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基于Ziegler-Natta催化剂和
ω -烯烃基甲基二氯硅烷共聚-水解化学制备长链支化高密度聚乙烯Synthesis of Long-chain-branched High-density Polyethylene with Ziegler-Natta Catalyst and
ω -Alkenylmethyldichlorosilane Copolymerization-Hydrolysis Chemistry- 高分子学报 2021年52卷第11期 页码：1488-1497
- 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.陕西延长中煤榆林能源化工有限公司 榆林 718500
- 作者简介：
E-mail: jydong@iccas.ac.cn
- 基金信息：国家自然科学基金(基金号 51973224)
DOI：10.11777/j.issn1000-3304.2021.21121
中图分类号：纸质出版日期：2021-11-20，
网络出版日期：2021-07-29，
收稿日期：2021-04-27，
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刘秀明,杜杰,霍金兰等.基于Ziegler-Natta催化剂和ω-烯烃基甲基二氯硅烷共聚-水解化学制备长链支化高密度聚乙烯[J].高分子学报,2021,52(11):1488-1497.
Liu Xiu-ming,Du Jie,Huo Jin-lan,et al.Synthesis of Long-chain-branched High-density Polyethylene with Ziegler-Natta Catalyst and ω-Alkenylmethyldichlorosilane Copolymerization-Hydrolysis Chemistry[J].ACTA POLYMERICA SINICA,2021,52(11):1488-1497.
刘秀明,杜杰,霍金兰等.基于Ziegler-Natta催化剂和ω-烯烃基甲基二氯硅烷共聚-水解化学制备长链支化高密度聚乙烯[J].高分子学报,2021,52(11):1488-1497. DOI： 10.11777/j.issn1000-3304.2021.21121.
Liu Xiu-ming,Du Jie,Huo Jin-lan,et al.Synthesis of Long-chain-branched High-density Polyethylene with Ziegler-Natta Catalyst and ω-Alkenylmethyldichlorosilane Copolymerization-Hydrolysis Chemistry[J].ACTA POLYMERICA SINICA,2021,52(11):1488-1497. DOI： 10.11777/j.issn1000-3304.2021.21121.
摘要
由Ziegler-Natta催化剂所制备的高密度聚乙烯(HDPE)不含有长链支化结构，导致其加工应用性能受限.如何在Ziegler-Natta催化剂所制备的HDPE中引入长链支化结构，是烯烃聚合研究面临的长期挑战之一. 本文报道通过
ω
-烯烃基甲基二氯硅烷共聚-水解化学，实现以Ziegler-Natta催化剂制备H型长链支化高密度聚乙烯(LCB-HDPE). 以5-己烯基甲基二氯硅烷作为长链支化助剂，首先在Ziegerl-Natta催化剂催化的乙烯聚合中实现其与乙烯共聚，在聚乙烯分子链侧基上引入反应性二氯硅烷基团；聚合反应结束后对聚合物进行水处理，使近邻聚合物链上的二氯硅烷基团发生水解缩合反应，即制备H型LCB-HDPE. 结果表明，Ziegler-Natta催化剂与
ω
-烯烃基甲基二氯硅烷共聚-水解化学的结合可实现LCB-HDPE的制备，长链支化密度可达0.15/1000C，而催化剂效率基本不受影响. 所合成的LCB-HDPE的熔体流变学响应明显，随长链支化密度增加，熔体弹性增大，零切黏度提高，熔体强度和拉伸应变强化效应不断增强. 同时，LCB-HDPE保持了高结晶性能，其熔点和结晶温度与线性聚乙烯相当，而结晶度有较大幅度提高.
Abstract
High density polyethylene (HDPE) prepared by Ziegler-Natta catalyst does not contain long chain branching structure
which results in limits in its processing and applications. How to introduce long chain branching structure into HDPE prepared by Ziegler-Natta catalyst is one of the long-term challenges in olefin polymerization research. This study discusses a new synthesis of long-chain-branched high-density polyethylene(LCB-HDPE) based on Ziegler-Natta catalysis.
ω
-Alkenylmethyldichlorosilane was used as LCB reagent
which is introduced into ethylene polymerization to generate PE chains containing pendant reactive dichlorosilane groups by ethylene/5-hexenylmethyldichlorosilane copolymerization. Followed by treating the polymer powders with water
the neigboring polymer chains-grafted dichlorosilane groups are hydrolyzed and H-type LCB structure is formed by hydrolytic condensation. The results indicate that the combination of Ziegler-Natta catalysts and the
ω
‑alkenylmethyldichlorosilane copolymerization-hydrolysis chemistry resulted in successful preparation of LCB-HDPE with LCB density up to 0.15/1000C and hardly affected catalyst activity. The LCB-HDPEs have significant rheological properties responses. Their melt elasticity
zero-shear viscosity
melt strenght and strain-hardening effect all increase/intensify with the increase of LCB densities. Meanwhile
the LCB-HDPEs maintain high crystallization properties. With melting temperatures and crystallization temperatures being largely equivalent to those of linear PE
their crystallinities increased to a noticeable degree. It is expected that the new LCB-HDPEs with simultaneously high crystallinity and high melt strength will have good applications in the fields where the melt strength is highly required.
关键词
5-己烯基甲基二氯硅烷乙烯聚合Ziegler-Natta催化剂长链支化聚乙烯
Keywords
5-HexenylmethyldichlorosilaneEthylene polymerizationZiegler-Natta catalystLong-chain-branched polyethylene
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