A radical mechanism is proposed for the formation of the 1,2-polymer 2 in the “spontaneous” polymerization of 4-vinylpyridinium salts 4-VP.HX (X=NO3, ClO4, HSO4, I) in aqueous solution on the basis of strong inhibition by oxygen and other radical inhibitors. Quantitative investigation of the influence of oxygen on the formation of the 1,2-polymer allowed the derivation of a formal kinetic scheme for the initiation and polymerization steps which is consistent with a free radical mechanism. Dependence of the average molecular weight of 2 on monomer concentration is in agreement with this model. Dependence of the inhibition time on the oxygen concentration as well as an acceleration of the fin…

Polyreaktionen in orientierten systemen, 6.Mizellare assoziationen in 4-vinylpyridiniumsalzlösungen

Kritische Mizellkonzentrationen (cmc) aus Oberflachenspannungsmessungen und durch Farbstoffsolubilisierung werden von 4-Vinylpyridinium- bzw. 4-Athylpyridinium-Salzlosungen bestimmt. Erhohung der Gegenionen-Konzentration erniedrigt die cmc; gleichzeitig damit andert sich auch die Zusammensetzung der Polymerisationsprodukte der spontanen Polymerisation in Wasser. Mogliche Erklarungen hierfur werden diskutiert. Critical micell concentrations (cmc) of 4-vinylpyridinium or 4-ethylpyridinium salt solutions are determined from surface tension measurements and solubilisation of a dyestuff. Increase of the concentration of the gegenions decreases the cmc; at the same time, the composition of the po…