 邻位大位阻取代基胺双酚钛(Ⅳ)配合物的合成、表征和催化乙烯(共)聚合研究
- o-Bulky Substituted Amine-bis(phenolate) Ti(Ⅳ) Complexes: Synthesis, Characterization, and Catalysis on Ethylene (Co)Polymerization
- 高分子通报 2021年34卷第6期页码：94-103
- 作者机构：
  
  吉林大学,超分子结构与材料国家重点实验室,长春 130012
- 作者简介：
  
  * 母瀛,E-mail: ymu@jlu.edu.cn.
- 基金信息：
  
  国家自然科学基金项目(51673078)
- DOI：10.14028/j.cnki.1003-3726.2021.06.009
  中图分类号：
- 纸质出版日期：2021-06-20，
  
  收稿日期：2020-11-30，
  
  修回日期：2021-02-20，
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李丰, 何江浩, 母瀛. 邻位大位阻取代基胺双酚钛(Ⅳ)配合物的合成、表征和催化乙烯(共)聚合研究[J]. 高分子通报, 2021,34(6):94-103.

Feng LI, Jiang-hao HE, Ying MU. o-Bulky Substituted Amine-bis(phenolate) Ti(Ⅳ) Complexes: Synthesis, Characterization, and Catalysis on Ethylene (Co)Polymerization[J]. Polymer Bulletin, 2021,34(6):94-103.
李丰, 何江浩, 母瀛. 邻位大位阻取代基胺双酚钛(Ⅳ)配合物的合成、表征和催化乙烯(共)聚合研究[J]. 高分子通报, 2021,34(6):94-103. DOI： 10.14028/j.cnki.1003-3726.2021.06.009.

Feng LI, Jiang-hao HE, Ying MU. o-Bulky Substituted Amine-bis(phenolate) Ti(Ⅳ) Complexes: Synthesis, Characterization, and Catalysis on Ethylene (Co)Polymerization[J]. Polymer Bulletin, 2021,34(6):94-103. DOI： 10.14028/j.cnki.1003-3726.2021.06.009.

摘要

合成了一系列邻位大取代基四齿胺双酚配体钛配合物Me

NCH

N[CH

-2-(3-R-5-

BuC

)O]

TiCl

[2a

R=CPhMe

;3a

R=CMePh

;4a

R=CPh

)

对其结构进行了表征

研究了其催化乙烯均聚、乙烯/丙烯共聚及乙烯/1-己烯共聚性能

考察了配体结构及聚合反应条件对聚合行为的影响。与R=

Bu 的已知配合物1a相比

这些新配合物在催化乙烯均聚和共聚时表现出较高的催化活性和良好的稳定性。在MAO 活化下

催化乙烯聚合活性最高达1170kg PE/(mol Ti·h);在Al

/Ph

CB(C

)

活化下

用配合物2a~4a得到的聚乙烯分子量最高可达113×104g/mol。在MAO 活化下

1a~4a催化乙烯/丙烯共聚及乙烯/1-己烯共聚活性分别达到640kg polymer/(mol Ti·h)和1220kg polymer/(mol Ti·h);乙烯-丙烯共聚物分子量为3.1×10

~17.4×10

g/mol、乙烯-1-己烯共聚物分子量为4.9×10

~15.5×10

g/mol;所得乙烯-丙烯共聚物中丙烯单元含量最高可达36.9%(mol)

乙烯-1-己烯共聚物中1-己烯单元含量最高为12.5%(mol)。催化剂配体空间位阻对共单体插入率有明显影响

随配体空间位阻增大

共单体插入率降低。

Abstract

A series of

-bulky substituted amine-bis(phenolate) tetradentate Ti(Ⅳ) Complexes: Me

NCH

N(CH

-(2-OC

-3-R-5-

Bu)

TiCl

(2a

R = CPhMe

; 3a

R = CMePh

; 4a

R = CPh

)

were synthesized and characterized. The catalytic performance of these complexes for ethylene polymerization

ethylene/propylene copolymerization and ethylene/1-hexene was studied and the effects of ligand structure and polymerization conditions on polymerization behavior were investigated. Compared with 1a(R=

Bu)

these synthesized catalysts showed high catalytic activity and excellent stability in ethylene (co)polymerization. In the presences of MAO

the highest activity of these catalysts toward ethylene polymerization was 1170kg PE/(mol Ti·h). Moreover

the highest Mw of polyethylene obtained by 2a~4a/AliBu

/Ph

CB(C

)

was 113×10

g/mol. When activated by MAO

the highest activities of 1a~4a toward ethylene/propylene copolymerization and ethylene/1-hexene copolymerization were 640kg polymer/(mol Ti·h) and 1220kg polymer/(mol Ti·h)

respectively; the molecular weight of obtained ethylene-co-propylene and ethylene-co-1-hexene are 3.1×10

~17.4×10

and 4.9×10

~15.5×10

g/mol

respectively. The highest content of propylene unit in the ethylene-propylene copolymer was 36.9mol%

and the highest content of 1-hexene unit in the ethylene-1-hexene copolymer was 12.5mol%. The content of comonomer in copolymers was dependent on steric hindrance of catalyst ligands

and it was found that the insertion of comonomer decreased with the increase of steric hindrance of catalyst ligands.A series of

-bulky substituted amine-bis(phenolate) tetradentate Ti(Ⅳ) Complexes: Me

NCH

N(CH

-(2-OC

-3-R-5-

Bu)

TiCl

(2a

R = CPhMe

; 3a

R = CMePh

; 4a

R = CPh

)

were synthesized and characterized. The catalytic performance of these complexes for ethylene polymerization

Bu)

these synthesized catalysts showed high catalytic activity and excellent stability in ethylene (co)polymerization. In the presences of MAO

the highest activity of these catalysts toward ethylene polymerization was 1170kg PE/(mol Ti·h). Moreover

the highest Mw of polyethylene obtained by 2a~4a/AliBu

/Ph

CB(C

)

was 113×10

g/mol. When activated by MAO

the highest activities of 1a~4a toward ethylene/propylene copolymerization and ethylene/1-hexene copolymerization were 640kg polymer/(mol Ti·h) and 1220kg polymer/(mol Ti·h)

respectively; the molecular weight of obtained ethylene-co-propylene and ethylene-co-1-hexene are3.1×10

~17.4×10

and 4.9×10

~15.5×10

g/mol

respectively. The highest content of propylene unit in the ethylene-propylene copolymer was 36.9mol%

and the highest content of 1-hexene unit in the ethylene-1-hexene copolymer was 12.5mol%. The content of comonomer in copolymers was dependent on steric hindrance of catalyst ligands

and it was found that the insertion of comonomer decreased with the increase of steric hindrance of catalyst ligands.

关键词

聚烯烃钛配合物烯烃聚合乙烯聚合

Keywords

PolyolefinTi complexesOlefine polymerizationEthylene polymerization

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