ISSN:
0025-116X
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The reactivity of dienes 1-8, trienes 9, 10 and polymer 11 towards autoxidation in benzene solution was studied systematically. Incorporation of oxygen into 1-8 and 10 was found to be characterized by an induction period, a nearly linear oxygen uptake during several days and a limit of 1 mol oxygen per diene or triene unit. 9 takes up two mole of oxygen, and solutions of 11 show no linear oxygen uptake. The rates of oxygen uptake of olefins 1-11 were measured using standardized reaction conditions. The resulting autoxidation rates are strongly influenced by the number of methyl groups at the diene unit as well as by the ring size. 13C NMR and GPC measurements of the isolated oxydation products from 1,4,5,6,7 and 10 show that linear chains of oligomeric polyperoxides are formed, which can be considered to be alternating copolymers of oxygen and the olefin. O2-incorporation predominantly takes place in 1,4-position of dienes 1,4,5,6,7 and in 1,6-position of triene 10. The formation of low-molecular-weight endoperoxides was not observed. A plausible reaction mechanism involves diradical intermediates of type 20 and 21-23.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/macp.1989.021901129
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