Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

Abstract

Nanostructured soft materials open up new opportunities in material design and application, and block copolymer self-assembly is one particularly powerful phenomenon that can be exploited for their synthesis. The advent of controlled/living radical polymerisation (CLRP) has greatly simplified block copolymer synthesis, and versatility towards monomer types and polymer architectures across the different forms of CLRP has vastly expanded the range of functional materials accessible. CLRP-controlled synthesis of block copolymers has been applied in heterogeneous systems, motivated by the numerous process advantages and the position of emulsion polymerisation at the forefront of industrial latex synthesis. In addition to the inherent environmental advantages of heterogeneous routes, the incidence of block copolymer self-assembly within dispersed particles during polymerisation leads to novel nanostructured materials that offer enticing prospects for entirely new applications of block copolymers. Here, we review the range of block copolymers prepared by heterogeneous CLRP techniques, evaluate the methods applied to maximise purity of the products, and summarise the unique nanoscale morphologies resulting from in situ self-assembly, before discussing future opportunities within the field.2

Nano‐Star‐Shaped Polymers for Drug Delivery Applications

“…The usage of LRP is of great convenience as it reduces the need for strict purification of the reactants and allows the utilization and presence of different functional groups during and after the polymerization process . The major techniques of LRP available are atom transfer radical polymerization, reversible addition–fragmentation chain‐transfer polymerization, and nitroxide mediated free‐radical polymerization . The various techniques of LRP have been adopted to grow the arms of the star‐shaped polymers.…”

Temporally Controlled Ultrasonication‐Mediated Atom Transfer Radical Polymerization in Miniemulsion

“…Additional eco‐friendly aspect in ATRP is replacing organic by heterogeneous media characterized by low toxicity, low viscosity, and also good heat transfer taking advantage in industrial application, especially in the context of biomedical and pharmaceutical application . Currently, there have been a few reports where ATRP was conducted in miniemulsion considered in two mechanism.…”

Facile Synthesis of Helical Rod–Coil Block Polymers by the Combination of ATRP and Pd(II)‐Initiated Isocyanides Polymerizations

“…Within the multiple construction manners, atom transfer radical polymerization (ATRP) is a mature and effective controlled radical polymerization which was well‐known because of the mild reaction condition and the adaptability of various vinyl monomers . Taking advantage of the tolerance to most solvents, the approved living method was widely applied to produce polymers with desired M n s and narrow M w / M n s. The initiator of ATRP possessed flexible structures with faithful properties, so that the modified and functionalized initiators provide infinite possibility in creating novel polymers with complicated structures .…”