Structural and morphological features of graft polystyrene (PS) and polyethylene (PE) copolymers produced by post-radiation chemical polymerization have been investigated by methods of X-ray microanalysis, electron microscopy, DSC and wetting angles measurement. The studied samples differed in the degree of graft, iron(II) sulphate content, sizes of PE films and distribution of graft polymer over the polyolefin cross section. It is shown that in all cases sample surfaces are enriched with PS. As the content of graft PS increases, its concentration increases both in the volume and on the surface of the samples. The distinctive feature of the post-radiation graft polymerization is the stepped curves of graft polymer distribution along the matrix cross section. A probable reason for such evolution of the distribution profiles is related to both the distribution of peroxide groups throughout the sample thickness and to the change in the monomer and iron(II) salt diffusion coefficients in the graft polyolefin layer. According to the results of electron microscope investigations and copolymer wettability during graft polymerization, a heterogeneous system is formed both in the sample volume and in the surface layer. It is shown that the melting point, glass transition temperature and degree of crystallinity of the copolymer decreases with the increasing proportion of graft PS. It is suggested that during graft polymerization a process of PE crystallite decomposition (melting) and enrichment of the amorphous phase of graft polymer by fragments of PE macromolecules occurs spontaneously. The driving force of this process is the osmotic pressure exerted by the phase network of crystallites on the growing phase of the graft PS.

A new approach is proposed for simulating binodal and spinodal curves of phase diagrams for binary polymer systems. It is shown that the Flory–Huggins theory makes it possible to predict phase behavior in a wide range of temperatures and concentrations based on limited data on the components’ solubility. The approbation data of the technique are presented in the example of PS–PB and PS–PMMA systems, for which generalized phase diagrams are constructed.

Phase equilibria, interdiffusion and structure in the initial uncured mixtures of epoxy oligomer–polysulfone–alkyl glycidyl ether were studied. Binodal curves were constructed on isothermal sections of the ternary phase diagram. Thermodynamic mixing parameters were calculated and spinodal curves were plotted. The interdiffusion coefficients of components, establishing the technological modes of mixing the components, were determined. To validate the phase diagram, the phase structure of mixtures, the composition of which at a temperature of 40 °C corresponds to heterogeneous and homogeneous regions, was studied.

The phase state diagram of the poly(vinyl methyl ether)-water system in a wide concentration range was obtained by the optical interferometry method. It was shown that this system was characterized by a complicated phase equilibrium with two lower critical solution temperatures, one of which was located in the concentrated region at 21 °C, and the other one in the region of a dilute solution at 31 °C. In the framework of the Flory–Huggins theory, pair interaction parameters were calculated for different parts of the binodal curves, and an attempt was made to reverse simulate the diagram in different conditions. It was suggested that the unusual character of the diagram was associated with the formation of a complicated complex between PVME and water in the middle region of the compositions. Concentration profiles for different temperatures were constructed. For the first time for this system, the numerical values of the diffusion coefficients of poly(vinyl methyl ether) (PVME) into water and water in PVME were obtained. Concentration and temperature dependences of diffusion coefficients were constructed and analyzed. The kinetics of water sorption in PVME was plotted, the clustering integral was calculated, and the approximate number of molecules in a water cluster was estimated. It was shown that in the dilute solution region upon passing through the binodal curve, the interphase disappeared immediately, and the remaining fluctuation of the concentration decreased in size with time. The kinetics of this process was estimated from the change in the size of such a particle.

Phase equilibria in polystyrene-poly(n-butyl acrylate) systems containing polystyrene of various molecular masses were studied for the first time via optical interferometry at temperatures between 280 and 500 K. The phase diagrams of the systems were obtained, the pair interaction parameters were determined, and the dependences of the parameters on the molecular mass of polystyrene and temperature were found. The possibility of thermodynamic analysis of phase diagrams in terms of the classical Flory-Huggins-Scott theory and the possibility to predict generalized phase diagrams of polystyrene-poly(n-butyl acrylate) systems on the basis of the experimental values of the pair interaction parameters were shown.

Qualitative and quantitative aspects of the formation of various types of phase structures, sizes and compositions were considered. For the studied polycaprolactone–epoxy resin/4,4′-diaminediphenylsulfone system, a phase diagram characterized by amorphous separation with a lower critical solution temperature was constructed and its evolution was traced with increasing conversion degree of epoxy groups. A method is proposed for determining the temperature–concentration parameters that determine the type of phase structure of composite materials, based on the optical interferometry method. All types of phase structures and features of structure formation in the phase reversal region and at its boundaries have been studied using optical and scanning electron microscopy methods. The dimensions of the structural elements were determined and their correlation with the temperature and concentration regimes of the system’s curing was established. The composition of phases in cured compositions was studied using FTIR spectroscopy, DSC and scanning electron microscopy. It is shown that by varying the temperature–concentration parameters of curing reactive thermoplastic systems, it is possible to specifically regulate the type of phase structure, phase sizes and their composition, which determine the operational properties of the material.