新型树枝状桥联镍配合物的合成及催化烯烃齐聚性能

doi:10.7503/cjcu20150385

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (9): 1813.doi: 10.7503/cjcu20150385

新型树枝状桥联镍配合物的合成及催化烯烃齐聚性能

王俊¹, 霍宏亮¹, 李翠勤¹(), 马立莉¹, 施伟光¹, 陈帅²

1. 东北石油大学石油与天然气化工省重点实验室, 大庆 163318
2. 中国科学院大连化学物理研究所, 大连 116023

收稿日期:2015-05-14 出版日期:2015-09-10 发布日期:2015-08-21
作者简介:联系人简介: 李翠勤, 女, 博士, 副教授, 主要从事树枝状大分子及高分子材料方面研究. E-mail:dqpilicuiqin@126.com
基金资助:
国家自然科学基金(批准号: 21576048)、中国石油科技创新基金研究项目(批准号: 2014D-5006-0503)和东北石油大学青年科学基金(批准号: 2013NQ130)资助

Synthesis of Novel Dendritic Bridging Nickel Complex for Oligomerization of Olefins^†

WANG Jun¹, HUO Hongliang¹, LI Cuiqin^1,^*(), MA Lili¹, SHI Weiguang¹, CHEN Shuai²

1. Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University, Daqing 163318, China
2. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Received:2015-05-14 Online:2015-09-10 Published:2015-08-21
Contact: LI Cuiqin E-mail:dqpilicuiqin@126.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.201576048), the PetroChina Innovation Foundation(No.2014D-5006-0503) and the Youth Science Foundation of Northeast Petroleum University, China(No.2013NQ130)

摘要/Abstract

摘要：

合成了一种N,N-二齿配位的新型树枝状桥联吡啶亚胺配体及其镍配合物, 利用元素分析、傅里叶变换红外光谱(FTIR)和电喷雾电离质谱(ESI-MS)对其结构进行了表征. 以二氯乙基铝(EtAlCl₂)为助催化剂, 考察了树枝状桥联镍配合物催化乙烯齐聚和1-戊烯齐聚的聚合条件对产物分布的影响. 结果表明, 当聚合时间为60 min, 聚合压力为0.5 MPa, Al/Ni摩尔比为150时, 乙烯齐聚产物中C₁₀~C₁₄的选择性最高, 达到93%, 催化活性为0.99×10⁶ g/(mol Ni·h); 当聚合时间为60 min, Al/Ni摩尔比为300时, 1-戊烯齐聚产物中C₂₀的选择性最高为70.5%, 催化活性为2.47×10⁵ g/(mol Ni·h). 该树枝状桥联镍配合物对乙烯齐聚反应和1-戊烯齐聚反应均具有良好的催化活性和较高碳数的齐聚产物选择性.

关键词: 树枝状大分子, 桥联镍配合物, 乙烯齐聚, 1-戊烯齐聚

Abstract:

A novel N,N-bidentate dendritic bridging pyridine-imine ligand and its nickel complex were prepared and characterized by elemental analysis, Fourier transform infrared spectrometry(FTIR) and electrospray ionization-mass spectrometry(ESI-MS). The dendritic nickel complex was used as a precatalyst in the oligomerization of ethylene with the co-catalyst ethyl dichloroaluminum(EtAlCl₂), as well as a precursor in the oligomerization of 1-pentene. The effects of the reaction time, reaction pressure and the molar ratio of Al/Ni on the catalytic activities and the distribution of the product in the oligomerization were investigated. The dendritic nickel complex revealed the selectivity of higher olefins(C₁₀—C₁₄) reached up to 93% and the catalytic activity was 0.99×10⁶ g/(mol Ni·h) at the reaction time of 60 min, ethylene pressure of 0.5 MPa and the molar ratio of Al/Ni of 150 in the oligometization of ethylene. At the reaction time of 60 min and the molar ratio of Al/Ni of 300, the catalyst also had excellent catalytic performance in the oligomerization of 1-pentene. The selectivity of C₂₀ reached to 70.5% and the catalytic activity was 2.47×10⁵ g/(mol Ni·h). The dendritic nickel complex exhibited good catalytic activities and selectivities for higher carbon number olefins in ethylene oligomerization and 1-pentene oligomerization.

