Synthesis of Novel Homogeneous Chromium-based Catalysts and Catalyze Ethylene Oligomerization†

doi:10.7503/cjcu20170109

Abstract

Abstract:

Three novel [NNN]-1,3,5-triazacyclohexane ligands containing O or N atom in the N-substituent of the type [NNN] were synthesized and characterized by ¹H NMR,¹³C NMR and electron ionization-mass spectrometry(EI-MS). Three kind of catalysts were prepared through the coordination of ligands with Cr(Ⅲ), and characterized by electrospray ionization-mass spectrometry(ESI-MS) and elemental analysis. Upon activation with methyl silane oxygen aluminum(MAO), Cr(Ⅲ) complexes were evaluated the activity to catalyze ethylene oligomerization as catalyst precursor. The effects of polymerization temperature, polymerization pressure and the molar ratio of Al to Cr on the activity and the selectivity for 1-hexene and 1-octene were investigated. The results showed that at the reaction temperature of 50 ℃ and ethylene pressure of 0.8 MPa and n(Al)/n(Cr) of 500, catalyst with 3-(dimethylamino)propy substituent possesses higher catalytic activity of 15.71×10⁵ g/(mol Cr·h) and the selectivity for 1-hexene and 1-octene can reach 91.02%. Otherwise catalyst with 3-ethoxypropyl substituent shows lower catalytic activity of 11.54×10⁵ g/(mol Cr·h), and the selectivity for 1-hexene and 1-octene is higher reaching 93.05% under the same polymerization condition.

Key words: NNN] Ligand, Chromium-complex, Homogeneous polymerization, Ethylene oligomerization, Linear α-olefin

CLC Number:

O631
O643.3

TrendMD:

LI Ping, MI Puke, GU Jinjing, XU Sheng. Synthesis of Novel Homogeneous Chromium-based Catalysts and Catalyze Ethylene Oligomerization^†[J]. Chem. J. Chinese Universities, 2017, 38(11): 2111.

