Controlled/living free radical polymerization of styrene and butyl acrylate was performed in
bulk and emulsion using a reversible addition−fragmentation transfer (RAFT) process. The effect
of the transfer agent to initiator ratio was explored in bulk and emulsion polymerizations. The
effect of monomer addition was investigated in emulsion, and two different processes were
used: batch and semicontinuous. Better control was obtained with the continuous addition of
the monomers, resulting in clear films of the styrene−butyl acrylate copolymers. These
copolymers were characterized and studied by size exclusion chromatography, scanning
differential calorimetry, dynamic mechanical analysis, transmission electron microscopy, and
simulation, indicating that the semicontinuous process produces copolymers with a block of
styrene and a block of tapered random copolymer.
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