双核苯氧亚胺类催化剂的制备及烯烃聚合

doi:10.7503/cjcu20180256

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (12): 2811.doi: 10.7503/cjcu20180256

双核苯氧亚胺类催化剂的制备及烯烃聚合

张翠¹, 王立娟², 吕中文¹, 许胜¹(), 米普科¹

1. 华东理工大学化学与分子工程学院, 材料科学与工程学院, 上海 200237
2. 中石油石油化工研究院, 大庆化工研究中心, 大庆 163714

收稿日期:2018-04-03 出版日期:2018-10-26 发布日期:2018-10-26
作者简介:
联系人简介: 许胜, 男, 博士, 副教授, 主要从事烯烃聚合催化剂合成研究. E-mail: xusheng@ecust.edu.cn
基金资助:
国家重点研发计划项目(批准号: 2017YFB0306701)和国家自然科学基金(批准号: U1362111)资助.

Synthesis of Binuclear Complexes Containing Phenoxyimine Ligands and Application for Ethylene Polymerization and Copolymerization^†

ZHANG Cui¹, WANG Lijuan², LÜ Zhongwen¹, XU Sheng^1,^*(), MI Puke¹

1. School of Chemistry and Molecular Engineering, School of Materials Science and Engineering,East China University of Science and Technology, Shanghai 200237, China
2. Daqing Petrochemical Research Center of Petrochemical Research Institute, Petrochina Co. Ltd, Daqing 163714, China

Received:2018-04-03 Online:2018-10-26 Published:2018-10-26
Contact: XU Sheng E-mail:xusheng@ecust.edu.cn
Supported by:
† Supported by the National Key R&D Program of China(No.2017YFBO306701) and the National Natural Science Foundation of China(No.U1362111).

摘要/Abstract

摘要：

合成了5个不同结构的苯氧亚胺配体L1~L5, 用Et₃N, Me₃SiCl或HNa处理后与TiCl₄·2THF或CpZrCl₃·DME进行配位反应得到不同取代基结构的化合物C1~C6, 经过 ¹H NMR, ¹³C NMR, IR和元素分析等表征, 确认了化学结构. 以甲基铝氧烷(MAO)为助催化剂, 化合物C1~C6为催化剂催化乙烯聚合, 考察了聚合温度、乙烯压力、铝钛或铝锆比对催化剂活性及聚合物分子量的影响. 聚合实验结果表明, 刚性桥基结构提高了双核化合物(LMCl₃)₂的稳定性, 催化剂的活性基本都能达到10⁵~10⁶ g/(mol M·h), 其中C5的催化活性最高, 达到1.23×10⁶ g/(mol Zr·h); C4在Al/Ti摩尔比为50:1时也具有较好的催化活性[5.89×10⁵ g/(mol Ti·h)], 聚合物分子量1.11×10⁶. 该类催化剂还可以有效催化乙烯与1-辛烯共聚, 1-辛烯插入率达到10.65%(摩尔分数).

关键词: 双核苯氧亚胺, 乙烯/1-辛烯, 共聚, 烯烃聚合催化剂

Abstract:

Binuclear complexes with phenoxyimine ligand were designed and synthesized, in which the ligands were synthesized by a condensation reaction of p-phenylenediamine and substituted salicylaldehyde. Binuclear complexes C1—C6 were synthesized by the TiCl₄·2THF or CpZrCl₃·DME reacted with the ligands treated with triethylamine, trimethylchlorosilane or sodium hydride. Both the ligands and the compounds were well characterized by ¹H NMR, ¹³C NMR, IR, element analysis and MS. When combined with methylaluminoxane(MAO), the binuclear complexes show higher activity for ethylene polymerization. The effects of polymerization factors such as temperature, pressure of ethylene, ratio of aluminum to titanium or zirconium on the catalytic activity and polymer molecular weight were also investigated. The experimental results show that the activity of the catalysts reached 10⁵—10⁶ g/(mol M·h); and the catalyst C5 has the highest catalytic activity of 1.23×10⁶ g/(mol Zr·h). However, the C4 could keep higher catalytic activity when the molar ratio of Al/Ti was lower to 50:1, and the molecular weight of the polymer was higher to 1.11×10⁶. It is also found that the catalyst could effectively catalyze the copolymerization of ethylene with 1-octene and the insertion rate of 1-octene could reach to 10.65%(molar fraction).

