synopsisThe synthetic details of solution polymerization in benzene and bulk polymerization of vinylferrocene are reported. In benzene solutions, with azobisisobutyro$trile (AIBN) as the initiator, small yields of low-polydispenity low molecular weight ( M , * 5000) polyvinylferrocene is obtained. However, high yields can be obtained by continuous or multiple AIBN addition. Higher molecular weight polymers and binodal polymers can be obtained as the monomer concentration is increased. In bulk polymerizations, yields of 80% can be obtained. The molecular weight increases as temperature decreases from 80 to 60°C in bulk polymerizations, and an increasing amount of insoluble polymer results. The soluble portion is often binodal, the higher molecular weight node consisting of an increasingly branched structure. Lower molecular weight polymer was readily fractionated into narrow fractions from benzene-methanol systems, but higher molecular weight polymer proved impossible to fractionate into narrow fractions due to branching.
A five-step sequence has been established for the room temperature reaction of sulfur with benzylamine. Benzylamine polysulfides and benzylidenimine polysulfides occur as interconverting intermediates in this system. The final products are benzylammonium polysulfides, ammonia, and N-benzylidene benzylamine.
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