Interfacial crosslinking of self‐assembled triblock copolymer nanoparticles via alkoxysilane hydrolysis and condensation

Abstract

The use of amphiphilic triblock copolymers bearing a reactive alkoxysilane middle block as polymeric stabilizers is reported in this work. A series of poly(ethylene glycol) methyl ether methacrylate‐b‐(3‐trimethoxysilyl)propyl methacrylate‐b‐benzyl methacrylate (PEGMA‐b‐MPS‐b‐BzMA) triblock copolymers were prepared by RAFT solution polymerization and polymerization‐induced self‐assembly (PISA), respectively, where the various block lengths and overall composition were varied. The copolymers prepared by solution polymerization were employed as oil‐in‐water stabilizers where upon application of a catalyst, the 3‐(trimethoxysilyl)propyl methacrylate (MPS) block at the droplet interface was crosslinked to yield capsule‐like structures. The effectiveness of interfacial crosslinking was validated by dynamic light scattering and electron microscopy. In situ self‐assembly by the PISA method resulted in spherical nanoparticles of controllable size that were readily crosslinked by addition of base, with significant enhancement of colloidal stability. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1897–1907

Organic–inorganic hybrid functional materials by nitroxide-mediated polymerization

“…Aside from the grafting of polymers from the surface of preformed silica colloids, NMP has also been combined with the sol-gel technique for in situ synthesis of silicon oxide-based hybrid materials of controlled morphologies. Indeed, as shown in several reports, unsaturated monomers containing reactive alkoxysilyl groups such as 3-acryloxypropyl triethoxysilane (APTES) can be readily homo-or copolymerized with acrylic or styrenic monomers by RDRP [189][190][191][192][193][194]. The resulting functional polymers can further undergo hydrolysis/condensation reactions or be combined with tetraethoxysilane after the polymerization step to afford organic/inorganic hybrid materials [195,196].…”

Investigation of segmental reorganization within amphiphilic block polymer nanoparticles derived from shell crosslinked micelle templates: Shell crosslinked knedel‐like inversion

“…In the 1990's, supramolecular assembly of amphiphilic block polymers in selective solvents, which thermodynamically favor one of the blocks, emerged as a general technique for the generation of micellar structures having morphological diversity. [1][2][3][4][5][6][7] Over the past couple of decades, tuning the composition and architecture of the block polymer building blocks [8][9][10][11][12][13][14][15][16] and incorporating environmentally responsive chemical functionalities have been shown to promote morphological switching and lead to enhanced behaviors and functions. [17][18][19][20][21][22][23][24] The covalent stabilization of micelles and other supramolecular assemblies was also recognized as a powerful method, analogous to that utilized in biology, 25 for the rapid and large-scale preparation of intricate and stable nanostructured materials.…”

An Exciting Time for Polymer Chemists in Australia

“…Zetterlund and co‐workers exploit the compartmentalization effects present in miniemulsion for the preparation of RAFT‐derived chains that exhibit significantly increased livingness. Thickett and co‐workers report the preparation of stabilized nano‐objects by way of polymerization‐induced self‐assembly. Various morphologies were elegantly crosslinked by way of alkoxysilane condensation.…”