Polymerization-induced self-assembly (PISA) enables the direct synthesis of a range of well-defined block copolymer nano-objects in concentrated solution, without requiring any post-polymerization processing. PISA syntheses are conducted via dispersion polymerization: a soluble RAFT macro-CTA (e.g. based on water-soluble poly(glycerol monomethacrylate) or PGMA; see part (a) in the schematic cartoon shown below) is chain-extended using a second monomer (e.g. 2-hydroxypropyl methacrylate or HPMA; see part (b) shown below) that is miscible with the continuous phase but forms an insoluble second block. Microphase separation of this growing second block drives in situ self-assembly, while the soluble first block confers steric stabilization (see part (c) shown below). This approach is highly versatile; it can be conducted in water, alcohol or n-alkanes at up to 50 % solids and is applicable to a wide palette of (meth)acrylic monomers. Copolymer morphologies include spheres, worms, vesicles, framboidal vesicles and lamellae. Phase diagrams can be constructed that serve as 'road maps' to enable the reproducible synthesis of the desired pure phase morphology. Selected PISA formulations will be presented and potential technological applications for this platform technology will be discussed.

Block copolymer nano-objects via RAFT-mediated polymerization-induced self-assembly

248th National Meeting (2014)

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