Abstract
The influence of hydrophobic initiators, temperature, type of chain transfer agent, and average particle diameter (Dp) of miniemulsions over the control of the RAFT/MADIX polymerization of vinyl acetate (VAc) was analyzed. The kinetic profiles demonstrated that polymerization displayed living controlled characteristics below 60% conversion but also showed a drop in the polymerization rate. The R group in the RAFT agent was critical: better control was observed when the R group was methyl ethoxycarbonyl than when it was cyanoisopropyl. As a part of the results, poly(vinyl acetate) (PVAc) with a number average molecular weight (MnGPC) of 105,000 g/mol and 75% conversion was obtained. The dispersity, Ð = 1.8, was close to previous reports, confirming the difficulty in the control of the RAFT polymerization of this less-active monomer. Dynamic light scattering analyses revealed variations in particle diameter and in the particle size distribution, particularly when an induction period was observed.
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