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

doi:10.7503/cjcu20180256

Abstract

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

CLC Number:

O631
O614.8

TrendMD:

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

Figures/Tables 12

References 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