Development of ICAR ATRP–Based Polymerization‐Induced Self‐Assembly and Its Application in the Preparation of Organic–Inorganic Nanoparticles

Abstract

The functionalization and application of nano‐objects generated using a polymerization induced self‐assembly (PISA) procedure is becoming a focus in recent years. In this contribution, using ethanol as solvent, poly(oligo(ethylene oxide) methyl ether methacrylate) (POEOMA) as macro‐initiator/stabilizer, and 2‐(perfluorohexyl)ethyl methacrylate (PFHEMA) and glycidyl methacrylate (GMA) as comonomers, the initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP)‐based PISA is realized. The lower GMA content system tends to form spheres with large diameters and heavy contrast, while the lower PFHEMA content system tends to form the spheres or short worms with small diameters. However, the system with further increased GMA content results in the failed ICAR ATRP PISA procedure with the formation of precipitates by the cross‐linking reaction between pendant epoxy groups. Furthermore, using the efficient reaction between the epoxy group on GMA and thiol group on mercapto‐succinic acid agent, the carboxyl groups can be introduced into the inner cavity of the nano‐objects and used for incorporation with the Fe2+ and Fe3+ ions, and the organic–inorganic nanoparticles Fe3O4@POEOMA are finally prepared in the presence of a reductant.

PhotoATRP-Induced Self-Assembly (PhotoATR-PISA) Enables Simplified Synthesis of Responsive Polymer Nanoparticles in One-Pot

“…4,[11][12][13][14] With the exception of one recent report 15 ; however, the solvophilic block is synthesized in homogenous media, and, after purification, is utilized as a macroinitiator for the block copolymerization of solvophobic blocks in selective solvents to form different NP morphologies in a second synthetic step. [16][17][18] Using this method the solid content and degrees of polymerization can be modulated to tune NP morphologies. [19][20][21][22] Further, to improve NP stability for biomedical applications, different strategies, such as core crosslinking (CCL) and shell crosslinking (SCL) procedures, are utilized, mostly via post-polymerization methods adding additional complications to synthetic protocols.…”

Switching between Thermal Initiation and Photoinitiation Redirects RAFT-Mediated Polymerization-Induced Self-Assembly

“…Morphologies of block copolymer nano-objects can be controlled by changing reaction conditions such as initial monomer concentrations, molecular weights of both blocks, polymer architecture, solvent compositions, reaction temperature, etc. Various polymerization techniques including reversible addition–fragmentation chain transfer (RAFT) polymerization, − atom transfer radical polymerization (ATRP), − and ring-opening metathesis polymerization (ROMP) − have been introduced into PISA. Particularly, RAFT-mediated PISA has become the most commonly studied PISA method owing to the absence of metal catalysts, mild reaction conditions, and tolerance toward various functional groups.…”

Synthesis and Applications of ZnO/Polymer Nanohybrids

“…Recently, a soluble poly­(2-(dimethylamino)­ethyl methacrylate) (PDMAEMA) chain transfer agent (PDMAEMA-CTA) was used as the surfactant in PISA to prepare stable phase-separated spherical block copolymers poly­(2-(dimethylamino)­ethyl methacrylate)- block -polystyrene (PDMAEMA- b -PS). These polymeric nanospherical templates are suitable and effective for nanoparticle synthesis, specifically gold, SiO 2 , Fe 3 O 4 , and TiO 2 nanoparticles, directly by loading the corresponded precursors into the anchoring amine groups distributed among the nanosphere shells. − …”