Volianiuk K. Polyoxazoline- and fluoroalkyl-containing surface-active macroinitiators and functional micro- and nanostructures based on them.

The dissertation is devoted to the synthesis of new surface-active functional macroinitiators with controlled structural and molecular mass characteristics, which contain blocks and/or side chains of polyoxazolines (pOx), fluoroalkyl alcohols (FA), and reactive terminal or side fragments, as well as the preparation of functional nano- and microstructures, micelles, and polymer nanoparticles of the core-shell structure. The work developed complex approaches to the synthesis of polyamphiphiles - precursors based on pOx and FA with terminal and side hydroxy, peroxide, and epoxy groups that form free radicals or attach synthetic and natural polymeric and low-molecular weight substances. The kinetic regularities of the formation, transfer and termination of free radicals in redox systems (ROS) in the presence of functional chain transmitters (FCT) based on isopropylbenzene (IPB) derivatives were studied, and derivatives of pOx and FA with peroxide, epoxide, and nitroxyl-radical terminal fragments were obtained for the first time. Polymerization of vinyl monomers initiated by terminal hydroxyl or peroxide groups of pOx and FA in the presence of FCT, as well as addition reactions with the participation of terminal epoxy groups of precursor polymers ensure the formation of block copolymers with unchanged structural and molecular weight characteristics of the initiator blocks and controlled lengths of grafted blocks. In the work, the synthesis and properties of surface-active linear and branched copolymers by attaching pOx to epoxy groups of Dian resin (DR) or triepoxycyanurate (TGIC) were investigated for the first time. The resulting triblock copolymers DR-block-(pOx)2 or star-shaped TGIC-graft- (pOx)3 contain secondary hydroxyl groups that initiate the polymerization of functional monomers in ROS with Cerium salt, as a result, branched and star-shaped polymers or dispersions of polymer particles of the ‘core-shell’ structure were synthesized. New approaches to the targeted synthesis of comb-like surface-active polymers with side pOx chains via addition reactions of side epoxy fragments of glycidyl methacrylate copolymers and (co)polymerization of a pOx-containing methacrylate macromer with functional vinyl monomers are researched. In the dissertation, for the first time, an approach to obtaining multi-center surface-active macroinitiators, which contain blocks of pOx or FA and oligomeric blocks with side peroxide and other functional groups, in particular, their coordination complexes with cations of metals of variable valence, was implemented. It was established that they are effective macroinitiators of waterdispersion polymerization in a wide temperature range and stabilizers of dispersions of functional particles of the "core-shell" structure. Considerable attention was paid in the dissertation to the study of the colloidal-chemical properties of functional polyamphiphiles with complex architecture and the morphology of the supramolecular structures formed by them, establishing their dependence on the nature, architecture, functionality and structural and molecular mass characteristics of the polymers. It is shown that the synthesized micelle-like supramolecular structures are effective non-toxic carriers of anticancer drugs, proteins, and oligonucleotides. This makes it possible to use them as theranostic carriers of therapeutic agents for real-time monitoring of therapy, recognition, labeling, and visualization of biological objects, including microorganisms.