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The kinetics of radical polymerization—XXVII. Investigation of the radical reactivity of 3,3′- and 4,4′-disubstituted azobenzenes in the polymerization of vinylacetate

✍ Scribed by S. Szakács; L. Jókay; T. Földes-Berezsnich; F. Tüdős

Publisher
Elsevier Science
Year
1978
Tongue
English
Weight
288 KB
Volume
14
Category
Article
ISSN
0014-3057

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✦ Synopsis

A study was made on the inhibition by some 3,3'-and 4,4'-disubstituted azobenzenes of the polymerization of vinylacetate initiated by azoisobutyronitrile at 50 °. The inhibitory effects of these substances can be attributed to their ability to engage in radical addition giving a less reactive hydrazyl type radical. The mechanism of the inhibition has been established by ESR and kinetic (stoichiometric) measurements. The value of ks/k 2 (characteristic of the reactivity of an inhibitor) was determined for 9 substituents. The radical reactivity of the aromatic azo group was decreased by electron donor substituents and increased by electron acceptors. The substituent effect can be well interpreted by the Hammett equation; the value of the reaction constant was O = +0.53.

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