基于氯硅烷功能化非共轭<italic style="font-style: italic">α</italic>,<italic style="font-style: italic">ω</italic>-双烯烃和Ziegler-Natta催化剂合成长链支化聚丙烯

周杭生; 李康; 秦亚伟; 董金勇

doi:10.11777/j.issn1000-3304.2019.19078

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基于氯硅烷功能化非共轭α,ω-双烯烃和Ziegler-Natta催化剂合成长链支化聚丙烯

研究论文 | 更新时间：2021-01-26

- 基于氯硅烷功能化非共轭α,ω-双烯烃和Ziegler-Natta催化剂合成长链支化聚丙烯
- Synthesis of Long Chain-branched Polypropylene Based on Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Ziegler-Natta Catalyst
- 高分子学报 2019年50卷第11期页码：1177-1186
- 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
- 作者简介：
  
  E-mail: ywqin@iccas.ac.cn
  E-mail: jydong@iccas.ac.cn
- 基金信息：
  
  国家自然科学基金(基金号 21574143，51373178)资助项目()
- DOI：10.11777/j.issn1000-3304.2019.19078
  中图分类号：
- 纸质出版日期：2019-11，
  
  网络出版日期：2019-6-11，
  
  收稿日期：2019-4-17，
  
  修回日期：2019-4-28，
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周杭生, 李康, 秦亚伟, 董金勇. 基于氯硅烷功能化非共轭α,ω-双烯烃和Ziegler-Natta催化剂合成长链支化聚丙烯[J]. 高分子学报, 2019,50(11):1177-1186.

Hang-sheng Zhou, Kang Li, Ya-wei Qin, Jin-yong Dong. Synthesis of Long Chain-branched Polypropylene Based on Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Ziegler-Natta Catalyst[J]. Acta Polymerica Sinica, 2019,50(11):1177-1186.
周杭生, 李康, 秦亚伟, 董金勇. 基于氯硅烷功能化非共轭α,ω-双烯烃和Ziegler-Natta催化剂合成长链支化聚丙烯[J]. 高分子学报, 2019,50(11):1177-1186. DOI： 10.11777/j.issn1000-3304.2019.19078.

Hang-sheng Zhou, Kang Li, Ya-wei Qin, Jin-yong Dong. Synthesis of Long Chain-branched Polypropylene Based on Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Ziegler-Natta Catalyst[J]. Acta Polymerica Sinica, 2019,50(11):1177-1186. DOI： 10.11777/j.issn1000-3304.2019.19078.

摘要

通过设计合成新型含二氯硅烷基团功能化

-双烯烃，以二氯硅烷在水或醇引发下缩合形成不同聚合物链之间的连接，替代通过直接

-双烯烃/丙烯共聚合形成长链支化结构，为基于Ziegler-Natta催化剂合成长链支化聚丙烯提供新方法. 结果表明，新型功能化

-双烯烃不会造成催化剂活性降低，二氯硅烷基团在水蒸汽处理和甲醇处理条件下都可有效促进聚合物链间连接形成支化. 所得到的长链支化聚丙烯样品在凝胶渗透色谱(GPC)测试中表现出Mark-Houwink曲线偏离线性，在熔体流变测试中出现零切黏度升高、剪切变稀指数降低以及应变硬化等典型特征.

Abstract

This study discusses a new strategy for synthesis of long chain-branched polypropylene (LCB-PP) with Ziegler-Natta catalysts

which

on the basis of conventional nonconjugated

-diolefin/propylene copolymerization incapable of affording LCB

utilizes a dichlorosilane-functionalized

-diolefin instead to carry out the copolymerization. Such a copolymerization with Ziegler-Natta catalysts will give PP bearing pending dichlorosilane functional groups

and it will undergo facile interchain condensations

leading to long chain-branched formation under methanol treatment and water vapor treatment. A MgCl

/TiCl

catalyst containing a diether-type internal electron donor

9-bis(methoxymethyl)fluorine (BMMF)

was employed to catalyze di(5-hexenyl)dichlorosilane/propylene copolymerization in slurry conditions. It was found that di(5-hexenyl)dichlorosilane neither did harm to catalyst activity

nor changed the chain transfer/chain termination reaction of the original propylene polymerization. Incorporations of the mono-polymerized di(5-hexenyl)dichlorosilane were found to be between 0.02 mol% and 0.1 mol%. After the copolymerization completed

the obtained copolymers were treated with methanol or water vapor

respectively. Both the treatments could effectively transform the polymer chains-pending dichlorosilane groups into siloxane groups. The condensation degrees were distributed

which were centralized between 2 and 3 with methanol treatment. Water vapor treatment showed higher efficiency for dichlorosilane condensation than methanol treatment did. It could be found that water-treated samples exhibited systematically higher degrees of long chain-branched than their methanol-treated counterparts did with multiple evidences. Gel permeation chromatography measurement showed that the molecular weights of the copolymerized samples treated by both water vapor and methanol were improved

and the copolymers treated by water vapor in the Mark-Houwink equation curve were more deviated from the linear polypropylene than those of methanol treatment. The linear viscoelasticity of copolymers with different di(5-hexenyl)dichlorosilane concentrations after water vapor treatment and methanol treatment was investigated by means of small amplitude oscillatory shear (SAOS) to verify the existence of long chain-branched structure. According to extensional rheometry measurement

the strain hardening phenomena of the copolymers treated with water vapor were more obvious than those treated with methanol.

关键词

长链支化聚丙烯非共轭αω-双烯烃二氯硅烷Ziegler-Natta催化剂缩合

Keywords

Long chain-branched polypropyleneNonconjugated αω-diolefinDichlorosilaneZiegler-Natta catalystCondensation

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基于氯硅烷功能化非共轭α,ω-双烯烃和Ziegler-Natta催化剂合成长链支化聚丙烯

Synthesis of Long Chain-branched Polypropylene Based on Dichlorosilane-functionalized Nonconjugated α,ω-Diolefin and Ziegler-Natta Catalyst

DOI：10.11777/j.issn1000-3304.2019.19078

摘要

Abstract

关键词

Keywords

references