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Effect of Temperature on the Number of Active Sites and Propagation Rate Constant at Ethylene Polymerization Over Supported Bis(imino)pyridine Iron Catalysts Full article

Journal Journal of Polymer Science, Part A: Polymer Chemistry
ISSN: 0887-624X , E-ISSN: 1099-0518
Output data Year: 2008, Volume: 46, Number: 19, Pages: 6621-6629 Pages count : 9 DOI: 10.1002/pola.22972
Tags Activation energy, Bis(imino)pyridine iron catalysts, Kinetics (polym.), Number of active sites, Polyethylene (PE), Propagation rate constant
Authors Barabanov Artem A. 1 , Bukatov Gennady D. 1 , Zakharov Vladimir A. 1
Affiliations
1 Boreskov Institute of Catalysis SB RAS, Pr. akademika Lavrentieva 5, 630090 Novosibirsk, Russia

Funding (1)

1 Russian Foundation for Basic Research 07-03-00311

Abstract: The inhibition of ethylene polymerization with radioactive carbon monoxide (14CO) was used to obtain data on the number of active sites (CP) and propagation rate constant (kP) at ethylene polymerization in the temperature range of 35–70 8C over supported catalysts LFeCl2/Al2O3, LFeCl2/SiO2, and LFeCl2/MgCl2 (L: 2,6-(2,6-(Me)2C6H3N ¼ CMe)2C5H3N) with activator Al(i-Bu)3. The values of effective activation energy (Eeff), activation energy of propagation reaction (EP), and temperature coefficients of variation of the number of active sites (ECp ¼ Eeff  EP) were determined. The activation energies of propagation reaction for catalysts LFeCl2/Al2O3, LFeCl2/SiO2, and LFeCl2/MgCl2 were found to be quite similar (5.2–5.7 kcal/mol). The number of active sites diminished considerably as the polymerization temperature decreased, the ECp value being 5.2–6.2 kcal/mol for these catalysts at polymerization in the presence of hydrogen. The reactions of reversible transformations of active centers to the surface hydride species at polymerization in the presence and absence of hydrogen are proposed as the derivation of ECp.
Cite: Barabanov A.A. , Bukatov G.D. , Zakharov V.A.
Effect of Temperature on the Number of Active Sites and Propagation Rate Constant at Ethylene Polymerization Over Supported Bis(imino)pyridine Iron Catalysts
Journal of Polymer Science, Part A: Polymer Chemistry. 2008. V.46. N19. P.6621-6629. DOI: 10.1002/pola.22972 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: Apr 18, 2008
Accepted: Jul 14, 2008
Published online: Aug 27, 2008
Published print: Oct 1, 2008
Identifiers:
Web of science: WOS:000259589300024
Scopus: 2-s2.0-54749110253
Elibrary: 13589966
Chemical Abstracts: 2008:1204315
Chemical Abstracts (print): 149:576875
OpenAlex: W2010636016
Citing:
DB Citing
Web of science 15
Scopus 16
Elibrary 16
OpenAlex 16
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