Figures/Tables 6

References 23

[1]	Kan L., Guo F., Li C. F., Ren H. P., Chem. J. Chinese Universities,2010, 31(11), 54-58
	(阚林, 郭峰, 李传峰, 任鸿萍. 精细石油化工进展, 2011, 12(11), 54-58)
[2]	Qian B. Z., Petrochemical Industry Technolog., 2011, 18(1), 32-35
	(钱伯章. 石化技术, 2011, 18(1), 32-35)
[3]	Gao L. Y., Wang Q. T., Guo R., Tang Y., Fei X. J., China Synthetic Resin and Plastics,2015, 32(4), 85-89
	(高凌雁, 王群涛, 郭锐, 唐岩, 裴小静. 合成树脂及塑料, 2015, 32(4), 85-89)
[4]	Zhang Y. J., Li H. X., Xie B., Wang L. J., Fu Y., China Synthetic Resin and Plastics,2014, 31(2), 81-84
	(张瑀健, 李洪兴, 谢彬, 王立娟, 付义. 合成树脂及塑料, 2014, 31(2), 81-84)
[5]	Fei Y. W., Guo F., Yao T., Yang H. W., Bian S., Chem. J. Chinese Universities,2010, 31(11), 44-46
	(费逸伟, 郭峰, 姚婷, 杨宏伟, 卞森. 广州化工, 2015, 43(11), 44-46)
[6]	Bian S., Fei Y. W., Yao T., Jiang H. Z., Chem. J. Chinese Universities,2010, 31(6), 50-53
	(卞森, 费逸伟, 姚婷, 姜会泽. 化工时刊, 2015, 29(6), 50-53)
[7]	Cao Y. Y., Liu T., Run Y. B., Sun E. Z., Jiang Y., Technology & Development of Chemical Industry,2015, 44(12), 35-38
	(曹媛媛, 刘通, 闰义斌, 孙恩浩, 蒋岩. 化工技术与开发, 2015, 44(12), 35-38)
[8]	Mao G. L., Li Y., Zhang M. M., Xu T., Wu K. X., Science & Technology in Chemical Industry,2015, 23(5), 75-81
	(毛国梁, 李颖, 张敏敏, 徐韬, 武可新. 化工科技, 2015, 23(5), 75-81)
[9]	Qin Y. C., Ye J., Jiang B. B., Wang J. D., Yang Y. R., Chem. J. Chinese Universities,2010, 31(9), 1825-1831
	(秦一超, 叶健, 蒋斌波, 王靖岱, 阳永荣. 高等学校化学学报, 2015, 36(9), 1825-1831)
[10]	Wang J., Huo H. L., Li C. Q., Ma L. L., Shi W. G., Chen S., Chem. J. Chinese Universities,2010, 31(9), 1813-1818
	(王俊, 霍宏亮, 李翠勤, 马立莉, 施伟光, 陈帅. 高等学校化学学报, 2015, 36(9), 1813-1818)
[11]	Wang J., Yang G., Li C. Q., Shi W. G., Chem. J. Chinese Universities,2010, 31(7), 1536-1540
	(王俊, 杨光, 李翠勤, 施伟光. 高等学校化学学报, 2014, 35(7), 1536-1540)
[12]	McGuinness D. S., Wassetscheid P., Kelm W., Hu C., Englert U., Dixon J. T., Grove C., Chem. J. Chinese Universities,2010, 31(3), 334-335
[13]	Peitz S., Peulecke N., Aluri B.R., Hansen S., Müller B. H., Spannenberg A., Rosenthal U., Al-Hazmi M. H., Mosa F. M., Wöhl A., Müller W.,European Journal of Inorganic Chemistry, 2010, (8), 1167-1171
[14]	Shaikh Y., Albahily K., Sutcliffe M., Fomitcheva V., Gambarotta S., Korobkov I., Duchateau R., Chem. J. Chinese Universities,2010, 31(6), 1366-1369
[15]	Stennett T. E., Hey T. W., Ball L. T., Flynn S. R., Radcliffe J. E., McMullin C. L., Wingad R. L., Wass D. F., Chemcatchem,2013, 5(10), 2946-2954
[16]	Pei H. X., Shi P. F., Chen Y. H., Jiang T., Chem. J. Chinese Universities,2010, 31(6), 61-65
	(裴海香, 时鹏飞, 陈延辉, 姜涛. 精细石油化工, 2014, 31(6), 61-65)
[17]	Chen Y. J., Zuo W. W., Hao P., Zhang S., Gao K., Sun W. H., Chem. J. Chinese Universities,2010, 31(4), 750-762
[18]	Xiao L., Zhang M., Sun W. H., Polyhedron,2010, 29(1), 142-147
[19]	McGuinness D. S., Organometallic., 2009, 28, 244-248
[20]	Zhang J., Li A., Hor T. S., Chem. J. Chinese Universities,2010, 31(42), 9327-9333
[21]	Orson L. S., Houton T. X., Anhydrous Chromium(Ⅲ) Halide Complex Preparation, US 8450511B1,2013-05-28
[22]	Fan Z.F., Chromatographic Quality and Quantify, Chemical Industry Press, Beijing, 2007, 128-165
	(汪正范. 色谱定性与定量, 北京: 化学工业出版社, 2007, 164-165)
[23]	Fan L. L., Zhang L., Chen Y. H., Jiang T., Chem. J. Chinese Universities,2010, 31(3), 6-10
	(范琳琳, 张乐, 陈延辉, 姜涛. 精细石油化工, 2016, 33(3), 6-10)

Catalyst	Temperature/℃	10⁵Activity/[g·(mol Cr·h)^-1]	Production distribution(%)
Catalyst	Temperature/℃	10⁵Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Cr-1	40	6.12	4.81	57.55	30.32	7.32
	50	15.71	2.96	59.37	31.65	6.02
	60	13.92	2.38	57.61	30.64	9.37
	70	10.36	1.71	43.54	41.21	13.54
	80	8.82	3.07	40.99	44.18	11.76
Cr-2	40	4.09	2.11	57.37	30.50	10.02
	50	5.34	1.23	59.42	31.46	7.89
	60	6.04	2.75	56.38	32.74	8.13
	70	5.86	4.08	49.27	34.81	11.84
	80	4.91	3.43	45.81	31.78	18.98
Cr-3	40	5.31	3.11	56.10	32.93	7.86
	50	11.54	1.93	60.58	32.47	5.02
	60	10.27	1.24	59.03	34.90	4.83
	70	8.91	2.98	50.76	29.49	16.77
	80	8.05	4.99	41.62	24.51	28.88

