Ajjm. Van Breemen et al., Optimization of the polymerization process of sulfinyl precursor polymers toward poly(p-phenylenevinylene), MACROMOLEC, 32(18), 1999, pp. 5728-5735
The prerequisites for the polymerization process of sulfinyl monomers towar
d precursor polymers for poly(p-phenylenevinylene) were investigated. In th
is process, proton abstraction affords the premonomer anion, which is conve
rted to the actual monomer, viz, a p-xylylene derivative. These p-xylylene
derivatives polymerize spontaneously without external initiation. In hydrog
en bond donor solvents (HBD solvents) like alcohols, three products can be
isolated. High molecular weight polymer is formed together with a residual
fraction that consists of a minor amount of premonomer and a large amount o
f solvent-substituted product. These solvent-substituted products are most
likely formed by addition of a solvent anion to the actual monomer and cann
ot participate in the polymerization process anymore. Solvent substitution
is therefore an important side reaction and has to be avoided. It was found
that, in branched alcohols such as s-butanol, conversion of premonomer to
actual monomer is very efficient, resulting in a rapid buildup of p-xylylen
e derivative. In this way the polymer yield was increased to 90%.