Currently, polymers with special properties are widely used in various areas, including medicine and electronic. However, specific of usage of such materials is determined by their structure. In this case, the development of novel polymeric macromolecules with controlled structure and studying of peculiarities their synthesis is an actual task for today. In this paper surface active block/comb-like copolymers were obtained via free radical polymerization by two-step polymerization. Firstly, telechelic oligoperoxides (TOs) with polyethylene glycol (PEG) side chains were received via radical polymerization of PEG-contained macromers in presence of functional peroxide-contained chain transfer agent – monoperoxine (MP) which possessing weakly inhibiting action which decreases polymerization rate value and lowers TOs molecular weight at the increase of MP concentration. It was shown that activity of polymeric radicals increases with the length of macromer PEG substituent at constant concentration of MP. The number of peroxide-contained macromolecules was incremented as a result. Order of reaction for such systems with respect to initiator was decreased that could be explained by inefficient consumption of initiator in the reaction mixture (streric and diffusion factors). Secondary, the terminal peroxide group was provided the usage of synthesized copolymers as macroinitiators in polymerization of monomers with low molecular weight, in particular hyrophilic N-vinylpyrrolidone (NVP). Kinetic parameters of NVP polymerization initiated by TOs in presence of epoxide contained chain transfer agent were obeyed regularities of weakly inhibiting radical polymerization. The structure of comb-like and block/comb-like copolymers was confirmed by elemental and functional analysis, spectral (IR spectra) and chromatographic (gas-liquid chromatography) methods. Comb-like oligoperoxide macroinitiator and block/comb-like copolymer based on it are surface active substances forming micelle-like structures of different size in water solutions. The presence of functional epoxide group in structure of diblock-copolymer make it possible to covalent bind of amino-contained natural macromolecules, such as peptides, oligonucleotides or aminoacids.
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