Effect of Hydrogen on Copolymerization between Dichlorosilane-functionalized Nonconjugated <italic style="font-style: italic">α</italic>,<italic style="font-style: italic">ω</italic>-Diolefin and Propylene

Xue-min Yin; Ya-wei Qin; Li-yang Zhang; Shuai Ma; Jin-yong Dong

doi:10.11777/j.issn1000-3304.2019.19187

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Effect of Hydrogen on Copolymerization between Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Propylene

更新时间：2021-01-26

- Effect of Hydrogen on Copolymerization between Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Propylene
- Acta Polymerica Sinica Vol. 51, Issue 4, Pages: 377-384(2020)
- 作者机构：
  
  1.中国科学院化学研究所中国科学院工程塑料重点实验室　北京 100190
  2.中国科学院大学　北京 100049
  3.中国石油天然气股份有限公司石油化工研究院　北京 102206
  4.中国石油天然气股份有限公司抚顺石化分公司研究院　抚顺 113000
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2019.19187
  CLC：
- Published：2020-4，
  
  Published Online：2 January 2020，
  
  Received：29 October 2019，
  
  Revised：27 November 2019，
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Xue-min Yin, Ya-wei Qin, Li-yang Zhang, Shuai Ma, Jin-yong Dong. Effect of Hydrogen on Copolymerization between Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Propylene. [J]. Acta Polymerica Sinica 51(4):377-384(2020)
DOI：

Xue-min Yin, Ya-wei Qin, Li-yang Zhang, Shuai Ma, Jin-yong Dong. Effect of Hydrogen on Copolymerization between Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Propylene. [J]. Acta Polymerica Sinica 51(4):377-384(2020) DOI： 10.11777/j.issn1000-3304.2019.19187.

摘要

基于Ziegler-Natta催化剂的氯硅烷功能化非共轭

-双烯烃与丙烯共聚，在水的引发下脱水缩合可有效地形成长支链结构的聚丙烯树脂. 而氢气常作为丙烯聚合中的链转移剂，调控聚丙烯的分子量，基于此，研究了氢气对氯硅烷功能化非共轭

-双烯烃与丙烯共聚物链结构的影响. 核磁共振氢谱(

H-NMR)测试结果表明，氢气抑制了氯硅烷功能化非共轭

-双烯烃的插入，随着氢气用量的增加，共聚物分子链中端基乙烯基含量由0.12 mol%降低到0.05 mol%. 熔体流变行为测试结果显示，聚合物熔体的储能模量、损耗模量和零剪切黏度均随着氢气用量增加而降低，这主要是由于相对分子质量减小和长支链密度的减少.

Abstract

Dichlorosilane functionalized nonconjugated

-diolefin and propylene copolymers

prepared by heterogeneous Ziegler-Natta catalysts

have been newly found to trigger dehydration condensation reaction among/between polypropylene chains to form long-chain branched (LCB) structures in the presence of water. Hydrogen is often used as a chain transfer agent to regulate the molecular weight of the polymer in olefin polymerization. Therefore

whether or how hydrogen affects the insertion of the di(5-hexenyl)dichlorosilane in the polymerization of propylene is a topic worthy of study. Herein

the copolymerization of di(5-hexenyl)dichlorosilane and propylene has been investigated based on MgCl

/TiCl

catalyst (9

9-bis(methoxymethyl)fluorine (BMMF)

as internal electron donor) in bulk polymerization conditions. The polypropylene microstructure was analysed by changing hydrogen content while the amount of di(5-hexenyl)dichlorosilane was fixed. It was found that hydrogen significantly improved the activity of catalyst and reduced the molecular weight of polymer. The

H-NMR results show that the pendant double bonds in the polypropylene chain decreased from 0.12 mol% to 0.05 mol%

illustrating that hydrogen inhibited the insertion of di(5-hexenyl)dichlorosilane in the polymerization. The higher the hydrogen content

the lower the insertion of di(5-hexenyl)dichlorosilane in the polypropylene chain

which corresponds to the decreasing density of long-branched chains in the polymer. Analysis of the insoluble portion of the polymer in the xylene showed that there is no gel in the presence of hydrogen. The creep test results exhibit that the value of

increases from 0.70 to 0.95

which quantitatively indicates that the long-chain branching density in the polymer decreases with the increasing hydrogen content. The long-branched chain density in polymer decreases with the increasing hydrogen content

which is also confirmed by the results of small amplitude oscillatory shear rheology test.

关键词

Ziegler-Natta催化剂氢气氯硅烷功能化αω-双烯烃长链支化结构链转移反应

Keywords

Ziegler-Natta catalystHydrogenDi(5-hexenyl)dichlorosilaneLong-branched chain structureChain transfer

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Shaanxi Yanchang Zhongmei Yulin Energy & Chemical Company

CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Acadamy of Sciences

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Effect of Hydrogen on Copolymerization between Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Propylene

DOI：10.11777/j.issn1000-3304.2019.19187

摘要

Abstract

关键词

Keywords

references