The object of study - associates and complexes of oxygen- and nitrogen-containing vinyl, allyl and cyclic monomers formed by the interaction inter se and with benzoyl peroxide. The purpose of the research is on the base of intermolecular donor-acceptor interactions study in aforenamed monomer systems to develop concepts of their complexes structure or monomer - benzoyl peroxide complexes, to develop a common approach to assessment of their reactivity; study of the cleavage and the contribution of complexes monomer1···monomer2, monomer···peroxide to the reaction initiation and chain growth in the radical copolymerization of two or three monomers in bulk. Methods of research - UV, IR, 1H and 13C NMR spectroscopy, dilatometry, viscometry, potentiometric titration, scanning electron microscopy, quantum-chemical calculations (methods AM1, PM3, DFT, HF, MP2). The thesis deals with the investigation of structure of self-associates and molecular complexes between acceptor monomers - maleic anhydride, acrylonitrile and donor monomers - styrene, methyl methacrylate, N-vinylpyrrolidone, diallylphthalate, diethylene glycol bis(allyl carbonate), 8-methyl-2-methylene-1,4,6,9-tetraoxaspiro[4,4]nonane, 9-methyl-4-methylene-3,5-dioxabciclo[5,4,0]undecane, 1-acryloyloxymethyl-3,4-epoxycyclohexane and their complexes with benzoyl peroxide. The formation of these complexes and self-associates in solution was proved and basic types of complexes and their relationship were identified. It was proved the structure of pi-H-complex between monomers which provides an increase of their activity in the radical addition and formation of the copolymer with alternating units in the chain, as well as the copolymerization in the absence of radical initiator. A scheme of decomposition of pi-H-complex of N-vinylpyrrolidone and maleic anhydride radicals was proposed. The formation of H-benzoyl peroxide complexes with vinyl monomers which accelerate decomposition of the peroxide bond was proved. It was found that the presence of molecular complexes leads to increasing of initiation and chain growth rate and to influence the composition and structure of the copolymer chain at bulk copolymerization of two or three monomers capable to homopolymerization. The results of the thesis extend the understanding of the processes of formation of associates and complexes of unsaturated compounds. The using of the most active interacting pairs monomer or monomers with a radical initiator allows to carry out radical reactions at low temperatures and to adjust their rate. The results are a scientific basis for the the synthesis of multi-purpose plastics, especially medical, purposes.
