Simultaneous redox
free radical polymerization (FRP) and redox
cationic polymerization (CP) are combined for the synthesis of methacrylate/diepoxide
interpenetrating polymer networks (IPN). At first, the Cu(acac)2/phosphine/iodonium salt operates according to the principles
of free radical promoted cationic polymerization (FRPCP). A photoactivation
of the reaction for that system was necessary to enhance the mild
methacrylate and diepoxide conversions. Second and at least, two complementary
copper catalytic cycles are used simultaneously: the recently developed
Cu(II)/reducing agent/peroxide FRP system combined with the older
Cu(II)/reducing agent/iodonium salt redox CP system. For this latter
hybrid system, outstanding efficiency was observed with more than
90% of epoxy functions conversion for the cationic difunctional monomers
and 78% conversion for the vinylic functions conversion for difunctional
monomers. The radical and cation generations are discussed in order
to fill the interrogations raised by the experimental results. The
relevance of dual FRP/CP in IPN synthesis is fully demonstrated. The
performance of the hybrid copper catalytic system is remarkable to
overcome the oxygen inhibition; i.e., almost no oxygen inhibited layers
are observed compared to the >60 μm inhibited layer obtained
with a reference redox FRP such as amine/BPO.
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