Herein, we demonstrate, for the first time, the use of photo-controlled atom transfer radical polymerization (PhotoATRP) for polymerization induced self-assembly (PISA) using UV light (λ = 365 nm) and ppm levels (ca. &lt; 20 ppm) of copper catalyst at ambient temperature. Utilizing Cu<sup>II</sup>Br<sub>2</sub>/tris(pyridin-2-ylmethyl)amine (TPMA) catalyst systems, PISA was accomplished all in one-pot starting from synthesis of solvophilic poly(oligo(ethylene oxide) methyl ether methacrylate) (POEGMA) blocks to core-crosslinked nanoparticles (NPs) utilizing poly(glycidyl methacrylate) (PGMA) and N,N-cystamine bismethacrylamide (CBMA) as the solvophobic copolymer and core-crosslinking agent, respectively. Sequential chain-extensions were performed for PGMA demonstrating potential capabilities for accessing multi-block copolymers with temporal control via switching the UV light on and off and accessing higher order morphologies all in one-pot without any work up. Thermal treatment of the NPs was implemented, revealing low to high order morphology transition occurred with the variety dependent on the original solid content (%) and treatment time. Further, core-crosslinking of PISA nanoparticles all in one-pot was achieved via the slow incorporation of the CBMA during the PISA process and without any interference with NPs’ morphology evolution. Finally, the disulfide installed in the CBMA core-crosslinks allowed for the stimuli-triggered dissociation of nanoparticles using DL-dithiothreitol at acidic pH.

One-pot, PhotoATRP Induced self-assembly (PhotoATR-PISA) enables simplified synthesis of responsive polymer nanoparticles

ACS Spring Meeting 2021

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