Polymerization‐Induced Self‐Assembly for the Synthesis of Poly(N,N‐dimethylacrylamide)‐b‐Poly(4‐tert‐butoxystyrene) Particles with Inverse Bicontinuous Phases

Abstract

Polymerization‐induced self‐assembly (PISA) has been routinely used to produce block copolymer (BCP) particles with various morphologies, but inverse bicontinuous phases have remained scarce. Herein, PISA preparation of poly(N,N‐dimethylacrylamide‐b‐poly(4‐tert‐butoxystyrene) (PDMA‐b‐PtBOS) BCP particles with inverse bicontinuous phases in ethanol/water at 30% w/v solid content is reported. The effect of solvent composition and degree of polymerization of the core‐forming PtBOS block is investigated. tBOS monomer conversion is enhanced on increasing water content, and inverse bicontinuous phases are effectively produced using a short PDMA stabilizer block. Morphology studies by both transmission and scanning electron microscopies reveal that transitions from vesicles to compound vesicles to inverse bicontinuous phases are the key mechanistic steps toward the formation of (partially) ordered mesophases.

RAFT-mediated polymerization-induced self-assembly (RAFT-PISA): current status and future directions

“…17, 18 and 19) and silicone oil. 20 Up to now, many morphologies have been realized via PISA, including spheres, rods, worms, vesicles, framboidal vesicles, 21,22 multilamellar vesicles, 23 lamellae, 24 spongosomes, 25–31 hexosomes, 25–27,32 cubosomes, 25,26,32 Janus particles, 33,34 colloidal molecules, 33,34 and many others. The synthesized particles have a broad range of applications in the areas of biomedical, 35–53 coating, 54,55 catalysis 56–60 and Pickering emulsions 22,61–64 and so forth.…”

Synthesis and applications of polymer cubosomes and hexosomes

“…Recently, PISA turned out to be an alternative way to prepare PCs 41–43,47–50 . A BCP is polymerized from a macroinitiator constituting the first block and a monomer in a good solvent.…”

Self-assembly of single-chain nanoparticles from block copolymers into inverse bicontinuous structures

“…22 An's group has made significant contributions to fabricating such structures using styrene and its derivatives as core-forming monomers, and employing a small amount of co-solvent to obtain individual particles. 23–26 A similar strategy of copolymerizing hydrophobic monomers and adding co-solvent was adopted by Armes et al to prepare inverse bicontinuous structures. 27 Additionally, Thang and colleagues have reported degradable inverse bicontinuous structures in response to H 2 O 2 .…”