Synthesis and Ethylene Oligomerization Behavior of Novel Dendritic PNP Chromium Catalyst†

doi:10.7503/cjcu20160687

Abstract

Abstract:

A novel dendritic PNP ligand was synthesized using 1.0G dendritic polyammidoamine(PAMAM) and chlorodiphenylphosphine as the raw materials through substitution reaction, and the dendritic PNP chromium(Ⅲ) catalyst was synthesized from the reaction with chromium(Ⅲ) chloride tetrahydrofuran complex as material. The structure of novel dendritic PNP ligand and PNP chromium(Ⅲ) catalyst were characterized by Fourier transform infrared(FTIR), ultraviolet-visible(UV-Vis), nuclear magnetic resonance(NMR), electrospray ionization-mass spectroscopy(ESI-MS) and elemental analysis. The results indicate that the structure of novel dendritic PNP ligand and PNP chromium(Ⅲ) catalyst are consistent with theoretical structure. The dendritic PNP chromium(Ⅲ) catalyst was used as a precatalyst in the oligomerization of ethylene with the co-catalyst methylaluminoxane(MAO). The effects of solvent, reaction temperature, reaction pressure and the molar ratio of Al/Cr on the catalytic activities and selectivity in the oligomerization were investigated. With MAO as co-catalyst and toluene as solvent, the selectivity of novel dendritic PNP chromium(Ⅲ) catalyst on ethylene trimer and tetramer reached up to 36.76% and the catalytic activity was 2.15×10⁵ g/(mol Cr·h) at reaction temperature of 25 ℃, reaction pressure of 0.9 MPa and Al/Cr molar ratio of 500.

Key words: 1.0G Polyammidoamine, Novel dendritic PNP ligand, Dendritic PNP chromium catalyst, Ethylene trimerization and tetramerization

TrendMD:

WANG Jun, GAO Rui, YU Yanlong, ZHANG Na, LI Cuiqin, SHI Weiguang. Synthesis and Ethylene Oligomerization Behavior of Novel Dendritic PNP Chromium Catalyst^†[J]. Chem. J. Chinese Universities, 2017, 38(7): 1257.

Figures/Tables 8

References 32

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Peak No.	Species of hydrogen proton	Types of peak	Number of protons	δ	J/Hz
1	—N—CH₂—CH₂—N—	t	4	2.19—2.28
2	—N—CH₂—CH₂—CO—	t	8	2.93—3.00	7.5
3	—CO—CH₂—	t	8	2.38—2.45	6.0
4	—CONH—	s	4	8.27
5	—CON—CH₂—	q	8	2.88—2.95
6	—CH₂—NP—	t	8	2.70—2.80	7.6
7,8,9	Ph—H	m	80	7.29—7.59

Peak No.	Species of hydrogen proton	Types of peak	Number of protons	δ	J/Hz
1	—N—CH₂—CH₂—N—	t	4	2.19—2.28
2	—N—CH₂—CH₂—CO—	t	8	2.93—3.00	7.5
3	—CO—CH₂—	t	8	2.38—2.45	6.0
4	—CONH—	s	4	8.27
5	—CON—CH₂—	q	8	2.88—2.95
6	—CH₂—NP—	t	8	2.70—2.80	7.6
7,8,9	Ph—H	m	80	7.29—7.59

Solvent	10^-5Activity/[g·(mol Cr·h)^-1]	Selectivity(%)
Solvent	10^-5Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Hexane	1.41	92.86	7.12	0.01	0.01
Cyclohexane	1.55	84.55	9.65	3.85	1.95
Toluene	2.05	77.65	7.77	11.13	3.45

Solvent	10^-5Activity/[g·(mol Cr·h)^-1]	Selectivity(%)
Solvent	10^-5Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Hexane	1.41	92.86	7.12	0.01	0.01
Cyclohexane	1.55	84.55	9.65	3.85	1.95
Toluene	2.05	77.65	7.77	11.13	3.45

Temperature/℃	10^-5Activity/[g·(mol Cr·h)^-1]	Selectivity(%)
Temperature/℃	10^-5Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
15	1.94	82.42	3.78	12.87	0.93
25	2.05	77.65	7.77	11.13	3.45
35	1.51	73.53	8.01	16.76	1.70
45	1.21	69.51	8.21	21.24	1.04
55	1.00	68.77	5.71	19.01	6.51