Alex Lubnin - Living Carbocationic Polymerization of Isobutyl Vinyl Ether and the Synthesis of Poly[isobutylene-b-(isobutyl vinyl ether)]

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  Publication Details (including relevant citation   information):

  Journal of Polymer Science: Polymer Chemistry, Vol.   31, No. 11,   pp. 2825-2834 (1993)


The MeCHClO-iso-Bu/TiCl4/AcNMe2 initiating system induced rapid living carbocationic polymn. of iso-Bu vinyl ether (I) at -100°.  Degrdn. by dealcoholation, which usually accompanies the polymn. of alkyl vinyl ethers by strong Lewis acids, does not occur at this low temp. and polymers with mol. wt. up to 40,000 g/mol and narrow mol. wt. distributions (Mw/Mn < 1.2) are readily obtained.  These polymers are not stereoregular.  The kinetics are discussed in terms of TiCl4 complexation with monomer and polymer.  The HCl (formal initiator)/TiCl4/AcNMe2 system also initiates living polymn. of isobutylene.  Polyisobutylene-poly-I-diblocks were prepd. by sequential monomer addn. using the 2-chloro-2,4,4-trimethylpentane/TiCl4/AcNMe2 initiating system.

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