Cationic Polymerization of 1,3-Pentadiene Initiated by Aluminum Chloride: Determination of the Various Side Reactions

The polymerization of 1,3-pentadiene initiated by AlCl3 was investigated in a nonpolar medium at room temperature. It was shown that, besides propagation, the system undergoes various side reactions such as cross-linking, cyclization, double bond isomerization, ... An examination of the various poss...

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Bibliographic Details
Published in:Macromolecules 1998-11, Vol.31 (22), p.7627-7635
Main Authors: Duchemin, Fabienne, Bennevault-Celton, Véronique, Cheradame, Hervé, Mérienne, Claude, Macedo, Anne
Format: Article
Language:English
Subjects:
Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
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Summary:The polymerization of 1,3-pentadiene initiated by AlCl3 was investigated in a nonpolar medium at room temperature. It was shown that, besides propagation, the system undergoes various side reactions such as cross-linking, cyclization, double bond isomerization, ... An examination of the various possible structures of the polymer showed that the comparison of the 1H and 13C quantitative NMR spectroscopies allows the determination of the relative importance of cyclization and double bond isomerization. It is shown that some of these side reactions can be kept under control: for instance cross-linking could be avoided at low monomer concentration, while cyclization could be strongly decreased at high monomer concentration and by catalyst sublimation. Double bond isomerization was eliminated in the presence of a transfer agent such as methyl-2-butene-2.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma980578h