Polymerization-induced self-assembly (PISA) is a method for synthesizing block copolymer nanoparticles at high weight concentrations. Recent computational studies postulate that the self-assembly of block copolymers can be controlled by manipulating the rate of polymerization. Recently, our lab developed a PISA process coined ring-opening polymerization-induced crystallization-driven self-assembly (ROPI-CDSA). In the ring-opening polymerization of L-lactide, the rate of polymerization can be altered by changing the organocatalyst used. Thus, in this work, the rate of polymerization in ROPI-CDSA is altered to study the effect rate has on the morphological outcome. In this ROPI-CDSA, a thiourea catalyst is used with a variety of co-catalysts to synthesis poly-(L)-lactide-block-polyethylene glycol. The kinetics of the polymerizations are tracked using <sup>1</sup>H nuclear magnetic resonance (NMR) spectroscopy. Characterization of subsequent organogels formed is studied through rheology. Slower rates of polymerization result in strong organogels while faster rates either result in no gels or weak organogels.

Studying the kinetics of ring-opening polymerization-induced crystallization-driven self-assembly

ACS Spring 2022

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