Ethylene/1-Hexene Copolymerization with Modified Ziegler-Natta Catalyst

doi:10.1007/s40242-019-9114-5

高等学校化学研究 ›› 2019, Vol. 35 ›› Issue (6): 1089-1094.doi: 10.1007/s40242-019-9114-5

Ethylene/1-Hexene Copolymerization with Modified Ziegler-Natta Catalyst

YIN Meng, ZHANG Zhiqiang, XIONG Yujie, LIU Min, ZHANG Yan, MI Puke

Key Laboratory for Ultrafine Materials, Ministry of Education, Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China

收稿日期:2019-04-22 修回日期:2019-07-24 出版日期:2019-12-01 发布日期:2019-11-29
通讯作者: MI Puke E-mail:pkm@ecust.edu.cn
基金资助:
Supported by the National Key R&D Program of China(No.2017YFB0306701) and the PetroChina Innovation Founda-tion(No.2014D-5006-0504).

Ethylene/1-Hexene Copolymerization with Modified Ziegler-Natta Catalyst

YIN Meng, ZHANG Zhiqiang, XIONG Yujie, LIU Min, ZHANG Yan, MI Puke

Key Laboratory for Ultrafine Materials, Ministry of Education, Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, P. R. China

Received:2019-04-22 Revised:2019-07-24 Online:2019-12-01 Published:2019-11-29
Contact: MI Puke E-mail:pkm@ecust.edu.cn
Supported by:
Supported by the National Key R&D Program of China(No.2017YFB0306701) and the PetroChina Innovation Founda-tion(No.2014D-5006-0504).

摘要/Abstract

摘要： Siloxane compounds were treated with the compounds containing internal donors, such as aromatic ester, phosphate, or 1,3-diether compounds, and the resulting intermediates were further reacted with TiCl₄ to form the modified Ziegler-Natta catalysts for ethylene/1-hexene(E-H) copolymerization. Using the modified Ziegler-Natta catalysts, the effect of the internal donors and the molar ratio of alcohol to magnesium on the catalyst performance was investigated by the orthogonal experiments. The synthetic method of the catalysts was also optimized by choosing the proper way to mix the internal donors. The branch degree, sequence structure, molecular weight, and molecular weight distribution of the copolymer products were determined by Fourier transform infrared spectroscopy(FTIR), carbon-13 nuclear magnetic resonance(¹³C NMR) spectrometry and gel permeation chromatography(GPC). Under the optimum conditions, the catalytic system with tetraethyl orthosilicate and 2,2-dimethoxypropane as the internal donors exhibited the best performance with an activity of 926.74 g copolymer/(g Cat·h^-1). The branch degree, 1-hexene content, and molecular weight distribution of the resulting copolymers reached up to 40 branches/1000C, 5.99% and 5.8, respectively.

关键词: Ziegler-Natta catalyst, Internal donor, Lewis base, Ethylene-olefin copolymerization, Copolymer structure

Abstract: Siloxane compounds were treated with the compounds containing internal donors, such as aromatic ester, phosphate, or 1,3-diether compounds, and the resulting intermediates were further reacted with TiCl₄ to form the modified Ziegler-Natta catalysts for ethylene/1-hexene(E-H) copolymerization. Using the modified Ziegler-Natta catalysts, the effect of the internal donors and the molar ratio of alcohol to magnesium on the catalyst performance was investigated by the orthogonal experiments. The synthetic method of the catalysts was also optimized by choosing the proper way to mix the internal donors. The branch degree, sequence structure, molecular weight, and molecular weight distribution of the copolymer products were determined by Fourier transform infrared spectroscopy(FTIR), carbon-13 nuclear magnetic resonance(¹³C NMR) spectrometry and gel permeation chromatography(GPC). Under the optimum conditions, the catalytic system with tetraethyl orthosilicate and 2,2-dimethoxypropane as the internal donors exhibited the best performance with an activity of 926.74 g copolymer/(g Cat·h^-1). The branch degree, 1-hexene content, and molecular weight distribution of the resulting copolymers reached up to 40 branches/1000C, 5.99% and 5.8, respectively.

Key words: Ziegler-Natta catalyst, Internal donor, Lewis base, Ethylene-olefin copolymerization, Copolymer structure

YIN Meng, ZHANG Zhiqiang, XIONG Yujie, LIU Min, ZHANG Yan, MI Puke. Ethylene/1-Hexene Copolymerization with Modified Ziegler-Natta Catalyst[J]. 高等学校化学研究, 2019, 35(6): 1089-1094.

YIN Meng, ZHANG Zhiqiang, XIONG Yujie, LIU Min, ZHANG Yan, MI Puke. Ethylene/1-Hexene Copolymerization with Modified Ziegler-Natta Catalyst[J]. Chemical Research in Chinese Universities, 2019, 35(6): 1089-1094.

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Ethylene/1-Hexene Copolymerization with Modified Ziegler-Natta Catalyst

Ethylene/1-Hexene Copolymerization with Modified Ziegler-Natta Catalyst

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