The homopolymerization of two hydroxy-functional monomers, glycerol monomethacrylate
[GMA] and 2-hydroxypropyl methacrylate [HPMA], has been investigated using ATRP chemistry in
aqueous, methanolic, or water/methanol solution. In methanol, both monomers are polymerized to high
conversion with reasonably good control (final polydispersities are 1.30 and 1.09 for GMA and HPMA,
respectively) within a few hours at 20 °C. “Self-blocking” chain growth experiments indicate good living
character under these conditions. Addition of water leads to much more rapid polymerizations in both
cases, but high polydispersities (e.g., M
w/M
n = 1.90 for a 50/50 water/methanol mixture) were always
obtained with GMA. With HPMA, relatively low polydispersities (M
w/M
n = 1.17) can be achieved under
the same conditions. Several new diblock copolymers were synthesized using poly(alkylene oxide)-based
macroinitiators. One of these hydrophilic−hydrophobic diblocks proved to be thermoresponsive and
aggregated reversibly in aqueous media.
Amphiphilic hairy nanoparticles are prepared in a one step, batch, heterogeneous polymerization of styrene or n-butyl acrylate, using a water-soluble poly(sodium acrylate) alkoxyamine macroinitiator based on the SG1 nitroxide.
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