Polymerization of dec-1-ene—III. Detailed kinetic analysis of total product formation provides reactivities and kinetic parameters for the free radical oligomerization

✍ Scribed by Derek R. Illsley; Roy S. Lehrle

• Publisher: Elsevier Science
• Year: 1991
• Tongue: English
• Weight: 334 KB
• Volume: 27
• Category: Article
• ISSN: 0014-3057
• DOI: 10.1016/0014-3057(91)90220-i

✦ Synopsis

For dec-l-ene oligomerizations in either ethylbenzene or decane as solvent, kinetic analyses are proposed which take account of all processes contributing to the formation of all types of product. These schemes have been applied to interpret the experimental data published in paper I of this series, and have permitted the evaluation of the following reactivities or kinetic parameters:

(a) the ethylbenzene molecule is ca 3 x more reactive than dec-1-ene in the degradative transfer process; (b) di-tert.butyl peroxide displays an initiator efficiency of ca 0.3 in the systems involving ethylbenzene solvent, and a similar value (possibly slightly higher) when decane is used as solvent; and (c) the ratio of the rate constant for monomer propagation to that for degradative chain transfer termination by monomer is ca 8. This result shows excellent agreement with experimental estimates of the mean degree of polymerization.