Key words: Binuclear phenoxyimine, Ethylene/1-octene, Copolymerization, Catalyst of ethyene polymerization

中图分类号:

O631
O614.8

TrendMD:

张翠, 王立娟, 吕中文, 许胜, 米普科. 双核苯氧亚胺类催化剂的制备及烯烃聚合. 高等学校化学学报, 2018, 39(12): 2811.

ZHANG Cui,WANG Lijuan,LÜ Zhongwen,XU Sheng,MI Puke. Synthesis of Binuclear Complexes Containing Phenoxyimine Ligands and Application for Ethylene Polymerization and Copolymerization^†. Chem. J. Chinese Universities, 2018, 39(12): 2811.

图/表 12

参考文献 25

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Catalyst	10^-4 Activity(g·mol^-1M·h^-1)	M_η	M_n	M_w	PDI
C1	7.6	47800
C2	8.7	52100
C3	11.7	31600	4995	32802	6.57
C4	56.2	61900	7332	76827	10.48
C5	123.0	49400	5222	45982	8.81
C6	15.6

Catalyst	10^-4 Activity(g·mol^-1M·h^-1)	M_η	M_n	M_w	PDI
C1	7.6	47800
C2	8.7	52100
C3	11.7	31600	4995	32802	6.57
C4	56.2	61900	7332	76827	10.48
C5	123.0	49400	5222	45982	8.81
C6	15.6

Entry	Cat.	T/℃	p/MPa	n(Al)/n(Ti)	10^-5 Activity/(g·mol^-1Ti·h^-1)	10^-4 M_η	M_n	M_w	PDI
1	C4	30	0.5	50/1	2.94	6.55	6715	55495	8.26
2	C4	30	1.0	50/1	4.71	9.91
3	C4	30	1.5	50/1	5.89	111.23
4	C4	30	1.0	300/1	7.83	3.52
5	C4	30	1.0	500/1	10.5	4.02
6	C4	30	1.0	1000/1	11.8	7.28
7	C4	60	1.0	1000/1	5.62	7.93	7787	79240	10.17
8	C4	90	1.0	300/1	3.37	1.41
9	C4	90	1.0	500/1	3.74	4.69
10	C4	90	1.0	1000/1	5.61	6.19	7332	76827	10.48
11	Cp₂TiCl₂	30	1.0	1000/1	4.65	32.09
12	C7	30	1.0	1000/1	8.35	68.84

Entry	Cat.	T/℃	p/MPa	n(Al)/n(Ti)	10^-5 Activity/(g·mol^-1Ti·h^-1)	10^-4 M_η	M_n	M_w	PDI
1	C4	30	0.5	50/1	2.94	6.55	6715	55495	8.26
2	C4	30	1.0	50/1	4.71	9.91
3	C4	30	1.5	50/1	5.89	111.23
4	C4	30	1.0	300/1	7.83	3.52
5	C4	30	1.0	500/1	10.5	4.02
6	C4	30	1.0	1000/1	11.8	7.28
7	C4	60	1.0	1000/1	5.62	7.93	7787	79240	10.17
8	C4	90	1.0	300/1	3.37	1.41
9	C4	90	1.0	500/1	3.74	4.69
10	C4	90	1.0	1000/1	5.61	6.19	7332	76827	10.48
11	Cp₂TiCl₂	30	1.0	1000/1	4.65	32.09
12	C7	30	1.0	1000/1	8.35	68.84

Sample	Sequence	Distribution
Diad	EE	0.7157
	EO	0.2727
	OO	0.0116
Triad	EEE	0.5556
	EEO	0.3202
	EOE	0.0833
	EOO	0.0232
	OEO	0.0177
	OOO	0.0000
1-Octene		0.1065
Ethylene		0.8935

双核苯氧亚胺类催化剂的制备及烯烃聚合

Synthesis of Binuclear Complexes Containing Phenoxyimine Ligands and Application for Ethylene Polymerization and Copolymerization^†

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双核苯氧亚胺类催化剂的制备及烯烃聚合

Synthesis of Binuclear Complexes Containing Phenoxyimine Ligands and Application for Ethylene Polymerization and Copolymerization†

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Synthesis of Binuclear Complexes Containing Phenoxyimine Ligands and Application for Ethylene Polymerization and Copolymerization^†