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

doi:10.7503/cjcu20150385

Abstract

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

CLC Number:

O631
O643.3

TrendMD:

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

Figures/Tables 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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