1H and 13C NMR Study of the Intermediates Formed by (Cp-R)2ZrCl2 Activation with MAO and AlMe3/[CPh3][B(C6F5)4]. Correlation of Spectroscopic and Ethene Polymerization Data | Sciact - CRIS-система Института катализа

1H and 13C NMR Study of the Intermediates Formed by (Cp-R)2ZrCl2 Activation with MAO and AlMe3/[CPh3][B(C6F5)4]. Correlation of Spectroscopic and Ethene Polymerization Data Научная публикация

Журнал

Macromolecular Chemistry and Physics
ISSN: 1022-1352 , E-ISSN: 1521-3935

Вых. Данные

Год: 2003, Том: 204, Номер: 8, Страницы: 1110-1117 Страниц : 8 DOI: 10.1002/macp.200390079

Ключевые слова

1H/13C NMR, Metallocene catalysts, Polyethylene (PE), Structure-property relations, Transition-metal chemistry

Авторы

Bryliakov Konstantin P. ^1,2 , Semikolenova Nina V. ¹ , Yudaev Dmitrii V. ¹ , Ystenes Martin ³ , Rytter Erling ^3,4 , Zakharov Vladimir A. ¹ , Talsi Evgenii P. ^1,2

Организации

1	Boreskov Institute of Catalysis, 630090 Novosibirsk, Prospect Akad. Lavrentieva, 5, Russia
2	Natural Sciences Department, Novosibirsk State University, 630090 Novosibirsk, Pirogova 2, Russia
3	Dept. of Chemical Engineering, Norwegian University of Science and Technology (NTNU), N-7491 Trondheim, Norway
4	Statoil Research Centre, N-7005, Trondheim, Norway

Using 1H and 13C NMR spectroscopy, cationic intermediates formed by activation of (Cp-R)2ZrCl2 (R = nBu, tBu and 1,2,3-Me3) with MAO in toluene were monitored at Al/Zr ratios from 50 to 1 000. The catalysts (Cp-R)2ZrCl2/AlMe3/CPh3+B(C6F5)4− (nBu, tBu and 1,2,3-Me3) were also studied for comparison of spectroscopic and polymerization data with MAO based systems. Complexes of type (Cp-R)2ZrMe+ ← Me−-Al[TRIPLE BOND]MAO (IV) with different Me-MAO− counter anions have been identified in the (Cp-R)2ZrCl2/MAO systems at low Al/Zr ratios. At Al/Zr ratios of 200–1 000, the complex [(Cp-R)2Zr(μ-Me)2AlMe2]+ Me-MAO− (III) dominates in all MAO-based reaction systems. Ethene polymerization activity strongly depends on the Al/Zr ratio (Al/Zr = 200–1 000) for the systems (Cp-nBu)2ZrCl2/MAO and (Cp-tBu)2ZrCl2/MAO, while it is virtually constant in the same range of Al/Zr ratios for the catalytic system (Cp-1,2,3-Me3)2ZrCl2/MAO. The data obtained are interpreted on the assumption that complex III is the actual precursor of active centers of polymerization in MAO based systems.

Bryliakov K.P. , Semikolenova N.V. , Yudaev D.V. , Ystenes M. , Rytter E. , Zakharov V.A. , Talsi E.P.
1H and 13C NMR Study of the Intermediates Formed by (Cp-R)2ZrCl2 Activation with MAO and AlMe3/[CPh3][B(C6F5)4]. Correlation of Spectroscopic and Ethene Polymerization Data
Macromolecular Chemistry and Physics. 2003. V.204. N8. P.1110-1117. DOI: 10.1002/macp.200390079 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	5 дек. 2002 г.
Принята к публикации:	18 мар. 2003 г.
Опубликована в печати:	1 мая 2003 г.
Опубликована online:	21 мая 2003 г.

Web of science:	WOS:000183607600008
Scopus:	2-s2.0-0037666113
РИНЦ:	13418964
Chemical Abstracts:	2003:500215
Chemical Abstracts (print):	139:197818
OpenAlex:	W2161586135

БД	Цитирований
Web of science	17
Scopus	19
РИНЦ	19
OpenAlex	16