Search

The state diagram of the low-density polyethylene–p-xylene system that contains the solubility curve of p-xylene in the polymer is first built using the optical method with the involvement of the DSC data. It has been shown that, at 72°C, in a blend with a polymer mass fraction of 0.28, the full amorphization of the polymer proceeds simultaneously with the dissolution of p-xylene in it. Blends with a lower polymer content are also homogenized at the same temperature, although the duration of this process can take several days. In blends with a high polymer content, homogenization occurs at a higher temperature. This process is preceded by the formation of microheterogeneous single-phase gel with network junctions as polymer crystallites and amorphous regions saturated by p-xylene. Cooling of the homogeneous blends to–20°С is not accompanied by the full separation of low- and high-molecular-mass phases; in this case p-xylene not only forms an individual crystalline phase, but also partially crystallizes in amorphous regions of the polymer.

A melting temperature of 90.4°C (complete amorphization) for macromolecular poly-3,3-bis(azidomethyl)oxetane is determined via the hydrostatic-weighing method. This value corresponds to the end of the endothermic peak of the DSC thermogram and is ~10°C higher than the maximum value. The amorphization of the polymer is found to proceed mainly owing to thermomechanical destruction of the crystallites, and only a very small part of them is melted purely thermally at the temperature of complete amorphization. The melting temperature is significantly reduced in the presence of the oligomer fraction in the polymer. The density and equilibrium heat of fusion of the crystalline regions, which coincide for various polymer samples, are found with consideration for the data of X-ray scattering.

The full phase diagram of a high-density polyethylene-1,2,4,5-tetrachlorobenzene (TeCB) mixture, which includes the solubility curve of TeCB in the polymer, is constructed for the first time by the optical method. It is shown that TeCB crystals are dissolved in polyethylene via vapor phase mechanism on heating, which leads to the polymer amorphization. The eutectic mixture composition corresponds to the situation when the crystallization of TeCB out of its solution in polyethylene is accompanied by the crystallization of elementary units of macromolecules. As a result, the polymer acquires a gel structure with crystallites as crosslinks and amorphous regions saturated with TeCB.

A comparative study of the viscoelastic properties of melts of vinyl acetate-vinyl alcohol copolymers with equimolar compositions characterized by different statistical distributions of chain units has been performed. It has been shown that the principle of temperature-frequency superposition is obeyed by copolymers close to a random copolymer, but is violated by copolymers with the block distribution of units. Unlike amorphous random copolymers, a multiblock copolymer is characterized by weak crystallinity, the absence of the relaxation flow state, and a more pronounced tendency to form interchain hydrogen bonds both between two hydroxyl groups and between hydroxyl and ester groups.

Thermal fractionation via the method of successive self-nucleation and annealing was used for the first time to study the crystallinity of vinyl acetate-vinyl alcohol copolymers with different random distributions of chain units. The lamella-thickness distribution was calculated through the Gibbs-Thomson equation. It was shown that, for all samples, the minimum lamella thickness is the same and corresponds to a block of no less than 15 vinyl alcohol units. On the basis of these data and with the use of the computer simulation of the polymer-analogous reaction via the Monte Carlo method, the block-length distribution in the crystalline phase was found. It was shown through a comparison of the lamella-thickness and block-length distributions that the maximum lamella thickness increases with the block length and vinyl alcohol content in the copolymer. In crystallites, blocks with lengths exceeding the maximum lamella thickness comprise a significant fraction. Thus, it is probable that these blocks form folds. The dependences of melting temperatures of crystalline lamellas on their thicknesses, as well as the dependences of the melting temperatures of copolymers not subjected to thermal fractionation on the chain-structure parameters, are adequately described by the Flory crystallization theory.

The dissipative particle dynamics method is employed to conduct the computer simulation of the phase separation occurring in a melt of a polymer containing monomer units of two types under the conditions of reversible polycondensation or interchain exchange. The chemical reactions are simulated via the Monte Carlo method. It is shown that growth in the Flory-Huggins parameter leads to macrophase separation, irrespective of the rate and type of the reactions and the spatial structure of an initial system. Relative changes in the probabilities of elementary reactions between units of different types shift the phase-transition point. Different levels of refinement are considered for description of the stationary states being developed. By the example of interchain exchange, it is shown that the structure of the polymer melt in the initial state can substantially affect the dynamics of the phase separation.

