Studies in ring-opening polymerization. The kinetics of the reactions between tungsten hexachloride and cyclopentene: A study of the metathesis initiation reaction

The complex series of reactions that takes place between WCl6 and cyclopentene was studied spectroscopically. The products of reaction remain soluble when chlorobenzene is used as solvent. A number of intermediates was observed and the kinetics of formation and removal of these was studied in detail...

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Veröffentlicht in:Die Makromolekulare Chemie 1987-09, Vol.188 (9), p.2121-2139
Hauptverfasser: Amass, Allan J., Lotfipour, Mahmoud, Zurimendi, Jon A., Tighe, Brian J., Thompson, Cheryl
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Sprache:eng
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Zusammenfassung:The complex series of reactions that takes place between WCl6 and cyclopentene was studied spectroscopically. The products of reaction remain soluble when chlorobenzene is used as solvent. A number of intermediates was observed and the kinetics of formation and removal of these was studied in detail. A complex series of reactions was postulated to account for these changes and the significance of each reaction to the overall scheme was determined by computer simulation of the changes that occur. One of the products has particular significance in the scheme of reactions since it is believed that this species is eventually responsible for the monometallic initiation of the polymerization of cyclopentene. The reaction was also studied gas chromatographically when it was shown that the reaction is accompanied by the formation of a complex mixture of products. One of these products was shown to have the mass spectrum that would be expected of 3‐chlorocyclopentene and a reaction scheme that would account for its formation is postulated. The reactions involved in the generation of centres active towards the formation of polypentenamer were considered for both monometallic and bimetallic (WCl6/AlR3) catalyst.
ISSN:0025-116X
0025-116X
DOI:10.1002/macp.1987.021880910