Imidazole-containing network polymers have been prepared via quaternization of linear poly(1-vinylimidazole). Owing to the affinity for water, crosslinked poly(1-vinylimidazole) is capable of limited swelling in water and concomitant formation of polyelectrolyte hydrogels. Imidazole-containing hydrogels can be doped with different metal ions and can serve as matrixes for stabilization of particles obtained via reduction of nanosize metals.

Реакцией кватернизации линейного поли-1-винилимидазола дигалогеналканами получены сетчатые имидазолсодержащие полимеры. Обладая сродством к воде, сшитый поли-1-винилимидазол способен ограниченно набухать в воде с образованием полиэлектролитных гидрогелей. Имидазолсодержащие гидрогели могут быть допированы ионами различных металлов и служить матрицей для стабилизации частиц, получаемых восстановлением металлов, существующих в наноразмерном состоянии.

Paired polymers are obtained by the reaction between linear poly(5-vinyltetrazole) and poly(vinyl chloride) in the presence of triethylamine. Poly(vinyl chloride) plays the role of a macromolecular alkylating agent with respect to the tetrazole-containing polymer. The combination of two types of covalently linked macromolecules promotes in the paired polymers the manifestation of some properties typical for both homopolymers.

The swelling in aqueous media of network poly-5-vinyltetrazole synthesized by various procedures using low-molecular-weight, oligomeric, and polymeric cross-linking agents was studied.

Radical polymerization of N-vinylcaprolactam with 5-vinyl- and 2-methyl-5-vinyltetrazole was used to synthesize water-compatible polymeric products whose aqueous solutions have phase diagrams with a lower critical solution temperature. The thermodynamics of the interaction of the copolymers with water and their behavior in aqueous systems were studied.

High-molecular-mass compounds (ionenes) containing charged imidazole and 1,2,4-triazole rings in the main chain are synthesized via the reaction of dihaloalkanes with bis(azoles) of various structures. It is shown that azole-containing ionenes can be involved in interpolymer reactions with negatively charged polyelectrolytes (polyacrylic acid and heparin) to form soluble and insoluble polyelectrolyte complexes of various compositions. The results confirm a potentially high antiheparin activity of azole-containing ionenes.

Crosslinked polymer samples are synthesized through the alkylation of linear poly(5-vinyltetrazole) with di- and multifunctional compounds containing mobile halogen atoms or oxirane cycles. In the ionized state, the crosslinked poly(5-vinyltetrazole) shows limited swelling ability in water and forms hydrogels. It is demonstrated that tetrazole-containing hydrogels may serve as matrices for stabilization of nanosized metal particles.

Polymer polyelectrolytes soluble in water in the ionized state are obtained by the free-radical copolymerization of 5-vinyltetrazole with N -vinylcaprolactam, N -vinylpiperidone, and N -vinylpyridone. The aqueous solutions of 5-vinyltetrazole- N -vinylcaprolactam copolymers are pH-thermosensitive and can be described by phase diagrams with a lower critical solution temperature.

Радикальной сополимеризацией 5-винилтетразола с N-винилкапролактамом, N-винилпиперидоном и N-винилпиридоном получены полимерные полиэлектролиты, растворимые в воде в ионизованном состоянии. Водные растворы сополимеров 5-винилтетразола и N-винилкапролактама характеризуются фазовыми диаграммами с нижней критической температурой растворения и являются рН-термочувствительными.

Interaction of cyanuric chloride and its mono and dichloro derivatives with ammonium or sodium 4-nitro-1,2,3-triazolates and polymer-analogous transformations of tetrazole-containing polymers were used to synthesize polynuclear systems and macromolecular compounds with heterocyclic structures bearing explosophoric groups.

The thermodynamics of interaction with water and the behavior of 5-vinyltetrazole copolymers with comonomers of different chemical natures and hydrophilicities in aqueous media have been studied. It has been shown that the presence of side perfluoroalkyl and disubstituted tetrazole fragments, which ensure a strong self-association of polymer chains in copolymer macromolecules, favors a greater decrease in water affinity of polymers compared to the effect of hydrophobic alkyl substituents.

