Polymerization of organometallic derivatives of styrene

Abstract

where M~V=Sn, Ge, or Pb [1-3]. It was shown that these compounds form highmolecular-weight polymers under the action of a high pressure in the presence of initiators of the radical type (tertiary butyl peroxide and azoisobutyronitrile). We also investigated the polymerization of p-trialkylsilylstyrenes and p-triethylsilyl-~-methylstyrene [4,5]. Polymers were obtained and their properties were determined. The polymerization of organometallic derivatives of styrene has been investigated by Kolesnikov et al. [6] using catalysts of the ionic type (TIC14, BF3, and (C2Hs)zA1/TiC14). They established that these catalysts cause practically no polymerization of styrene derivatives of the general formula R3MIVCeH4CH----CH~, where R----CH 3 or C2H 5 and MIV=Sn, Si, or Ge. No polymers were obtained when tri-isobutylboron and the difluoride of butylboric acid were used as initiators. Polymers have been obtained by Koton et al. [7] from p-triphenylstannyl-, p-triphenylplumbyl-, and p-phenylmercuristyrenes. Noltes, Budding, and Van der Kerk [8] have recently reported the preparation and polymerization of derivatives of styrene and ~-methylstyrene of the type (CH3)3MIVCeHaCH =CH 2 and (CH3)3MIVCeH4C(CH3)----CH2, where M----Si, Ge, Sn, or Pb. These authors confirm the results of an investigation of the polymerization of ~-methylstyrene derivatives which we had obtained previously [1-5]. Like us, they established that these monomers are incapable of forming polymers in the presence of free-radical initiators at atmospheric pressure. In contrast to this, the corresponding p-substituted styrenes polymerize with the formation of transparent solid polystyrenes, as we showed earlier, using p-trialkylsilylstyrenes as examples [4].