Browsing by Author "Zagorodko, Oleksandr"
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Zagorodko, Oleksandr (2015)Polymeric ionic liquids (PILs) belong to a new class of materials which combine the properties of both conventional ionic liquids and polymers that make them promising for many different applications. The aim of this thesis is to develop a new approach for PILs synthesis based on thiolactone chemistry. The main starting material used for modification is a novel polyacryloylthiolactone (pAHT) polymer that has thiolactone moiety in the side chain. This can be modified with amine- and vinyl-containing compounds in an one or two step reaction. The amine-containing ionic liquid was designed specially for aminolytic opening of polythiolactone. Reaction conditions were carefully optimized as the ionic liquid part of the molecule can influence the reactivity of the compound. Additionally, detailed study of aminolysis with conventional amines of different nature is also performed, including NMR-kinetics. In general, under optimized conditions yields higher than 90 % were reached for all amines, including the ionic liquid. A second degree of modification is introduced by click thiol-Michael addition reaction of thiol groups produced by the ring opening of the pAHT in the presence of amine. Modification was studied for two classes of vinyl monomers - (meth)acrylates and styrenes. (Meth)acrylates appeared to be more suitable for synthesis of block copolymer, while styrenes are better for thiol-ene addition. By using a chiral styrene-based ionic liquid, PILs were synthesized by modification of double bonds. Combination of two approaches allowed the synthesis of novel PILs with two ionic liquid moieties of different polarities in the polymer backbone. Properties of the new polymer and its modification with vinyl-containing compounds were studied as well. Synthesis and properties of materials with different morphologies, such as monoliths and gels were studied.
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