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Structure and reactivity of peroxide monomers

✍ Scribed by S. A. Voronov; Eu. M. Kiselyov; S. S. Minko; O. G. Budishevska; Yu V. Roiter

Publisher
John Wiley and Sons
Year
1996
Tongue
English
Weight
386 KB
Volume
34
Category
Article
ISSN
0887-624X

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✦ Synopsis

The reactivity of both the peroxide (2-tert-butylperoxy-2-methyl-5-hexene-3-yne) and hydroperoxide (2-hydroperoxy-2-methyl-5-hexene-3-yne) monomers in the radical copolymerization was compared. Using the Alfrey-Price Q and e scheme, Hammett correlations, and MNDO quantum-chemical model it was shown that both peroxy-and hydroperoxyisopropylic substituents pronounce a similar positive effect of hyperconjugation. Despite that these monomers showed different reactivity due to the ability of the hydroperoxide monomer to form complexes with protonoacceptors. IR spectroscopy was employed for the evaluation of energies of hydrogen bonds and equilibrium constants. 0

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