新型均相铬系催化剂的制备与催化乙烯齐聚

doi:10.7503/cjcu20170109

摘要/Abstract

摘要：

合成了3种新型的N取代基中含有O/N杂原子的1,3,5-三氮杂环己烷[NNN]型配体, 利用氢核磁共振谱(¹H NMR)、碳核磁共振谱(¹³C NMR)及电子轰击质谱(EI-MS)等方法对其进行表征. 将[NNN]型配体与Cr(Ⅲ)络合制备相应的均相铬催化剂, 采用电喷雾质谱(ESI-MS)及元素分析分别对其进行表征. 以甲基烷氧铝(MAO)为助催化剂, 考察了反应温度、反应压力及铝铬摩尔比等因素对催化乙烯齐聚催化性能的影响. 研究结果表明, 在以甲苯为溶剂, 反应温度50 ℃, 反应压力0.8 MPa , 铝铬摩尔比为500:1, Cr浓度为 2.0×10^-4 mol/L的反应条件下, 取代基为3-二甲氨基丙基的均相铬催化剂的催化活性能够达到15.71×10⁵ g/(mol Cr·h), 对1-己烯和1-辛烯的选择性达到91.02%, 而取代基为3-乙氧基丙基的均相铬催化剂的催化活性比较低, 为11.54×10⁵ g/(mol Cr·h), 但对1-己烯和1-辛烯的选择性较高, 达到93.05%.

关键词: NNN]型配体, 铬配合物, 均相聚合, 乙烯齐聚, 线性α-烯烃

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

中图分类号:

O631
O643.3

TrendMD:

李平, 米普科, 顾瑾璟, 许胜. 新型均相铬系催化剂的制备与催化乙烯齐聚. 高等学校化学学报, 2017, 38(11): 2111.

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

图/表 6

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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