“One-pot”N-(2-Benzamidophenyl)-salicylaldehyde Imine/TiCl4·2THF for Catalytic Ethylene Polymerization †

doi:10.7503/cjcu20190175

Abstract

Abstract:

Four ligands, N-(2-benzamidophenyl)-salicylaldehyde imine(L1), N-(2-Benzamidophenyl)-3-methylsalicylaldehyde imine(L2), N-(2-benzamidophenyl)-3-tert-butyl-salicylaldehyde imine(L3) and N-(2-benzamidophenyl)-3,5-dibromosalicyl aldehyde imine(L4) were synthesized and characterized by ¹H NMR and HRMS. Under activated with methylaluminoxane(MAO), L3/TiCl₄·2THF, as model catalytic system, aging conditions of the catalytic system were studied systematically. The optimum conditions are as follows: the aging temperature is 25 ℃, the aging time is 30 min, and the molar ratio of L3/TiCl₄·2THF is 3∶1. Based on the optimum conditions, ethylene polymerization by L1—L4/TiCl₄·2THF was performed under different polymerization parameters, such as molar ratio of Al/Ni, polymerization time and temperature, pressure. It reveals that the ligand with more bulky frame work exhibits higher catalytic activities and higher molecule weight. L3 reaches the highest activity of 224 kg PE/(mol Ti?h). Besides, the microstructures and thermoal properties of obtained polyethylene samples with L1—L4/TiCl₄·2THF were characterized by high temperature ¹H NMR, ¹³C NMR, GPC-IR and DSC. It exhibited that the PE samples are of typical linear high density PE, M_n are between 5.9×10 ⁴ and 11.9×10 ⁴, PDI are around 21.9 to 72.1. The research results help us to understand ethylene polymerization in situ deeply.

Key words: Salicylaldehyde imine ligand, TiCl₄·2THF;, Olefin polymerization catalyst, Ethylene polymerization

CLC Number:

O631
O614.81

TrendMD:

ZHANG Danfeng, ZHAO Maoyu, GUO Ning, TANG Songchao, ZHENG Anna. “One-pot”N-(2-Benzamidophenyl)-salicylaldehyde Imine/TiCl₄·2THF for Catalytic Ethylene Polymerization ^†[J]. Chem. J. Chinese Universities, 2019, 40(9): 2012.

Figures/Tables 8

Fig.1 1H NMR spectrum of L3(CDCl3, 500 MHz) Inset: structural formula of L3.

Entry	Time/min	Temperature/℃	n(L)/n(Ti)	Activity/(kg PE?mol^-1 Ti?h^-1)	10^-5M_η
1	0	25	2∶1	196	5.5
2	30	25	2∶1	208	5.8
3	60	25	2∶1	194	5.3
4	120	25	2∶1	98	4.3
5	30	45	2∶1	60	1.7
6	30	65	2∶1	34	1.5
7	30	25	1∶1	74	3.3
8	30	25	2∶1	104	7.7
9	30	25	3∶1	184	8.6
10	30	25	4∶1	82	5.2

Entry	Ligand	n(Al)/n(Ti)	Time/min	Temperature/℃	$p C 2 H 4$ /MPa	Activity/ (kg PE?mol^-1 Ti?h^-1)	10^-5M_η	T_m/℃	10^-4Mn	PDI
1	L3	0	30	45	10
2	L3	100	30	45	10	116	2.3
3	L3	300	30	45	10	224	5.7	131.3	11.9	21.9
4	L3	500	30	45	10	198	4.3
5	L3	300	60	45	10	135	6.0
6	L3	300	120	45	10	96	6.3
7	L3	300	30	25	10	184	8.6
8	L3	300	30	65	10	136	3.4
9	L3	300	30	45	5	30	1.3
10	L3	300	30	45	20	198	7.9
11	L1	300	30	45	10	116	3.5	133.0	9.10	54.9
12	L2	300	30	45	10	82	3.7	132.5	9.40	58.7
13	L4	300	30	45	10	102	3.0	131.4	5.90	72.1

Entry	Ligand	n(Al)/n(Ti)	Time/min	Temperature/℃	$p C 2 H 4$ /MPa	Activity/ (kg PE?mol^-1 Ti?h^-1)	10^-5M_η	T_m/℃	10^-4Mn	PDI
1	L3	0	30	45	10
2	L3	100	30	45	10	116	2.3
3	L3	300	30	45	10	224	5.7	131.3	11.9	21.9
4	L3	500	30	45	10	198	4.3
5	L3	300	60	45	10	135	6.0
6	L3	300	120	45	10	96	6.3
7	L3	300	30	25	10	184	8.6
8	L3	300	30	65	10	136	3.4
9	L3	300	30	45	5	30	1.3
10	L3	300	30	45	20	198	7.9
11	L1	300	30	45	10	116	3.5	133.0	9.10	54.9
12	L2	300	30	45	10	82	3.7	132.5	9.40	58.7
13	L4	300	30	45	10	102	3.0	131.4	5.90	72.1

Fig.2 1H NMR spectum of PE(L3, entry 3 in Table 2)

Fig.3 13C NMR spectum of PE(L3, entry 3 in Table 2)

Fig.4 GPC-IR of PE(entry 3 in Table 2)

Fig.5 DSC curves of PE(entries 3, 11—13 in Table 2)

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“One-pot”N-(2-Benzamidophenyl)-salicylaldehyde Imine/TiCl₄·2THF for Catalytic Ethylene Polymerization ^†

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