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Cationic Complexes of Monovalent Nickel as Catalysts for Styrene Polymerization |
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| Authors: | V. V. Saraev P. B. Kraikivskii V. V. Annenkov A. I. Vil'ms D. A. Matveev E. N. Danilovtseva T. G. Ermakova N. P. Kuznetsova K. Lammertsma |
| Affiliation: | (1) Irkutsk State University, Irkutsk, 664033, Russia;(2) Institute of Limnology, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033, Russia;(3) Favorskii Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033, Russia;(4) Vrije Universiteit, Amsterdam, the Netherlands |
| Abstract: | The interaction of the [Ni(PPh3)3]BF4 complex with styrene and the products of styrene conversion in the polymerization reaction were studied by EPR and 13C NMR spectroscopy. The structure of the σ-carbocationic complex of Ni(I) formed by the interaction of styrene with the [Ni(PPh3)3]BF4 cationic phosphine complex of Ni(I) was characterized in detail. It was found that the reaction of styrene polymerization occurred with the participation of the coordination center of the σ-carbocationic complex (coordination catalysis), whereas the reaction of telomerization occurred with the participation of the cationic center of this complex (ionic catalysis). The resulting polymer contained active terminal double bonds; it is a promising macromonomer for the synthesis of grafted copolymers. The discovered capacity of alcohols to undergo nucleophilic addition to a growing polymer chain offers strong possibilities for preparing functional polymers and block copolymers. |
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