Key words: Dendrimer, Bridging nickel complex, Ethylene oligomerization, 1-Pentene oligomerization

中图分类号:

O631
O643.3

TrendMD:

王俊, 霍宏亮, 李翠勤, 马立莉, 施伟光, 陈帅. 新型树枝状桥联镍配合物的合成及催化烯烃齐聚性能. 高等学校化学学报, 2015, 36(9): 1813.

WANG Jun, HUO Hongliang, LI Cuiqin, MA Lili, SHI Weiguang, CHEN Shuai. Synthesis of Novel Dendritic Bridging Nickel Complex for Oligomerization of Olefins^†. Chem. J. Chinese Universities, 2015, 36(9): 1813.

图/表 5

Scheme 1 Synthetic routes of dendritic bridging pyridine imine ligand(Ⅲ) and dendritic nickel complex(Ⅴ)

Table 1 Infrared spectral data of ligand and complex

Compd.	IR(cm^-1)
Compd.	ν_—CONH	$ν — C H 2 —$	$ν — CO$	$ν — CN$	δ_—CONH	ν_—N<	ν_N—Ni
Ligand	3288	2950	1680	1640	1540	1120
Complex	3244	2939	1617	1600	1570	1116	644

Table 1 Infrared spectral data of ligand and complex

Compd.	IR(cm^-1)
Compd.	ν_—CONH	$ν — C H 2 —$	$ν — CO$	$ν — CN$	δ_—CONH	ν_—N<	ν_N—Ni
Ligand	3288	2950	1680	1640	1540	1120
Complex	3244	2939	1617	1600	1570	1116	644

Fig.1 ESI-MS spectra of ligand(A) and complex(B)

Table 2 Results of oligomerization of ethylene using complex/EtAlCl2 as catalyst

Entry	t/min	p/MPa	n(Al)/n(Ni)	10^-6Activity/ [g·(mol Ni·h)^-1]	Selectivity(%)
Entry	t/min	p/MPa	n(Al)/n(Ni)	10^-6Activity/ [g·(mol Ni·h)^-1]	C₁₀	C₁₂	C₁₄	C₁₀—C₁₄	C₁₆₊
1	60	0.5	500	2.89	17	57	15	89	11
2	90	0.5	500	2.00	8	36	33	77	23
3	120	0.5	500	1.30	0	20	41	61	39
4	60	0.1	500	0.05	33	22	20	75	25
5	60	0.3	500	0.80	25	35	25	85	15
6	60	0.5	100	0.45	20	40	32	92	8
7	60	0.5	150	0.99	12	44	37	93	7
8	60	0.5	250	1.34	4	48	30	82	18

Table 3 Results of oligomerization of 1-pentene using complex/EtAlCl2 as catalyst

Entry	n(Al)/n(Ni)	10^-5 Activity/ [g·(mol Ni·h)^-1]	Selectivity(%)
Entry	n(Al)/n(Ni)	10^-5 Activity/ [g·(mol Ni·h)^-1]	C₁₅	C₂₀	C₂₅₊
1	100	2.01	3.0	24.3	72.7
2	150	2.63	1.1	44.3	54.6
3	250	2.35	1.2	48.5	50.3
4	300	2.47	4.5	70.5	25.0
5	350	2.11	1.4	63.1	35.5
6	500	2.06	2.4	65.2	32.4

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新型树枝状桥联镍配合物的合成及催化烯烃齐聚性能

Synthesis of Novel Dendritic Bridging Nickel Complex for Oligomerization of Olefins^†

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新型树枝状桥联镍配合物的合成及催化烯烃齐聚性能

Synthesis of Novel Dendritic Bridging Nickel Complex for Oligomerization of Olefins†

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Synthesis of Novel Dendritic Bridging Nickel Complex for Oligomerization of Olefins^†