Key Intermediates in Metalloceneand Post-metallocene-Catalyzed Polymerization Full article
| Journal |
Kinetics and Catalysis
ISSN: 0023-1584 , E-ISSN: 1608-3210 |
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| Output data | Year: 2007, Volume: 48, Number: 4, Pages: 490-504 Pages count : 15 DOI: 10.1134/S0023158407040052 | ||||
| Tags | Catalytic System; Lewis Acid Site; TIBA; Titanocene; Zwitterionic Intermediate | ||||
| Authors |
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| Affiliations |
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Funding (4)
| 1 | Russian Foundation for Basic Research | 03-03-33034 |
| 2 | Russian Foundation for Basic Research | 06-03-32700 |
| 3 | International Association for the Promotion of Co-operation with Scientists from the New Independent States of the Former Soviet Union | 00-00841 |
| 4 | Royal Society | 2004/R1-FSU |
Abstract:
The structures of intermediates formed upon the activation by methylaluminoxane (MAO) of a wide range of metallocene and post-metallocene catalysts of olefin polymerization were studied by 13C, 1H, and 19F NMR. For all metallocenes considered (L2ZrCl2 and L2TiCl2), under conditions similar to real polymerization conditions (Al/Zr > 200), two types of intermediates were identified in the reaction solution, namely, heterodinuclear ion pairs [L2 M(μ-Me)2AlMe2]+[Me-MAO]− (III) and zwitterionic intermediates L2 MMe+←Me-Al−≡MAO (IV (M = Zr, Ti). The relative concentration of III increases with an increase in the Al/Zr ratio. In the post-metallocene/MAO catalytic systems, the reaction solution can be dominated either by heterodinuclear pairs of type III (bis(imino)pyridyl iron complexes) or by zwitterionic intermediates of type IV (half-titanocenes, complexes with restricted geometry). Both species III and species IV catalyze olefin polymerization. Both the species initiating polymerization, [L 2 ′ TiMe(S)]+[Me-MAO]−, and the species responsible for chain growth, [L [L 2 ′ TiP]+[Me-MAO]− (P is the polymer chain, and S is a solvent molecule), were characterized in the bis(phenoxyimine) titanium complex/MAO system.
Cite:
Talsi E.P.
, Bryliakov K.P.
, Semikolenova N.V.
, Zakharov V.A.
, Bochmann M.
Key Intermediates in Metalloceneand Post-metallocene-Catalyzed Polymerization
Kinetics and Catalysis. 2007. V.48. N4. P.490-504. DOI: 10.1134/S0023158407040052 WOS Scopus РИНЦ ANCAN OpenAlex
Key Intermediates in Metalloceneand Post-metallocene-Catalyzed Polymerization
Kinetics and Catalysis. 2007. V.48. N4. P.490-504. DOI: 10.1134/S0023158407040052 WOS Scopus РИНЦ ANCAN OpenAlex
Original:
Талзи Е.П.
, Брыляков К.П.
, Семиколенова Н.В.
, Захаров В.А.
, Бохман М.
Ключевые интермедиаты металлоценовой и постметаллоценовой полимеризации
Кинетика и катализ. 2007. Т.48. №4. С.521-536. РИНЦ
Ключевые интермедиаты металлоценовой и постметаллоценовой полимеризации
Кинетика и катализ. 2007. Т.48. №4. С.521-536. РИНЦ
Dates:
| Submitted: | Jun 23, 2006 |
| Published print: | Jul 1, 2007 |
Identifiers:
| Web of science: | WOS:000248855200005 |
| Scopus: | 2-s2.0-34548023272 |
| Elibrary: | 13562525 |
| Chemical Abstracts: | 2007:913029 |
| Chemical Abstracts (print): | 149:224593 |
| OpenAlex: | W2021202520 |