The temperature dependences of the heat capacities of 5-vinyltetrazole and poly-5-vinyltetrazole were measured by adiabatic vacuum calorimetry over the temperature range 6-(350–370) K with errors of ∼0.2%. The results were used to calculate the thermodynamic functions of the compounds, C p ∘ , H ∘ ( T ) - H ∘ (0), S ∘ ( T ), and G ∘ ( T ) - H ∘ (0), over the temperature range from T → 0 to 350–370 K. The energy of combustion of 5-vinyltetrazole and poly-5-vinyltetrazole was measured in an isothermic-shell static bomb calorimeter. The standard enthalpies of combustion Δ c H ∘ and thermodynamic characteristics of formation Δ f H ∘ , Δ f S ∘ , and Δ f G ∘ at 298.15 K and p = 0.1 MPa were calculated. The results were used to determine the thermodynamic characteristics of polymerization of 5-vinyltetrazole over the temperature range from T → 0 to 350 K.

Copolymers of 1-vinyl-1,2,4-triazole and 5-vinyltetrazole with 1,1,5-trihydrooctafluoropentyl methacrylate and 1,1,7-trihydrododecafluoroheptyl methacrylate were prepared under the conditions of radical initiation. These copolymers were used for modification of the surface of a glassy carbon electrode, and the effect of the modification on the electrochemical behavior of the electrode in anodic oxidation of dopamine and NO was studied. The possibility of enhancing the selectivity of the electrochemical sensor for monitoring NO in biological media was demonstrated.

The rheological properties of dilute and moderately concentrated aqueous solutions of sodium salt of poly(5-vinyltetrazole) were studied in the presence of a high content of a low-molecular-mass electrolyte. As was found, at high ionic strength of aqueous salt-containing solutions (c(s) > 2 mol/l), the intrinsic viscosity of polymer is not a linear function of c(s)(-0.5). A transition from a dilute to moderately concentrated solution takes place when the concentration of polyelectrolyte is two times higher than the concentration of crossover as estimated from the reciprocal intrinsic viscosity of the polymer. The process of gel formation in aqueous salt-containing solutions of tetrazole-containing polymers in the presence of chromium (III) salts was studied. The minimum concentration of polymer at which gel formation takes place coincides with the concentration boundary of the formation of a fluctuation entanglement network in the initial aqueous salt-containing solution.

The kinetics of alternating radical copolymerization of vinylphenyl ester with fumaronitrile was studied by IR spectroscopy and quantum-chemical methods. Interaction of the double bond of fumaronitrile With the pi-system of benzene ring in a planar conformation of ester leads to the formation of a donor-acceptor complex between monomers. This accounts for lower reactivity of monomers in the complex as compared to that of the free monomer molecules. The polymer chain propagation occurs by alternating addition of free I monomers to the reactive end of the chain.

A kinetic study of the mechanism of radical alternating copolymerization of p-chlorophenol vinyl ether and maleic anhydride is conducted. Based on IR spectroscopic data and quantum chemical calculations, it is shown that the donor-acceptor complex formed by the monomers is mainly stabilized by the benzene ring pi-system, which applies both to a planar and to a nonplanar conformation of the vinyl ether. This is indicative of a lower reactivity of the complexed monomers compared to the free ones. The growth of the polymer chain occurs through addition of the free monomers to the growing macroradical. Despite an appreciable concentration of the donor-acceptor complexes, they are not involved in the reaction of the chain growth.

The mechanism of radical, alternating copolymerization of vinylphenyl ether with diethyl maleate was studied by kinetic methods. An alternating copolymer is formed in the absence of donor-acceptor interactions between the comonomers. The macroradical grows by adding free monomer molecules with the mixed rate constants considerably larger than the rate constants of homoaddition.