Preparation of Cross‐Linked Micelles from Glycidyl Methacrylate Based Block Copolymers and Their Usages as Nanoreactors in the Preparation of Gold Nanoparticles

Abstract

This study reports the synthesis of poly(ethylene glycol)methyl ether‐block‐poly(glycidyl methacrylate) (MPEG‐b‐PGMA) diblock, and poly(ethylene glycol)methyl ether‐block‐poly(glycidyl methacrylate)‐block‐poly(methyl methacrylate) (MPEG‐b‐PGMA‐b‐PMMA) triblock copolymers via atom transfer radical polymerization and their self‐assembly behaviors in aqueous media by using acetone as cosolvent. These block copolymers formed near monodisperse core–shell micelles having cross‐linkable cores. Two types of cross‐linked micelles, namely spherical MPEG‐b‐PGMA core cross‐linked (CCL) micelles and MPEG‐b‐PGMA‐b‐PMMA interlayer cross‐linked (ILCL) micelles, were also successfully prepared from these block copolymers by using various bifunctional cross‐linkers such as hexamethylenediamine (HMDA), ethylenediamine (EDA), and 2‐aminoethanethiol (AET). Cross‐linking was successfully carried out via ring‐opening reactions of epoxy residues of hydrophobic‐cores with primary amine or thiol groups of bifunctional cross‐linkers. Finally, these cross‐linked micelles were successfully used as nanoreactors in the synthesis of gold nanoparticles (AuNPs) in aqueous media. Both CCL and ILCL micelles were found to be good stabilizers for AuNPs in aqueous media. Both CCL‐ and ILCL‐stabilized AuNP dispersions were stable for a long time without any size changes and flocculation at room temperature. These cross‐linked stabilized AuNPs exhibited good catalytic activities in the reduction of p‐nitrophenol. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 514–526.

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

“…Depending on the location of PGMA blocks in micellar structure, the core crosslinked (CCL) micelles, shell crosslinked (SCL) micelles, and interlayer crosslinked (ILCL) micelles were selectively prepared. [30][31][32][33] Recently, the GMA was also introduced into the core-forming block through a reversible addition fragmentation chain transfer (RAFT) polymerization based PISA system, either by copolymerization with 2-hydroxypropyl methacrylate (HPMA), [9] or homopolymerization. [34,35] In these systems, the functionalization or crosslinking of the nanoparticles should be in a separate step that occurs after the chain extension polymerization.…”

“…For example, using bifunctional ethylene diamine (EDA) or 2‐aminoethanethiol (AET) as crosslinking agent, the PGMA blocks in a micellar system can be easily crosslinked. Depending on the location of PGMA blocks in micellar structure, the core crosslinked (CCL) micelles, shell crosslinked (SCL) micelles, and interlayer crosslinked (ILCL) micelles were selectively prepared . Recently, the GMA was also introduced into the core‐forming block through a reversible addition fragmentation chain transfer (RAFT) polymerization based PISA system, either by copolymerization with 2‐hydroxypropyl methacrylate (HPMA), or homopolymerization .…”

Preparation and catalytic properties of modified PGMA‐based pH‐responsive hydrogel films as a novel template for in situ synthesis of Au, Ag, and Au:Ag nanoparticles

“…Spherical mono‐ and bimetallic alloy nanoparticles such as Au (from 490 to 530 nm), Ag (from 400 to 420 nm), and Au:Ag (from 470 to 510) are known to display a strong SPR band. These SPR signals can be significantly different depending on the nanoparticle size, crystal type, and content.…”

“…38 In our previous study, combination of both DLS and NMR studies indicated core-shell nanostructures with the PMMA block forming the core and the MPEG and PHMPPMA blocks forming the shell of the MPEG-b-PHMPPMA-b-PMMA triblock copolymer micelles in aqueous solution. 39 Accordingly, it was claimed that the PEG block would form brushes on the surface of the hydrogel film in the aqueous medium. In accordance with the above description, the surface structure of the produced film in water can be schematized as given in Figure 2.…”

Microspheres with Tunable Porosity Based on Reactive Block Copolymer: Preparation and Vapor‐Healing Behavior

“…[33] Particularly, the resulted poly cations obtained from ring open reaction with amine showed various applications in NPs-loading, gene delivery, water purification, etc. [34][35][36][37][38][39][40][41] Hydroxypropyl methacrylate (HPMA) is water soluble monomer with hydroxyl groups, but its polymer PHPMA is only partially hydrophilic and a water insoluble polymer which is widely applied in biomedical field. [42,43] Herein, we reported a route to prepare PMS base on PHPMA-b-PGMA with controllable porous structure via W 1 /O/W 2 emulsion for the first time so far as we know.…”