The Catalytic Transformation of Ethylene Using Chromium(III) Complexes with Bidentate Nitrogen-Containing Ligands
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The Catalytic Transformation of Ethylene Using Chromium(III) Complexes with Bidentate Nitrogen‑Containing Ligands Ilya A. Babenko1 · Evgeniy V. Kondrashov2 · Igor B. Rozentsveig1,2 · Gennadiy P. Belov3 · Alexey I. Vilms1 Received: 1 October 2019 / Accepted: 15 December 2019 © Springer Science+Business Media, LLC, part of Springer Nature 2020
Abstract It has been shown that catalytic systems of the type Cr(III)/TEA/L, where Cr(III) is tris(2-ethylhexanoate)chromium(III) (Cr(EH)3), tris(acetylacetone)chromium(III) (Cr(acac)3); TEA is triethylaluminum; L is 2,2′-bipyridyne (bipy), 1,10-phenanthroline (Phen), N,N′-bis-(cyclohexyl)diazabutadiene-1,3 (DCy-DABD) and N,N′-bis-(2,6-diisopropylphenyl)diazabutadiene-1,3 (DPPh-DABD), can be employed for ethylene poly- and olygomerization at 60–80 °C and under pressure 2–3 MPa. The proton affinity of the used bidentate nitrogen-containing ligands is evaluated using quantum chemical calculations. The DCy-DABD, which has the lowest basicity, turns out to be the best ligand for the selective di- and trimerization of ethylene. Graphic Abstract
III
+
Cr + L + TEA
n
+ PE
L= N
N
,
N
N
,
N
N
,
N
N
Keywords Ethylene · Oligomerization · Polymerization · Tris(acetylacetonate)chromium(III) · Tris(2-ethylhexanoate) chromium(III)
1 Introduction The processes of ethylene oligomerization involving catalytic systems (CS) based on transition metals/organic ligands to afford higher linear alpha-olefins (LAO) have Gennadiy P. Belov—deceased. * Ilya A. Babenko [email protected] * Gennadiy P. Belov [email protected] Evgeniy V. Kondrashov [email protected] Igor B. Rozentsveig [email protected]
been comprehensively studied [1–8]. Nevertheless, interest in this problem is still not fading away [9–11]. This is due to the fact that LAO are highly demanded in the chemical industry because of their widespread use in various processes, e.g. in large-scale production of ethylene, propene copolymerization, as well as in manufacturing the low Alexey I. Vilms [email protected] 1
Irkutsk State University, Karl Marks St., 1, Irkutsk, Russia 664003
2
Irkutsk Institute of Chemistry. A.E. Favorsky SB RAS, Favorsky St., 1, Irkutsk, Russia 664033
3
Institute of Problems of Chemical Physics RAS, Prospect Academician Semenov, 1, Chernogolovka, Russia 142432
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molecular weight products (higher alcohols, acids, bases of synthetic oils and etc.). Among numerous stabilizing ligands, used in combination with chromium complexes [1–11], N-donor organic ligands are of special importance. It is known that bidentate nitrogen-containing ligands containing the diazabutadiene fragment –N=CR1–CR2=N– are generally employed together with different transition metals in CS for ethylene polymerization [12]. In patent [13] it was claimed the application of such ligand in the system chromium(III)/ triethylaluminum/N,N′-bis-(1,1,3,3-tetramethylbutyl)diazabutadiene-1,3 (DTMeBu-DABD) at 120 °C and 4 MPa with an activity of 22,995 g prod (gCr h)−1 and a content of the
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