Systheisis of Vanadium Complexes Bearing Tridentate <italic style="font-style: italic">β</italic>-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization

Ling-pan Lu; Kai-ti Wang; Yi Liu; Jia-jun Wu

doi:10.11777/j.issn1000-3304.2019.19128

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Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization

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- Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization
  增强出版
- Acta Polymerica Sinica Vol. 51, Issue 2, Pages: 174-182(2020)
- 作者机构：
  
  1.郑州工业应用技术学院药学与化学工程学院　郑州 451199
  2.重庆理工大学材料科学与工程学院　重庆 400054
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2019.19128
  CLC：
- Published：2020-2，
  
  Published Online：6 September 2019，
  
  Received：3 July 2019，
  
  Revised：25 July 2019，
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Ling-pan Lu, Kai-ti Wang, Yi Liu, Jia-jun Wu. Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization. [J]. Acta Polymerica Sinica 51(2):174-182(2020)
DOI：

Ling-pan Lu, Kai-ti Wang, Yi Liu, Jia-jun Wu. Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization. [J]. Acta Polymerica Sinica 51(2):174-182(2020) DOI： 10.11777/j.issn1000-3304.2019.19128.

摘要

合成了6种三齿

-酮亚胺钒(III)配合物{[(R)X(C

)N＝CH(C

O]VCl

(THF):

R = CH

X = S;

R = CF

X = S;

R = Ph

X = S;

R =

X = S;

R = Ph

X = P;

R = Ph

X = O}，并对其结构进行了表征和证明.

在催化乙烯均聚及其与环烯烃共聚时表现出了较高的催化活性和较为优异的稳定性，所得聚合物的分子量均呈单峰分布. 在催化乙烯与降冰片烯(NBE)共聚以及乙烯与外型-1

10-六氢-9

10(1 ′

2′)-桥苯亚基-1

4-桥亚甲基蒽(HBM)共聚时，部分催化剂表现出了“正共单体效应”. 催化所得乙烯/NBE共聚物的分子量为43.1 ~ 66.4 kg/mol，NBE单元含量为30.9 mol% ~ 42.1 mol%，玻璃化转变温度为84 ~ 105 °C；乙烯/HBM共聚物的分子量为90.2 ~ 138 kg/mol，HBM单元含量为14.7 mol% ~ 25.0 mol%，玻璃化转变温度为173 ~ 188 °C.

Abstract

Vanadium catalysts always show outstanding catalytic properties towards ethylene (co)polymeriztaion

while the high-valent vanadium species would be deactivated because of the generation of inactive or less active low-valent species at elevated temperature and/or in prolonged time. As proved

introducing of bulky groups into the ligands is benefit to improving the catalytic properties of vanadium complexes. Herein

in order to well control the oxidation state of vanadium species

a series of tridentate

-ketoimine type vanadium(III) complexes bearing cyclic skeleton {[(R)X(C

)N＝CH(C

O]VCl

(THF):

R = CH

X = S;

R = CF

X = S;

R = Ph

X = S;

R =

X = S;

R = Ph

X = P;

R = Ph

X = O}

were synthesized and characterized. Because of the constrained effects of the cyclic skeleton and the stabilizing effects of the bi-chelating ring

these synthesized catalysts showed high activities and improved stabilities in ethylene (co)polymerization. In the presences of Et

AlCl and ethyl trichloroacetate

catalysts

−

showed 8.16 − 19.9 kg

polymer

/(mmol

·h)

7.68 − 26.9 kg

polymer

/(mmol

·h) and 4.80 − 42.2 kg

polymer

/(mmol

·h) of catalytic activities towards ethylene polymerization

ethylene/norbornene (NBE) copolymerization and ethylene/exo-1

10-hexahy-dro-9

10(1′

2′)-benzeno-1

4-methanoanthracene (HBM) copolymerization

respectively. All of the resultant polymers exhibited a unimodal distribution

indicating that these vanadium catalysts showed single-site catalytic behaviour

even at elevated temperatures (50 − 70 °C). Catalysts

and

showed “positive” comonomer effects in both ethylene/NBE copolymerization and ethylene/HBM copolymerization. Besides

and

also exhibited “positive” comonomer effects in ethylene/HBM copolymerization. Cyclic olefin copolymers possessing high molecular weights (NBE: 43.1 − 66.4 kg/mol; HBM: 90.2 − 138 kg/mol) and high comonomer incorporations (NBE: 30.9 mol% − 42.1 mol%; HBM: 14.7 mol% − 25.0 mol%) were obtained facilely

via

direct copolymerization. The glass transition temperature is dominantly affected by the cyclic olefin incorporations and the steric hindrance of the cyclic olefin. Compared with the ethylene/NBE copolymers

the obtained ethylene/HBM copolymers showed much higher glass transition temperatures (NBE: 84 − 105 °C versus HBM: 173 − 188 °C).

关键词

钒配合物烯烃聚合聚乙烯环烯烃共聚物

Keywords

Vanadium complexsOlefin polymerizationPolyethyleneCyclic olefin copolymers

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⁰

Systheisis of Vanadium Complexes Bearing Tridentate β-Ketoimine Ligands and Their Catalytic Capabilities towards Ethylene (Co)polymerization

DOI：10.11777/j.issn1000-3304.2019.19128

摘要

Abstract

关键词

Keywords

references