The self-organization of statistical multiblock and Bernoulli AB copolymers is studied. The initial ensemble is generated via the polymer-analogous reaction A→B that proceeds with the accelerating effect of neighboring B units. In a two-dimensional model, the reaction is performed in a rectangle composed of stretched chains. Then, the rectangle is closed into a cylinder, so that ring chains are located on its side surface. The self-organization of the ensemble is simulated via the successive rotation of each upper ring over the lower ring until arrangement with the maximum (in modulus) energy of attraction between chains is attained. Self-organization by energy is accompanied by lateral ordering: the sizes of clusters—accumulations of the one-type units—and mean heights HA (HB) of stems—columns consisting of A or B units perpendicular to chains—increase. The ratio between the values of HA, as well as HB, for ordered and initial ensembles is independent of the average composition of the system and as a rule increases as the length of blocks increases and the length of chains decreases. Features of generation of the ensemble of short chains and their ordering are revealed. It is shown that, during ordering of multiblock copolymers, the probabilistic properties (the stochastic behavior) of the ensemble are disturbed. The self-organization of statistical multiblock copolymers in a three-dimensional model is investigated via rotation of rings in the torus of the rectangular cross-section. The effects of various factors on self-organization by energy and local ordering in 2D and 3D models are similar; however, the efficiency of ordering in the three-dimensional system is always lower because, in this case, arrangements with the maximum energy of attraction simultaneously to two neighboring chains, rather than to one, are implemented for the majority of chains.

The dissipative particle dynamics method and parallel computing are employed for computer simulation of phase separation in melts of regular and random (Markovian) AB multiblock copolymers of symmetric compositions. For the first time, it is shown that, as the Flory-Huggins parameter χ is increased, lamellar microstructures are formed in all these systems. At preset block length M, the microstructures arise in regular copolymers at lower χ values than those in random copolymers, while the formed lamellas are narrower and have smaller amounts of defects. At χM > 100, a superstrong segregation regime develops in the regular copolymers. In random copolymer melts, bicontinuous structures are observed for a long time; in the long run, they are likewise transformed into lamellar structures whose imperfection substantially increases with M.

For films based on poly(amidoimide) with a comb-shaped structure and long side chains, the specific features of the mechanical and thermomechanical behavior and their dependence on the concentration of the above chains are studied. With variation of the composition of the material, changes in the mechanical characteristics show a nonmonotonic character. Comparison of the results of mechanical tests and densimetric measurements allows certain conclusions to be drawn about the character of variations in the structural organization of films with an increase in the concentration of side fragments in macrochains. The role of plasticization in the behavior of the above materials during heating is demonstrated. The advantages of the practical use of the above phenomena for the optimization of the regimes of thermally stimulated polarization of films are discussed.

The nonuniformity of nitrile-butadiene rubber solutions in toluene and chloroform has been studied. Dynamic-light-scattering measurements show that these solutions contain two kinds of scattering particles: small particles 10–16 nm in radius corresponding to the macromolecular coil and large particles 400–500 nm in radius corresponding to aggregates. The aggregates are stable in solutions for at least several days. Such stability may be interpreted in terms of topological factors supposing that the aggregates are formed via noncovalent interactions of tens of thousands of highly branched entangled chains. The chains become disentangled even during slight shear. Thus, the solution of nitrile-butadiene rubber subjected to soft rolling mostly contains small particles. However, in the absence of external fields, such a structure is very stable in solution and even more so in the rubber block. During storage of nitrile-butadiene rubber, formation of a relatively small quantity of covalent crosslinks suffices for fixing the structure of aggregates and prevents the disentanglement of chains. Thus, the crosslinking of the aggregates may be primarily responsible for the natural aging of nitrile-butadiene rubber during storage.

The interchain exchange and interdiffusion in blends of poly(ethylene terephthalate) and poly(ethylene naphthalene-2,6-dicarboxylate) are investigated with reprecipitated commercial samples (Mη ∼ 104) and samples containing no polycondensation catalyst (Mη ∼ 103) synthesized in the course of this study. The kinetics of multiblock copolymer formation and gradual reduction of the mean block length in quasi-homogeneous blends were shown to fit a simple theoretical model of a second-order reaction. The increase of the reaction-rate constants on the transition from commercial samples to synthesized ones revealed a significant role of chain ends in interchain exchange. The detected activation energy of the interchange in the absence of catalysts (97 kJ/mol) was noticeably less than that previously reported for the polymer pair under study (120–170 kJ/mol). The obtained data were applied for analysing the interdiffusion between melts of the same polymers accompanied by the interchain exchange. By means of the microinterference method, the interdiffusion in the synthesized samples was shown to be much faster than that in the reprecipitated commercial samples, a result that may be due to the better compatibility of the initial polyesters as their molecular mass decreased. In later stages of the process in both systems, the interpenetration of components was slower than that predicted by Fick’s law, owing to formation of copolymer species that diminished the thermodynamical factor of mixing.

