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A photomediated approach allows a one-pot fabrication of stable coatings of polyelectrolyte complexes with a reversible crosslinking. 

This works reports on novel polyimine vitrimers from a bio-based and fully aromatic scaffold. The dynamic networks possess high-performance thermal stability and charring behavior with facile thermomechanical and viscoelastic tunability. 

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.