Hybrid Photoiniferter and Ring-Opening Polymerization Yields One-Pot Anisotropic Nanorods

Paul Joshua Hurst; Junsik Yoon; Riya Singh; Mohammed Faris Abouchaleh; Kevin A Stewart; Brent S Sumerlin; Joseph P Patterson

doi:10.1002/marc.202400100

Hybrid Photoiniferter and Ring-Opening Polymerization Yields One-Pot Anisotropic Nanorods

Macromol Rapid Commun. 2024 Mar 23:e2400100. doi: 10.1002/marc.202400100. Online ahead of print.

Authors

Paul Joshua Hurst¹, Junsik Yoon¹, Riya Singh¹, Mohammed Faris Abouchaleh¹, Kevin A Stewart², Brent S Sumerlin², Joseph P Patterson^{1

3}

Affiliations

¹ Department of Chemistry, University of California, Irvine, Irvine, CA, 92697, USA.
² George & Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science and Engineering, Department of Chemistry, University of Florida, Gainesville, FL, 32611, USA.
³ Department of Materials Science and Engineering, University of California, Irvine, Irvine, CA, 92697, USA.

PMID: 38520318
DOI: 10.1002/marc.202400100

Abstract

Polymerization-induced self-assembly (PISA) has emerged as a scalable one-pot technique to prepare block copolymer (BCP) nanoparticles. Recently, a PISA process, that results in poly(l-lactide)-b-poly(ethylene glycol) BCP nanoparticles coined ring-opening polymerization (ROP)-induced crystallization-driven self-assembly (ROPI-CDSA), was developed. The resulting nanorods demonstrate a strong propensity for aggregation, resulting in the formation of 2D sheets and 3D networks. This article reports the synthesis of poly(N,N-dimethyl acrylamide)-b-poly(l)-lactide BCP nanoparticles by ROPI-CDSA, utilizing a two-step, one-pot approach. A dual-functionalized photoiniferter is first used for controlled radical polymerization of the acrylamido-based monomer, and the resulting polymer serves as a macroinitiator for organocatalyzed ROP to form the solvophobic polyester block. The resulting nanorods are highly stable and display anisotropy at higher molecular weights (>12k Da) and concentrations (>20% solids) than the previous report. This development expands the chemical scope of ROPI-CDSA BCPs and provides readily accessible nanorods made with biocompatible materials.

Keywords: block copolymers; photoiniferter; polymerization induced crystallization driven self‐assembly; ring‐opening polymerization.

Abstract

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