In Situ Crosslinking of Nanoparticles in Polymerization‐Induced Self‐Assembly via ARGET ATRP of Glycidyl Methacrylate

Abstract

Polymerization-induced self-assembly (PISA) and in situ crosslinking of the formed nanoparticles are successfully realized by activators regenerated by electron-transfer atom transfer radical polymerization (ARGET ATRP) of glycidyl methacrylate (GMA) or a mixture of GMA/benzyl methacrylate (BnMA) monomers in ethanol. Poly(oligo(ethylene oxide) methyl ether methacrylate) was employed as macroinitiator/stabilizer, and a cupric bromide/tris(pyridin-2-ylmethyl)amine complex as catalyst. Tin (2-ethylhexanoate) was used as reducing agent for ARGET ATRP, and simultaneously acted as a catalyst for ring-opening polymerization of oxirane ring in GMA. The kinetics shows that the double bond in GMA was completely polymerized in 4.0 h, while only a 33% conversion of oxirane ring in GMA was reached at 117.0 h. Such a large difference would guarantee a smooth PISA and a subsequent in situ crosslinking of formed nanoparticles. The transmission electron microscopy and dynamic light scattering show spherical nanoparticles formed. With a feed molar ratio [BnMA] /[GMA] = 150/50, 100/100, and 50/150, the nanoparticles formed in ethanol can dissociate or swell in toluene. When pure GMA was used, the solid nanoparticles were observed in toluene or ethanol. The ARGET ATRP provides an efficient strategy to stabilize the nanoparticles formed in the PISA of GMA-containing system.

RAFT‐Mediated Polymerization‐Induced Self‐Assembly

“…Theoretically, any RDRP technique or living polymerization technique can be selected to produce these block copolymer nanoobjects by PISA. Indeed, nitroxide‐mediated polymerization (NMP), atom‐transfer radical polymerization (ATRP), Cu‐mediated controlled polymerization, iodine‐transfer polymerization (ITP), organotellurium‐mediated radical polymerization (TERP), Co‐mediated radical polymerization, ring‐opening metathesis polymerization (ROMP), or reversible complexation‐mediated polymerization (RCMP) have been successfully implemented. However, RAFT‐mediated PISA remains the most employed strategy.…”

Reactive and Functional Nanoobjects by Polymerization‐Induced Self‐Assembly

“…Reactive and functional nanoobjects are now targeted, taking advantage of the simplicity of implementation, the morphological variety, and the functional group tolerance of most PISA systems. This is clearly showcased in the present special issue on PISA . The aim of the present review is to gather and discuss most of the literature on the synthesis of reactive/functional nanoobjects by PISA up to May 2018.…”

Polymerization‐Induced Self‐Assembly

“…For instance, two articles report ATRP-mediated PISA, namely ICAR ATRP [2] and ARGET ATRP. [3] Interestingly, the former contribution [2] also compares ICAR ATRP-PISA to a standard RAFT-PISA system. Zhang, Cheng, Zhu, and co-workers [4] used light to develop an efficient ITP-based PISA system relying on in situ bromine-iodine transformation.…”

“…The presence of a crosslinker during PISA can also prevent nanoparticle reorganization and inhibit the formation of higher-order morphologies. As such, in the work of Wang, Matyjaszewski, and co-workers, [3] reporting on the simultaneous ARGET ATRP PISA (in dispersion) and the in-situ crosslinking through ring opening of glycidyl methacrylate (GMA), only spherical particles were obtained. Two additional contributions propose alternative strategies to crosslink the core of the block copoly mer particles: O'Reilly et al [6] propose the polymerization of pentafluorophenyl methacrylate (PFMA) as a core mono mer yielding spherical particles, which could be successfully crosslinked after polymerization by the addition of diamines in a dry solvent (DMSO) to avoid side reactions.…”

“…Most of the articles make use of RAFT polymerization (see below) but other techniques are also explored. For instance, two articles report ATRP‐mediated PISA, namely ICAR ATRP and ARGET ATRP . Interestingly, the former contribution also compares ICAR ATRP‐PISA to a standard RAFT‐PISA system.…”