Influence of oligomeric unsaturated polyketone on the vulcanization of elastomeric compositions in the presence of sulfe
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Influence of oligomeric unsaturated polyketone on the vulcanization of elastomeric compositions in the presence of sulfenamide C V. D. Voronchihin,a O. V. Sorochenko,a S. V. Semikolenov,b D. P. Ivanov,b D. E. Babushkin,b and К. А. Dubkovb aM.
F. Reshetnev Siberian State University of Science and Technology, 31 prosp. Gazety Krasnoyarsky Rabochy, 660037 Krasnoyarsk, Russia Federation. Fax: +7 (391) 264 4709 bFederal Research Center G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 5 prosp. Akad. Lavrentieva, 630090 Novosibirsk, Russia Federation. Fax: +7 (383) 330 8056. E-mail: [email protected] Effect of the oligomeric unsaturated polyketone (UPK) additive on the rheological properties, vulcanization, and structural characteristics of elastomeric compositions based on butadiene and nitrile-butadiene rubbers containing N-cyclohexyl-2-benzothiazolylsulfenamide (sulfenamide C) as vulcanizing accelerator is investigated. It was demonstrated using IR and NMR spectroscopy that sulfenamide C reacts with polyketone. A mechanism for such interaction, which includes the sequential addition of benzothiazyl sulfide and amine fragments to the oligomeric chain, was proposed. Key words: vulcanization, polyketone, rubber, sulfenamide C.
An introduction of oligomer additives into the elastomeric compositions is a promising method for modification of the technological properties of rubber compounds and the physical and mechanical characteristics of vulcanizates.1—3 The oligomers are able not only to act as plasticizers for compositions, but also to be incorporated into the elastomeric matrix during vulcanization, leading to a change in the structure of the vulcanization network.4 The use of the oligomers containing various functional groups opens up additional possibilities for modification of the elastomer properties. Functional oligomers of a new type, namely, oligomeric unsaturated polyketones (UPK) obtained by the reaction of diene rubbers with nitrous oxide (nitric oxide (I), N2O) are of particular interest in this regard.5—8 The reaction includes selective oxidation of a part of the C=C double bonds in rubbers with the selective formation of predominantly ketone groups statistically distributed in the polymer chain (ketonization reaction). For example, oligomeric UPKs obtained by the reaction of N2O with cis-1,4-butadiene rubber contain butadiene units with C=C bonds and units with ketone groups. We have shown previously that such oligomers are promising for modifying the properties of rubber compositions based on different types of rubbers.9,10 It was found
that the introduction of UPK into the composition significantly affects the induction period and the rate of vulcanization. At the same time, these parameters largely depend on the reactivity of the accelerator of the sulfur vulcanization.11—14 The aim of this work is to elucidate the effect of the addition of oligomeric unsaturated polyketone obtained by ketonization of cis-1,4-butadiene rubber on the vulcanizing activity of su
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