NMR and EPR Trapping of the Active Species in the Ethylene Polymerization and Trimerization Catalyst Systems
Full article
Общее |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
Journal |
Catalysis for Sustainable Energy
ISSN: 2084-6819
|
Output data |
Year: 2016,
Volume: 3,
Number: 1,
Pages: 15-24
Pages count
: 10
DOI:
10.1515/cse-2016-0004
|
Tags |
Ethylene; Intermediate; Mechanism, NMR and EPR; Polymerization; Post-metallocene |
Authors |
Soshnikov I.E.
1,2
,
Semikolenova N.V.
1
,
Antonov A.A.
1,2
,
Bryliakov K.P.
1,2
,
Zakharov V.A.
1,2
,
Talsi E.P.
2
|
Affiliations |
1 |
Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation
|
2 |
Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russian Federation
|
|
Funding (2)
1
|
Russian Foundation for Basic Research
|
16-53-53014
|
2
|
Russian Foundation for Basic Research
|
16-03-00236
|
In this work, previously undetected intermediates of several practically promising catalyst systems for ethylene polymerization and trimerization are discussed. In particular, the activation of ethylene polymerization catalysts (1) LNiCl2 (L = 2,4,6-trimethyl- (N-5,6,7-trihydroquinolin-8-ylidene)phenylamine) with AlEt2Cl and AlMe2Cl, (2) activation of bis(imino)pyridine vanadium(III) chloride L1VIIICl3 (L1 = 2,6-(ArN=CMe)2C5H3N, Ar = 2,6-iPr2C6H3; 2,6-Me2C6H3; 2,4,6-Me3C6H2; 3,5- F2C6H3) with AlMe3/[Ph3C]+[B(C6F5)]4¯ and MAO, and (3) selective ethylene trimerization catalyst (FI)TiCl3 (FI = phenoxyimine ligand with an additional aryl-OCH3 donor) with MAO have been assessed by NMR and EPR spectroscopy. The nature of ion-pair intermediates – the closest precursors of the propagating species – has been established, and the major catalyst deactivation pathways are discussed.