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Study on Oligomerization of Ethylene to Linear Low Carbon α-olefins by ⅣB、Ⅷ Groups Metal Complexes

Author: ZhangYuLiang
Tutor: HeRen
School: Dalian University of Technology
Course: Industrial Catalysis
Keywords: Ethylene oligomerization α-olefin Indenyl zirconium complexes Iron , cobalt , nickel complexes Bidentate phosphine ligands Computational Chemistry
CLC: O643.3
Type: PhD thesis
Year: 2002
Downloads: 160
Quote: 1
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Straight-chain low-carbon α-olefin comonomers for the production of linear low density polyethylene and high density polyethylene, domestic and foreign demand, but currently there is no the ethylene oligomerization law industrialized production of α-olefins. In order to form the technology with independent intellectual property rights in China, the paper of the of Ⅳ B family and Ⅷ metal Complexes for Ethylene gathered in the preparation of α-olefins reaction. Explore (Ind) Z rCl 2 , (1-η 5 -But-Ind) 2 ZrCl < sub> 2 , (η 5 -4,7-Me 2 -Ind) 2 ZrCl 2 with Et 2 Aluminium from AlCl catalyst system consisting of the catalysis of ethylene oligomerization and found that they have a moderate catalytic activity and a higher carbon α-olefin selectivity. Alkyl substituted indenyl, base number, the increase in catalytic activity; the indenyl substituents volume increases, the selectivity improvement of the low-carbon α-olefin. Investigated (η 5 -4,7-Me 2 -Ind) 2 ZrR 2 (R = Me CH 2 Ph, Ph) / Et 2 AlCl system for ethylene oligomerization catalysis. The results show that, (η 3 -4,7-Me 2 -Ind) 2 ZrCl 2 / Et 2 AlCl catalyst system performance the best in the optimal reaction conditions, the catalytic activity of 1714g / g · Zr · h C 4-10 olefin selectivity of 97.6 %, the linear C 4-10 alpha-olefin selectivity of 90.3%. (C 6 H 4-o- RN = CC 6 H 4-o -O-) 2 / sub> ZrCl the 2 (R = Me, H, CL) / Et the 2 AlCl catalyzed ethylene gathered in the synthesis of low-carbon α-olefin reaction . Found that the order in which the activity of the catalyst for the R = Me> R = H> R = Cl. The reaction temperature of 120 ° C, (C 6 H 4-o- Me-N = CC 6 H 4-o - O-) 2 ZrCl 2 the / Et 2 AlCl catalytic activity for 5590g / g Zr · h (C 4-10 ) = selective selectivity of 96.4% ,1-C 4-10 = 91.2%. (Dppe) MCl 2 [M = Fe (II), Co (II), Ni (II)] / EAO system for ethylene oligomerization catalysis. Reaction temperature of 200 ° C (dppe) of CoCl 2 / EAO catalyzed ethylene oligomerization activity 4021g / g · Co · h C 4-10 olefin choose of 95.5% ,1-C 4-10 = selectivity of 75.4%. (DPPP) MCl 2 [M = Fe (Ⅱ), Co (Ⅱ), Ni (Ⅱ)] / EAO also can catalyze the oligomerization of ethylene. Under the same reaction conditions, the five-membered ring with the slightly higher the catalytic activity than the six membered ring metal. The bidentate phosphine complexes / EAO catalytic system was added triphenylphosphine and 1,2 - bis (diphenyl phosphino) ethane to ethylene oligomerization activity and selectivity. Divalent metal complexes: (bipy) CoCl 2 ; (the C 6 H 4 -oRN = CC 6 H 4 -oO-) 2 M (M = Fe, Co); (acac) 2 Co with EAO catalysis of ethylene gathered. The results showed that the highest activity of bidentate nitrogen complex catalyzed. In the reaction temperature of 180 ° C, the catalytic activity of 2441g / g · Co · h, the selectivity of light olefins to 95.9%. (* Po) * the CI * white purple eve spectrum teeth Mu Township, Fort spoon spectrum Table loss, active catalytic Sarkozy. Got the idea is the cation Npo plant Ah. Korea drilling complex structure and charge parameters, calculated semi-empirical points at the orbit P * 3 methods well with the catalytic performance associated, also verify the catalytic active center anionic in nature. For an alkyl group containing the same fried ring either SI agent, has the same catalytic activity. 0.

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Chemical kinetics,catalysis > Catalytic
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