Homo- and Copolymerization of 4-Methyl-1-pentene and 1-Hexene with Pyridylamido Hafnium Catalyst

Ling-zhi Wang; Xing-qiang Ni; He Ren; Yu-xin Gao; Hai-yang Gao

doi:10.11777/j.issn1000-3304.2021.21114

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Homo- and Copolymerization of 4-Methyl-1-pentene and 1-Hexene with Pyridylamido Hafnium Catalyst

Articles | 更新时间：2022-07-08

- Homo- and Copolymerization of 4-Methyl-1-pentene and 1-Hexene with Pyridylamido Hafnium Catalyst
- ACTA POLYMERICA SINICA Vol. 52, Issue 11, Pages: 1481-1487(2021)
- 作者机构：
  
  1.聚合物复合材料及功能材料教育部重点实验室中山大学材料科学与工程学院广州 510006
  2.中国石油兰州石化榆林化工有限公司榆林 719000
  3.中国石油石油化工研究院大庆化工研究中心大庆 163714
- 作者简介：
  
  Hai-yang Gao, E-mail: gaohy@mail.sysu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2021.21114
  CLC：
- Published：20 November 2021，
  
  Published Online：22 July 2021，
  
  Received：21 April 2021，
  
  Revised：13 May 2021，
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王凌志,倪兴强,任鹤等.吡啶胺基铪催化4-甲基-1-戊烯与1-己烯聚合研究[J].高分子学报,2021,52(11):1481-1487.

Wang Ling-zhi,Ni Xing-qiang,Ren He,et al.Homo- and Copolymerization of 4-Methyl-1-pentene and 1-Hexene with Pyridylamido Hafnium Catalyst[J].ACTA POLYMERICA SINICA,2021,52(11):1481-1487.
王凌志,倪兴强,任鹤等.吡啶胺基铪催化4-甲基-1-戊烯与1-己烯聚合研究[J].高分子学报,2021,52(11):1481-1487. DOI： 10.11777/j.issn1000-3304.2021.21114.

Wang Ling-zhi,Ni Xing-qiang,Ren He,et al.Homo- and Copolymerization of 4-Methyl-1-pentene and 1-Hexene with Pyridylamido Hafnium Catalyst[J].ACTA POLYMERICA SINICA,2021,52(11):1481-1487. DOI： 10.11777/j.issn1000-3304.2021.21114.

摘要

吡啶胺基铪催化剂作为新一代的烯烃聚合催化剂体系，具有独特的单体插入修饰配体的活化机理以及催化

-烯烃高等规选择性的特点. 本文研究了吡啶胺基铪催化剂催化4-甲基-1-戊烯与1-己烯的聚合反应，重点研究了4-甲基-1-戊烯与1-己烯的共聚合. 结果表明吡啶胺基铪催化剂能够高活性地催化4-甲基-1-戊烯与1-己烯共聚. 通过调控单体的进料比，合成了不同组成的4-甲基-1-戊烯和1-己烯的无规共聚物. 核磁共振(NMR)、示差扫描量热(DSC)以及广角X射线衍射(WAXD)对聚合物的分析表明，1-己烯单元的插入能够调控共聚物的熔融温度以及结晶性能.

Abstract

As a new generation of olefin polymerization catalyst

pyridylamido hafnium catalysts have unique ligand-modified activation mechanism and high isoselectivity for

α‍

-olefins polymerization. In this study

polymerizations of 4-methyl-1-pentene (4MP) and 1-hexene (Hex) catalyzed by classic pyridylamido hafnium catalyst were investigated

especially for the copolymerizations of 4MP and Hex. The pyridylamido hafnium catalyst showed high activity toward homo- and copolymerizations of 4MP and Hex. Isoselective homopolymerization of 4MP afforded narrowly polydispersed poly(4-methyl-1-pentene) (PMP) with high melting temperature up to 239 ℃

while homopolymerization of Hex produced amorphous poly(1-hexene) with a bimodal distribution. Random copolymers of 4MP and Hex with different compositions were synthesized by adjusting the feed ratio of monomers. With decreasing feeding ratio of 4MP/Hex

monomer conversion and copolymerizataion activity increased because the hex-inserted hafnium active species was more active than the 4MP-inserted hafnium active species. Besides

decreasing feeding ratio of 4MP/Hex also led to a decrease in molecular weight and melting temperature of copolymer but caused a broadening in molecular weight distribution.

H- and

C-NMR spectrocopies clearly proved the resultant random copolymers were highly isotactic ([mmmm]

99%). The analysis results of differential scanning calorimetry (DSC)

and wide-angle X-ray diffraction (WAXD) of polymers showed that the insertion of Hex unit into PMP changed its melting temperature and crystallization property.

关键词

铪催化剂4-甲基-1-戊烯共聚等规选择性

Keywords

Hafnium catalysts4-Methyl-1-penteneCopolymerizationIsotacticity

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State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University

MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University

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School of Chemical Engineering, Dalian University of Technology, Liaoning High Performance Polymer Engineering Research Center, Liaoning Key Laboratory of Polymer Science and Engineering

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