2-Oxazolines are widely used as building blocks for the controlled synthesis of self-assembling polymer systems. The cationic ring-opening polymerization (CROP) is usually used for the synthesis of poly-2-oxazolines. In the absence of moister and other nucleophilic impurities, the CROP proceeds in a living mode allowing the precise control of the blocks ratio and, thus, obtaining well-defined polymers. Meanwhile, this approach is not applicable for the synthesis of fluorinated 2-oxazolines. It is known that the synthesis of fluorinated 2-oxazoline-based homo- and copolymers suffers from extremely low activity of 2-perfluoroalkyl-2-oxazolines in the CROP both in the initiation and in the propagation. Recently, we reported a detailed study of increasing the polymerization reactivity of fluorophilic 2-oxazolines by the insertion of alkyl spacers between the fluorinated substituent and the 2-oxazoline ring. This approach offers a new platform for the synthesis of various of copoly(2-oxazoline)s with fluorinated blocks. A series of poly(2-oxazoline)-based block copolymers containing hydrophilic (2-methyl-2-oxazoline, 2-ethyl-2-oxazoline), thermo-responsive (2-n-propyl-2-oxazoline, 2-i-propyl-2-oxazoline), hydrophobic (2-n-octyl-2-oxazoline, 2-phenyl-2-oxazoline) and fluorophilic blocks (Figure 1) was synthesized. By combination of experimental methods including dynamic light scattering (DLS), small angle X-ray and neutron scattering (SAXS and SANS), cryo-TEM microscopy, we proved that synthesized copolymers self-assemble into the micellar-like structures in diluted aqueous solutions.

Poly-2-oxazolines block copolymers with fluorophilic blocks: New frontiers for the design of self-assembling systems

256th National Meeting (2018)

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