The autocatalytic polymer-analogous reaction A → B in a blend composed of two contacting layers of compatible homopolymers A and B is studied by numerical simulation using the dynamic continuum Monte Carlo method. The evolution of the numerical density of units A and units initially belonged to the chains of homopolymer A is investigated in the course of the reaction and interdiffusion. Local characteristics of the distribution of the homopolymer with respect to its composition and blocks A and B with respect to their length are calculated at different times. The dispersions of the above distributions are appreciably higher than the corresponding dispersion of the Bernoullian copolymer of the same average composition, despite the random character of the reaction. This effect can be provided by changes in the composition of the blend on the scale of the reacting chain as well as by the diffusive mixing of the above chains. For the products of the polymer-analogous reaction, the broadening of the compositional distribution is predicted also by the theoretical model, which describes interdiffusion in the reacting system on scales that are markedly greater than the size of a polymer chain.

A procedure is developed for preparing conducting films by their casting from polymer solutions containing polyaniline in the form of a protonated emeraldin base and polyimides in two cosolvents, N-methylpyrrolidone or m-cresol. Self-supporting films cast from composites based on polyimides and camphorsulfonic acid-protonated polyaniline combine a conductivity of 10−1−10−2S/cm with good mechanical properties: elastic modulus E = 2.0−2.4 GPa, breaking strength σb = 55−60 MPa, and elongation at break ɛb = 8−10%. It has been shown that, when m-cresol and N-methylpyrrolidone are used as cosolvents, the maximum film conductivity is achieved at polyaniline amounts in the composites of 20 and 3%, respectively. In the latter case, films with good strength parameters are formed.

Soluble polyimides containing triphenylamine residues as substituents at the imide nitrogen atom and polyquinazolones with diphenyl oxide, diphenylpropane, benzimidazole, benzoxazole, benzothiazole, oxadiazole, and triphenylamine moieties in the diamine component of the repeating unit have been synthesized. The spectroscopic study of polyquinazolones indicates their capability for donor-acceptor interactions. Emission bands of the polymers are of the exciplex nature. The photogeneration of current carriers in the polymers under study has been examined by the method of surface potential photoinduced decay. It has been shown that the intrinsic photosenitivity of polyquinazolones is nearly the same as (or somewhat higher than) that of the corresponding polyimides, but the former polymers are characterized by a less efficient spectral sensitization by dyes and donor-acceptor additives.

The local forms of molecular mobility of comb-shaped random copoly(methacrylates) have been studied by the method of dielectric spectroscopy. Side branches of these copolymers are composed of alternating chromophore-containing chains and flexible fluoromethylene sequences. Two regions of relaxation of dipole polarization, γ2 and β processes, related to the mobility of end polar groups and the reorientation of chromophore groups relative to their long axes, respectively, have been discovered in the glassy state. The times of relaxation of the γ2 process depend on the ratio between the flexible and rigid parts of the copolymer. In the region of the β process, the molecular mobility appears to be slightly dependent on the chromophore structure and its intensity is determined by the degree of substitution of chromophore groups.

The interchain exchange reaction in a blend composed of two contacting layers of incompatible A and B homopolymers was simulated by means of the dynamic off-lattice Monte Carlo method. The evolution of local molecular-mass and block mass distributions, depending on the effective temperature and the reaction rate, was studied for the first time. It was shown that the components interpenetrate as the copolymer forms in the interphase layer and the average block length decreases below a certain, temperature-dependent value. The state of dynamic equilibrium, whose characteristics are determined mainly by temperature, is established in the system. The time of establishment of equilibrium and the intensity of compatibilization at the early steps of the process are controlled by the rate of the reaction. The results of the study allow the contribution of the reaction to the interchange processes to be evaluated.

