水杨醛亚胺镍配合物催化乙烯与甲基丙烯酸甲酯的共聚反应

doi:10.7503/cjcu20170256

摘要/Abstract

摘要：

以4种基于水杨醛亚胺配体的镍配合物bis[N-(2,6-diisopropylphenyl)salicylaldiminate]-nickel(Ⅱ)(C1), bis[N-(2,6-diisopropylphenyl)-3-methylsalicylaldiminate]-nickel(Ⅱ)(C2), bis[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ⅱ)(C3)和[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ph)(PPh₃)(C4)为催化剂, 在甲基铝氧烷(MAO)作用下, 对乙烯与甲基丙烯酸甲酯(MMA)进行催化共聚. 以C3为模型催化剂, 研究了Al/Ni摩尔比、聚合温度、聚合时间等对共聚反应的影响. 在最佳的聚合条件下, 探索了不同的催化剂结构对共聚反应的影响. 结果表明, 对于双(水杨醛亚胺)镍配合物, C2的活性高于C1和C3, 为13.1 kg/(mol Ni·h), 而C3的插入率最低, 为14.1%. 对于具有相同配体不同结构的配合物C3和C4, 含双水杨醛亚胺配体的C3的催化活性高于含单水杨醛亚胺配体的C4, 而两者在共聚单体MMA的插入率方面差别不大. 对所得共聚物微观结构和热性能进行了表征.

关键词: 水杨醛亚胺镍配合物, 聚烯烃, 乙烯-甲基丙烯酸甲酯共聚, 催化活性

Abstract:

Four salicylaldiminate-based nickel(Ⅱ) complexes: bis[N-(2,6-diisopropylphenyl)salicylaldiminate]-nickel(Ⅱ)(C1), bis[N-(2,6-diisopropylphenyl)-3-methylsalicylaldiminate]-nickel(Ⅱ)(C2), bis[N-(2,6-diisopropylphenyl)-3-isopropylsalicylaldiminate]-nickel(Ⅱ)(C3) and [N-(2,6-diisopropyl-phenyl)-3-isopropylsalicylaldiminate]-nickel(Ph)(PPh₃)(C4), in the presence of methylaluminoxane(MAO), were applied in copolymerization of ethylene and methyl methacrylate(MMA). The influences of polymerization parameters, such as molar ratio of Al/Ni, polymerization temperature and time, on the copolymerization were studied with complex C3 as a model catalyst. Based on these results, the effect of the structure of the nickel complexes on the copolymerization was explored under optimized polymerization conditions. Complex C2 exhibits higher catalytic activity of 13.1 kg/(mol Ni·h) than C1 and C3, while C3 gives the lowest comonomer MMA incorporation of 14.1% in the obtained copolymers. For complexes C3 and C4, with the same ligand but different structures, C3 displays better catalytic activity than C4, but their comonomer MMA incorporations are similar. The microstructures and thermo-properties of the obtained copolymers were characterized by means of FTIR, ¹H NMR,¹³C NMR, GPC and DSC.

Key words: Salicylaldiminate-based nickel(Ⅱ) complex, Polyolefin, Copolymerization of ethylene and methyl methacrylate, Catalytic activity

中图分类号:

O631
O614.81

TrendMD:

张丹枫, 张玉军, 喻国聪, 高文豪. 水杨醛亚胺镍配合物催化乙烯与甲基丙烯酸甲酯的共聚反应. 高等学校化学学报, 2017, 38(11): 2082.

ZHANG Danfeng, ZHANG Yujun, YU Guocong, GAO Wenhao. Copolymerization of Ethylene and Methyl Methacrylate with Salicylaldiminate Nickel(Ⅱ) Complexes^†. Chem. J. Chinese Universities, 2017, 38(11): 2082.

图/表 7

参考文献 36

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Entry	Cat.	Molar ratio of Al/Ni	t/h	T/℃	Activity/ (kg·mol^-1Ni·h^-1)	10^-4M_n	PDI	MMA Incorp. (%, molar fraction)	T_m/℃
1	C3	0	2	45
2	C3	100	2	45	6.2	2.6	2.4		112.0
3	C3	150	2	45	8.7	2.0	6.4	14.1	112.0
4	C3	200	2	45	6.5	2.1	6.0		122.0
5	C3	150	2	25	4.0	1.6	5.1		118.1
6	C3	150	2	65	3.3	1.6	3.9		119.1
7	C3	150	1	45	7.2				124.6
8	C3	150	4	45	4.5	2.4	4.0		107.5
9^b	C3	150	2	45	4.1	2.3	6.7		109.4
10	C1	150	2	45	6.3	2.1	6.2	60.4	118.5
11	C2	150	2	45	13.1	3.1	10.9	51.5	93.0
12	C4	150	2	45	3.7	2.3	3.3	12.6	119.1

Entry	Cat.	Molar ratio of Al/Ni	t/h	T/℃	Activity/ (kg·mol^-1Ni·h^-1)	10^-4M_n	PDI	MMA Incorp. (%, molar fraction)	T_m/℃
1	C3	0	2	45
2	C3	100	2	45	6.2	2.6	2.4		112.0
3	C3	150	2	45	8.7	2.0	6.4	14.1	112.0
4	C3	200	2	45	6.5	2.1	6.0		122.0
5	C3	150	2	25	4.0	1.6	5.1		118.1
6	C3	150	2	65	3.3	1.6	3.9		119.1
7	C3	150	1	45	7.2				124.6
8	C3	150	4	45	4.5	2.4	4.0		107.5
9^b	C3	150	2	45	4.1	2.3	6.7		109.4
10	C1	150	2	45	6.3	2.1	6.2	60.4	118.5
11	C2	150	2	45	13.1	3.1	10.9	51.5	93.0
12	C4	150	2	45	3.7	2.3	3.3	12.6	119.1