Abstract
Reversible addition–fragmentation chain transfer (RAFT) living radical polymerization of poly(methyl methacrylate)-block-polystyrene (PMMA-b-PS) was investigated by a combined method of gel permeation chromatography (GPC) and in situ and time-resolved ultra small-angle neutron scattering (tr-USANS) measurements. GPC enables us to examine a growing single molecule as a function of polymerization time, with respect to monomer conversion, molecular weight (Mn) and polydispersity index (Mw/Mn) of PMMA-b-PS. On the other hand, tr-USANS, observing in meso-length scales from nm to µm, reveals polymerization-induced molecular self-assembly, such as microphase separation by PMMA-b-PS or macrophase separation between PMMA-b-PS and homo-polystyrene (by-product). By combining these two experimental methods, we elucidated that RAFT living polymerization was retarded by micro- and macrophase separations.
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