A number of styrylquinoline chromophores with carboxyl groups have been prepared through the interaction of 2-methylcinchonic acid with aromatic aldehydes of various chemical structures. The copolymer of glycidyl methacrylate and methyl methacrylate carrying side epoxide groups has been synthesized, and the chemical modification of the copolymer with the above chromophores has been performed. The thermal, spectral, and nonlinear optical properties of the chromophores and modified polymers have been studied.

The molecular mobility of copoly(methacrylates) with chromophore-containing side groups of various structures has been studied by the dielectric method. The region of relaxation of dipole polarization related to the segmental mobility (α process) has been discovered. At temperatures that are ∼30°C higher than those corresponding to the α process, the relaxation transition reflecting the reorientation of chromophore-containing side groups (δ process) takes place. It is suggested that the occurrence of the δ process is a general phenomenon for such systems. This effect allows one to determine the temperature at which the polarization of polymer films under application of corona discharge should be carried out so that a high level of nonlinear optical properties associated with the macroscopic noncentrosymmetrical orientation of chromophores may be achieved.

The structure of mixed amide solvents used for the preparation of polyimide Langmuir-Blodgett films and the structural organization of water, on which nanofilms are formed, have been studied by polarized light scattering. Fluctuation supramolecular structures are found to exist in water and in its mixtures with amide solvents, and the dimensions of the structures are comparable with the light wavelength. When a mixture contains more than 20 vol % water, associates show microanisotropic properties. In snowmelt water, the dimensions of associates are larger than those in distilled water. In the DMAA-water mixture, the dimensions of supramolecular structures are virtually independent of composition.

Morphology of asymmetric membranes based on poly((diphenyl oxide amido)-N-phenylphthalimide) was studied by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The effect of preparation conditions on the morphology and transport properties of the membranes was investigated. The test membranes were prepared by the phase-inversion method under the conditions of “wet” casting in the polymer-solvent (N-methyl pyrrolidone)-nonsolvent (water, ethanol, 2-propanol, or aqueous alcohol solutions) systems. Feed casting solutions with a concentration of 10–14 wt %, including those containing a weak nonsolvent (ethyl acetate) were used. A comparative analysis of the structural features and water permeability of the test membranes allows the conclusion that some types of membranes can be used in nanofiltration processes.

With the use of light scattering and viscometry, as well as the employment of various aprotic solvents for the polymer synthesis, the molecular characteristics of two poly(amic acids), namely, poly[4,4′-bis(4″-N-phenoxy)diphenylsulfone]amic acid of 1,3-bis(3′,4-dicarboxyphenoxy)benzene and poly[4,4′-bis(4″-N-phenoxy)diphenyl]amic acid of 1,3-bis(3′,4-dicarboxyphenoxy)benzene, have been studied at various molar ratios of the starting reagents and concentrations of the polycondensation solution. The molecular masses of poly(amic acids) depend on the thermodynamic quality of a solvent which may be changed by varying the nature of the solvent, the structure of the resulting polymer, or the chemical nature of the mixture.

Soluble poly(amido imides) and copoly(amido imides) containing main-and side-chain chromophore chalcone groups have been synthesized. Thermo-and photocrosslinking of polymer chains in films under UV irradiation have been studied. The mechanical properties, dielectric behavior, and photosensitivity and photoconductivity characteristics of the polymers have been investigated.

Structural organization is studied for dilute solutions of the comblike N,N-dimethylhexadecylammonium salt of polyamic acid based on 3,3′,4,4′-diphenyltetracarboxylic dianhydride and o-tolidine by the method of polarized light scattering in mixed dimethylacetamide-benzene and N-methylpyrrolidone-benzene solvents. The statistical structural parameters of the solutions are calculated according to the Debye-Stein theory. The dimensions of ordered scattering fluctuation-type formations are shown to be much greater than the molecular dimensions and to depend on the chemical nature and composition of the mixed solvent. At polymer concentrations below 0.2 g/dl, the corresponding concentration dependences of the statistical structural parameters are characterized by extreme patterns for all systems under study.

New polyamic acids with biquinoline units in the backbone, which are prepolymers of polybenzoxazinones, as well as their metal-polymer complexes containing [Ru(bpy)2]2+, were prepared. The electronic structure of these polymers was studied with the use of cyclic voltammetry, electronic absorption spectroscopy, and quantum-chemical calculations, and the location sites of electronic changes upon electrochemical reduction and oxidation were determined.