Guidelines for the Synthesis of Block Copolymer Particles of Various Morphologies by RAFT Dispersion Polymerization

• Published in: Macromolecular rapid communications. Vol. 36; no. 16; pp. 1458 - 1471
• Main Author: Rieger, Jutta
• Format: Journal Article
• Language: English
• Published: Germany Blackwell Publishing Ltd 01.08.2015; Wiley Subscription Services, Inc; Wiley-VCH Verlag
• Subjects: Addition polymerization; Block copolymers; Chain transfer; Chemical Sciences; Chemical synthesis; Crosslinking; dispersion polymerization; Dispersions; emulsion polymerization; Emulsions - chemistry; Guidelines; heterogeneous polymerization; Methacrylates - chemical synthesis; Methacrylates - chemistry; Morphology; Nanoparticles - chemistry; PISA; Polymerization; polymerization-induced self-assembly; Polymers; Polymers - chemical synthesis; Polymers - chemistry; Rafts; Self assembly; emulsion polymerization; PISA; polymerization-induced self-assembly; heterogeneous polymerization; dispersion polymerization
• ISSN: 1022-1336; 1521-3927; 1521-3927
• DOI: 10.1002/marc.201500028

This article presents the recent developments of radical dispersion polymerizaton controlled by reversible addition fragmentation chain transfer (RAFT) for the production of block copoly­mer particles of various morphologies, such as core‐shell spheres, worms, or vesicles. It is not meant to be an exhaustive review but it rather provides guidelines for non‐specialists. The article is subdivided into eight sections. After a general introduction, the mechanism of polymerization‐induced self‐assembly (PISA) through RAFT‐mediated dispersion polymerization is presented and the different parameters that control the morphology produced are discussed. The next two sections are devoted to the choice of the monomer/solvent pair and the macroRAFT agent. Afterwards, post‐polymerization morphological order‐to‐order transitions (i.e. morphological transitions triggered by extrinsic stimuli) or order‐to‐disorder transitions (i.e. disassembly of chains) are discussed. Assemblies based on more complex polymer architectures, such as triblock copolymers, are presented next, and finally the possibility to stabilize these structures by crosslinking is reported. The manuscript ends with a short conclusion and an outlook. RAFT dispersion polymerization is a versatile and efficient tool to prepare core‐shell particles of various morphologies by polymerization‐induced self‐assembly. This article reviews recent developments in this field, critically comments on them, and gives an outlook on further expected developments. It provides guidelines for non‐experts by highlighting important aspects that must carefully be considered when planning the preparation of core‐shell nanoobjects using this approach.