RAFT‐Mediated Polymerization‐Induced Self‐Assembly

Abstract

After a brief history that positions polymerization‐induced self‐assembly (PISA) in the field of polymer chemistry, this Review will cover the fundamentals of the PISA mechanism. Furthermore, this Review will also give an overview of some of the features and limitations of RAFT‐mediated PISA in terms of the choice of the components involved, the nature of the nanoobjects that can be obtained and how the syntheses can be controlled, as well as some potential applications.

In situ SAXS studies of a prototypical RAFT aqueous dispersion polymerization formulation: monitoring the evolution in copolymer morphology during polymerization-induced self-assembly

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] Within the last two decades, polymerization-induced self-assembly (PISA) has become widely recognized as a powerful platform technology for the efficient synthesis of a wide range of block copolymer nanoparticles of controllable size and morphology. [19][20][21][22][23][24][25][26][27][28] In essence, PISA involves growing a second block from a soluble precursor block in a suitable solvent. As the second block grows, it becomes insoluble at some critical chain length, which leads to in situ self-assembly to form nascent sterically-stabilized diblock copolymer nanoparticles (or micelles).…”

“…In practice, most literature reports have utilized reversible addition-fragmentation chain transfer (RAFT) polymerization. 26,38,39 In the context of aqueous PISA syntheses, many studies have involved RAFT emulsion polymerization using waterimmiscible vinyl monomers. [40][41][42] However, a signicant body of research has been devoted to RAFT aqueous dispersion polymerization.…”

Progress and Perspectives Beyond Traditional RAFT Polymerization

“…[123] morphology. [117,[124][125][126][127][128][129] Compared to conventional self-assembly techniques that are conducted at high dilution (<1% (w/w)), the in situ chain extension of a solvophilic macroRAFT agent under dispersion or emulsion conditions facilitates reproducible syntheses of nanoparticles at significantly higher concentrations (10-50% (w/w)). Building on the robustness of conventional, thermally initiated RAFT, there has been recent focus on the photoregulation of PISA.…”

Controllable Vesicular Size and Shape in Polymerization-Induced Self-assembly Aided by Aromatic Interactions

“…In the last two decades, polymerization-induced self-assembly (PISA), which combines polymerization and self-assembly in one-pot in a concentrated solution (up to 50 wt % solid content), has been established as a powerful strategy for fabrication of polymeric vesicles. [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] Although the size and shape of vesicles are signi cantly important, regulation of vesicular size/shape in PISA system has been rarely reported. [42][43][44][45] Particularly, formation of sub-100nm vesicles or vesicles with anisotropic membrane structures via PISA is quite an unusual phenomenon.…”