Grekova A. Features of initiation of the vinyl monomers polymerization by tertiary hydroperoxides in the presence of 3d-metal chelates with S(S) - and O(O)-containing organic ligands

The object of research is the development of effective initiating systems of the radical polymerization of vinyl monomers. The purpose of the work was to study of the catalytic and initiating activity of two-component systems on the basis of tertiary hydroperoxides and 3d-metals complexes in the polymerization of styrene and methyl methacrylate. The main results were obtained using the methods of dilatometry and gravimetry, gel permeation chromatography, viscometry, IR and NMR spectroscopy, the method of mixed initiation gasometrical and iodometric methods. The kinetics of hydroperoxides decomposition was studied in the presence of 3d-metals N,N-diethyldithiocarbamates in ethylbenzene in the range 333-363 K. It is proved that these catalysts are the chelates of hydroperoxides decomposition. The process features characteristic for controlled radical polymerization were identified in the polymerization of vinyl monomers initiated by systems hydroperoxides - 3d-metals N,N-diethyldithiocarbamates. Two effective initiating systems based on hydroperoxides and Cu (II), Ni (II) N, N-diethyldithiocarbamates and a mechanism of controlled polymerization were proposed. Among the copper (II) chelates with ligands of different nature was identified catalytic activity of the complex of copper chloride (II) with piperidin-1-yl piperidin-1-carbodithioate in the reactions of hydroperoxides decomposition during the polymerization. Application of aminoacetate and glytsilglytsinate bis (4-fenylthiosemikarbazid) Cu (II) in the polymerization of MMA allows one to obtain the products with syndiotactic structure.