Interfacial RAFT Miniemulsion Polymerization: Architectures from an Interface

Abstract

Directing polymerization from a liquid–liquid interface is an emergent field delivering new insights into polymerization mechanisms, while creating interesting and novel poly­mer architectures. This review aims to explore how reversible addition–fragmentation chain‐transfer (RAFT) polymerization has been utilized in miniemulsion to perform controlled polymerizations at the biphasic liquid–liquid interface. Highlighted herein are the initial investigations that led to a new class of interfacially active macro‐RAFT agents. These are capable of stabilizing emulsions, directing polymer growth from that interface, and subsequently producing capsule‐like architectures. A comprehensive description is provided concerning the various macro‐RAFT agents employed and the importance of performing this under miniemulsion conditions to obtain either nanoparticles, nanocapsules, and/or core–shell morphologies. Finally, a focus on exciting applications of such systems for the production of nanomaterials including delivery vehicles with stimuli‐responsive properties is presented.

Semiconductor Quantum Dots Are Efficient and Recyclable Photocatalysts for Aqueous PET-RAFT Polymerization

“…Light-triggered reversible-deactivation radical polymerization (RDRP) − combines the defined reaction kinetics and narrow molecular weight distributions of reversible addition–fragmentation chain transfer (RAFT), atom transfer radical polymerization (ATRP), − and nitroxide-mediated polymerization (NMP) with the spatial and temporal resolution and mild reaction conditions of photochemical methods. , Of the three types of RDRP, RAFT is the most versatile in its scope of monomers and solvents, including water. − Photodriven RAFT is typically triggered by photoinduced electron transfer or energy transfer (PET) from a molecular photocatalyst to a chain transfer agent (CTA) and is thus termed PET-RAFT (Figure ). ,,,,,− …”

Core–shell microgels having zwitterionic hydrogel core and temperature-responsive shell prepared via inverse miniemulsion RAFT polymerization

“…Controlled radical polymerization from a liquid-liquid interface of inverse miniemulsion has attracted significant attention for synthesizing polymer particles and capsules with well-defined structures. 20,21 For example, the Zetterlund group synthesized various nanocapsules using reversible addition fragmentation chain transfer (RAFT) polymerization away from a droplet interface of a water-in-oil (W/O) emulsion stabilized with an amphiphilic block copolymer with a RAFT agent terminus. [22][23][24][25] Water-dispersible nanocapsules were also synthesized by introducing the hydrophilic groups onto the nanocapsules via a post-polymerization reaction.…”

RAFT miniemulsion polymerisation of benzyl methacrylate using non-ionic surfactant

“…18,39,40 However, the use of RAFT agents in miniemulsion polymerisation is sometimes problematic, causing colloidal instability, 41,42 broad particle size distributions, 20,43 low polymerisation rates, 44,45 low monomer conversions 32,46,47 and broad molecular weight distributions. [48][49][50][51] Furthermore, some RAFT miniemulsion polymerisation systems experience inhibition or retardation of the polymerisation. 20,44 Acrylic and methacrylic monomers are crucial for manufacturing of a wide range of polymeric materials for a variety of applications.…”