Polymerization-induced self-assembly

Wan, W.M. Pan, C.Y. One-pot synthesis of polymeric nanomaterials via RAFT dispersion polymerization induced self-assembly and re-organization. Polym. Chem. 2010,1 (9), 1475-1484. 

Warren NJ, Armes SP (2014) Polymerization-induced self-assembly of block copolymer nano-objects via RAFT aqueous dispersion polymerization. J Am Chem Soc 136 10174-10185... 

Charleux B, Delaittie G, Rieger J, D Agosto F (2012) Polymerization-induced self-assembly from soluble macromolecules to block copolymer nano-objects in one step. Macromolecules 45 6753-6765... 

Fig. 17 Synthesis of multipod-like silica/polymer particles by NMP-mediated polymerization-induced self-assembly (PISA) of block copolymers by means of a PEO-based brush-type macroalkoxyamine initiator previously adsorbed at the surface of colloidal silica nanoparticles. Reproduced from [99] with permission from the American Chemical Society...

Qiao XG, Fansalot M, Bourgeat-Lami E, Charleux B (2013) Nitroxide-mediated polymerization-induced self-assembly of poly(poly(ethylene oxide) methyl ether methacrylate-co-styrene)-h-poly(n-butyl methacrylate-co-styrene) amphiphilic block copolymers. Macromolecules 46 4285 295... 

Fig. 2.12 General principle of the polymerization-induced self-assembly method. Reproduced from [36] with permission from Royal Society of Chemistry...

Ferguson, Hawkett and coworkers have pioneered the field of polymerization-induced self-assembly by employing RAFT emulsion polymerization of acrylic acid and n-butyl acrylate in aqueous media [39]. This approach led to in situ self-assembled nanoparticles formed by an amphiphilic block copolymer. First, acrylic acid was polymerized in the water phase to yield a water-soluble macro-RAFT agent, followed by the polymerization of hydrophobic n-butyl acrylate. At the completion of the polymerization, self-stabilized micelle-like PAA-b-PnBA particles of number-average diameter of 60.3 nm were obtained. When polymerization was continued by feeding of another hydrophobic monomer, styrene, spherical core-shell particles composed of poly(acrylic acid)-b-poly(butyl acrylate)-b-polystyrene triblock copolymer were formed [40]. 

The polymerization-induced self-assembly is a facile, efficient, and reproducible strategy for preparation of families of polymeric nanoparticles having various morphologies via a one-pot process. Direct preparation of the block copolymer aggregates in the dispersion and emulsion polymerizations at high concentration of sohds provides the possibihty for large-scale industrial production. Preferentially, the polymerization-induced self-assembly should be conducted in aqueous media at quantitative monomer conversion. 

Karagoz B, Esser L, Duong HT, Basuki JS, Boyer C, Davis TP (2014) Polymerization-induced self-assembly Control over the morphology of nanoparticles for drug delivery applications. 

Sun J-T, Hong C-Y, Pan C-Y (2012) Formation of the block copolymer aggregates via polymerization-induced self-assembly and reorganization. Soft Matter 8 7753-7767... 

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