Catalyst	Temperature/℃	10⁵Activity/[g·(mol Cr·h)^-1]	Production distribution(%)
Catalyst	Temperature/℃	10⁵Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Cr-1	40	6.12	4.81	57.55	30.32	7.32
	50	15.71	2.96	59.37	31.65	6.02
	60	13.92	2.38	57.61	30.64	9.37
	70	10.36	1.71	43.54	41.21	13.54
	80	8.82	3.07	40.99	44.18	11.76
Cr-2	40	4.09	2.11	57.37	30.50	10.02
	50	5.34	1.23	59.42	31.46	7.89
	60	6.04	2.75	56.38	32.74	8.13
	70	5.86	4.08	49.27	34.81	11.84
	80	4.91	3.43	45.81	31.78	18.98
Cr-3	40	5.31	3.11	56.10	32.93	7.86
	50	11.54	1.93	60.58	32.47	5.02
	60	10.27	1.24	59.03	34.90	4.83
	70	8.91	2.98	50.76	29.49	16.77
	80	8.05	4.99	41.62	24.51	28.88

Catalyst	p/MPa	10⁵Activity/[g·(mol Cr·h)^-1]	Production distribution(%)
Catalyst	p/MPa	10⁵Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Cr-1	0.1	5.21	30.03	38.72	29.14	2.11
	0.2	7.89	21.76	45.38	28.40	4.46
	0.4	9.05	3.44	51.53	37.21	7.82
	0.8	13.92	2.38	57.61	30.64	9.37
	1. 6	16.38	1.21	36.20	21.56	41.03
Cr-2	0.1	4.72	24.98	36.97	32.83	5.22
	0.2	5.43	4.93	47.23	41.42	6.42
	0.4	5.97	4.92	54.51	36.12	4.45
	0.8	6.04	2.75	56.38	32.74	8.13
	1.6	9.13	1.33	41.02	23.61	34.04
Cr-3	0.1	4.85	26.88	43.92	28.46	3.74
	0.2	5.46	7.32	51.68	34.57	6.43
	0.4	7.83	1.85	56.83	37.29	4.03
	0.8	10.27	1.24	59.03	34.90	4.83
	1.6	12.51	0.76	39.74	21.09	38.41

Catalyst	p/MPa	10⁵Activity/[g·(mol Cr·h)^-1]	Production distribution(%)
Catalyst	p/MPa	10⁵Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Cr-1	0.1	5.21	30.03	38.72	29.14	2.11
	0.2	7.89	21.76	45.38	28.40	4.46
	0.4	9.05	3.44	51.53	37.21	7.82
	0.8	13.92	2.38	57.61	30.64	9.37
	1. 6	16.38	1.21	36.20	21.56	41.03
Cr-2	0.1	4.72	24.98	36.97	32.83	5.22
	0.2	5.43	4.93	47.23	41.42	6.42
	0.4	5.97	4.92	54.51	36.12	4.45
	0.8	6.04	2.75	56.38	32.74	8.13
	1.6	9.13	1.33	41.02	23.61	34.04
Cr-3	0.1	4.85	26.88	43.92	28.46	3.74
	0.2	5.46	7.32	51.68	34.57	6.43
	0.4	7.83	1.85	56.83	37.29	4.03
	0.8	10.27	1.24	59.03	34.90	4.83
	1.6	12.51	0.76	39.74	21.09	38.41

Catalyst	n(Al)/n(Cr)	10⁵Activity/[g·(mol Cr·h)^-1]	Production distribution(%)
Catalyst	n(Al)/n(Cr)	10⁵Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Cr-1	200	7. 93	20.31	37.71	36.96	5.02
	300	9.12	14.79	41.06	37.38	6.77
	500	13.92	2.38	57.61	30.64	9.37
	800	14.63	4.54	55.12	32.72	7.62
	1000	12.87	1.96	56.47	32.77	8.80
Cr-2	200	1.21	9.67	41.56	29.01	19.76
	300	4.35	7.08	50.27	29.73	12.92
	500	6.04	2.75	56.38	32.74	8.13
	800	5.81	4.23	58.71	30.44	6.62
	1000	5.08	5.03	55.30	29.62	10.05
Cr-3	200	2.28	15.64	40.64	27.93	15.79
	300	9.72	7.31	51.72	33.67	7.30
	500	10.27	1.24	59.03	34.90	4.83
	800	9.43	3.53	58.10	31.26	7.11
	1000	6.19	6.08	49.58	27.61	16.73