Upon extending a hydrophobic polymer chain from the end of a preceding hydrophilic chain in aqueous solutions, the resultant block copolymers may eventually undergo self-assembly owing to microphase separation and further chain propagation continues in the newly formed hydrophobic polymer rich domain. This process is referred to as polymerization-induced self-assembly (PISA). Its kinetics consists of polymerization and micelle formation/growth, possibly leading to a highly complex process of structural development. In this study, we studied PISA in aqueous solution accompanied by the reversible addition fragmentation chain transfer (RAFT) polymerization of poly(N-acryloylmorpholine)-b-poly(N-acryloylthiomorpholine). By useing in situ small-angle X-ray scattering (SAXS) and nuclear magnetic resonance spectroscopy (NMR), we found that the kinetics of the two above-mentioned events can be decupled when the following conditions are satisfied: (i) the time scale of the micelle formation/growth is much shorter than that of the polymerization, (ii) the micellar core is swollen by solvent so as not to interfere with the monomer supply into the core, and (iii) the core formation or segregation of the hydrophobic block occurs at quite an early stage. As a result, the rate constants characterizing RAFT do not change during PISA and the overall micellar structural development can be quantitatively described by a simple kinetic model.

Kinetical analysis of RAFT-polymerization-induced self-assembly by decoupling chain propagation and micelle formation

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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