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

Author:

Hurst Paul Joshua1ORCID,Yoon Junsik1,Singh Riya1,Abouchaleh Mohammed Faris1,Stewart Kevin A.2,Sumerlin Brent S.2,Patterson Joseph P.13ORCID

Affiliation:

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

Abstract

AbstractPolymerization‐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.

Funder

National Science Foundation

Publisher

Wiley

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