Ethylene/Isoprene Copolymerization with Supported Ziegler-Natta Catalyst Containing Internal Electron Donor

Wen-qi Guo; Xiao-yu Liu; Shao-fei Song; Hao Zhang; Zhi-sheng Fu; Zhi-qiang Fan

doi:10.11777/j.issn1000-3304.2020.20271

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Ethylene/Isoprene Copolymerization with Supported Ziegler-Natta Catalyst Containing Internal Electron Donor

Research Article | 更新时间：2021-05-07

- Ethylene/Isoprene Copolymerization with Supported Ziegler-Natta Catalyst Containing Internal Electron Donor
- Acta Polymerica Sinica Vol. 52, Issue 5, Pages: 522-530(2021)
- 作者机构：
  
  高分子合成与功能构造教育部重点实验室浙江大学高分子科学与工程学系　杭州 310027
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2020.20271
  CLC：
- Published：3 May 2021，
  
  Published Online：22 March 2021，
  
  Received：12 December 2020，
  
  Revised：5 February 2021，
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Wen-qi Guo, Xiao-yu Liu, Shao-fei Song, Hao Zhang, Zhi-sheng Fu, Zhi-qiang Fan. Ethylene/Isoprene Copolymerization with Supported Ziegler-Natta Catalyst Containing Internal Electron Donor. [J]. Acta Polymerica Sinica 52(5):522-530(2021)
DOI：

Wen-qi Guo, Xiao-yu Liu, Shao-fei Song, Hao Zhang, Zhi-sheng Fu, Zhi-qiang Fan. Ethylene/Isoprene Copolymerization with Supported Ziegler-Natta Catalyst Containing Internal Electron Donor. [J]. Acta Polymerica Sinica 52(5):522-530(2021) DOI： 10.11777/j.issn1000-3304.2020.20271.

摘要

乙烯与共轭双烯烃催化共聚是实现聚烯烃功能化和提高聚烯烃可降解性的新途径. 本文用含有内电子给体的氯化镁负载Ziegler-Natta催化剂催化乙烯和异戊二烯(Ip)的共聚反应. 在乙烯压力为0.1 MPa、异戊二烯初始浓度([Ip]

)

$$\leqslant $$

http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=14490532&type=

2 mol/L条件下合成的共聚产物包含2种有显著差异的级分，一种级分的异戊二烯含量低于2 mol%且分子量较高，另一级分的异戊二烯含量大于20 mol%且分子量较低. 两部分共聚物的异戊二烯单元均以反式-1

4-结构为主，共聚反应表现出很高的区域/立体选择性. 随着[Ip]

增大，共聚活性先持续增大，当[Ip]

1 mol/L时转为降低，同时高异戊二烯含量级分的比例增大，2种级分的异戊二烯含量也分别增大. 相较于三异丁基铝为助催化剂的共聚反应，以三乙基铝为助催化剂时聚合活性较低，但产物的异戊二烯含量较高，分子量分布较宽. 在共聚体系中加入硅氧烷外给电子体使得共聚物中高异戊二烯含量的级分显著减少，产物的组成分布变成以低异戊二烯含量共聚物为主的单峰分布.

Abstract

Catalytic ethylene-conjugated diene copolymerization could be a new route of preparing functionalized polyolefins and degradable polyolefins. In this work a MgCl

-supported Ziegler-Natta catalyst containing internal electron donor was used to catalyze copolymerization of ethylene and isoprene (Ip). Under 1.01×10

Pa ethylene pressure and 0−2 mol/L initial Ip concentration ([Ip]

)

the copolymerization product was composed of two fractions with remarkably different chain structures: one fraction with

2 mol% Ip content and high molecular weight

and the other fraction with

20 mol% Ip and low molecular weight. More than 75% of Ip units in both fractions had

trans

-1

4-configuration

showing high regio/stereo selectivity of the copolymerization. Copolymerization activity increased when [Ip]

was raised from 0 mol/L to 1 mol/L

and decreased with further increase of [Ip]

to 2 mol/L

meanwhile the fraction of high Ip content increased with [Ip]

. Copolymerization using TIBA as cocatalyst showed higher catalytic activity than using TEA

slightly lower Ip incorporation rate and narrower molecular weight distribution. Adding siloxane type external electron donor in the polymerization system strongly reduced the fraction of high Ip content

converting the bimodal composition distribution into monomodal one with the low Ip content copolymer as the major component.

关键词

Ziegler-Natta催化剂乙烯异戊二烯共聚

Keywords

Ziegler-Natta catalystEthyleneIsopreneCopolymerization

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