Ovdenko V. Synthesis and study of new bis-azometine-containing methacrylates for optoelectronics

The thesis is devoted to the synthesis and investigation of the properties of new monomers based on bis-azomethines and azo-/azomethine compounds with 1-phenyl-3-methyl-5-pyrazolone fragments. 14 new hydroxyl-containing compounds and 12 methacrylic derivatives based on them were synthesized. Also, 6 new methacrylates of bis-azomethines and 3 new methacrylates with pyrazolone fragments have been synthesized and methods for its synthesis of have been optimized. Using spectral techniques the structures of new monomers and polymers have been confirmed. It has been proven that monomers with electron-acceptor group can’t be synthesized by direct acylation with methacrylic compounds. The polymerization ability of the new monomers for radical homopolymerization and copolymerization were investigated kinetically by using dilatometric method.Kinetic studies have shown that new monomers are capable of thermoinitiated homo- and copolymerization by a radical mechanism with vinyl monomers in DMF solutions. The synthesized polymers exhibited glass transition temperatures in the range of 43–168°C. The photochemical properties of new synthesized initial azomethines and azo-benzenes, monomers, as well as polymers based on them, have been studied. The ability to irreversible E-Z photoisomerization by UV irradiation in solution for all hydroxyl derivatives of bis-azomethines and some monomers and polymers based on them was established. The possibility of reversible photoinduced E-Z-E isomerization in films for hydroxyl derivatives and polymers of bis-azomethines was also proved. The thermostabilizing effect of azo- and azomethine-containing monomers on polystyrene was studied upon their covalent introduction into the polymer chain. It has been shown that they can be used as inhibitors of the thermo-oxidative destruction of polystyrene, and some of them can be used to reduce the processing temperature of polystyrene products by 50°C. On the basis of new monomers, promising materials with low softening temperatures for recording media in holography have been created. Also, the prospect of creating materials with nonlinear-optical properties was shown. Key words: bis-azomethines, azo compounds, radical polymerization, photoisomerization, thermal stabilization, holography.