A series of linear high molecular weight acrylonitrile homopolymers have been synthesized using controlled anionic polymerization. The possibility of producing polyacrylonitrile with a wide range of molecular weights by controlling the concentrations of metal-free initiator and water has been demonstrated. The resulting homopolymers exhibit excellent spinnability.

A new method for the synthesis of azido-propargyloxy derivatives of 1,3,5-triazine has been developed utilizing the nitrosation of hydrazyno-1,3,5-triazines. New hydrazines (2-hydrazino-4,6-bis(propargyloxy)-1,3,5-triazine and 2,4-dihydrazino-6-propargyloxy-1,3,5-triazine) were synthesized and characterized via FTIR, NMR spectroscopy and elemental analysis. The hyperbranched polymers with azide (diazide monomer) and propargyloxy terminal groups were obtained via the azide-alkyne polycycloaddition reaction of diazide and monoazide AB2-type monomers. The antibacterial activity against Escherichia coli bacteria of 2,4,6-trispropargyloxy-1,3,5-triazine, 2-azido-4,6-bispropargyloxy-1,3,5-triazine, and 2,4-diazido-6-propargyloxy-1,3,5-triazine and their hyperbranched polymers was studied. Only 2,4-diazido-6-propargyloxy-1,3,5-triazine has weak antibacterial activity in comparison with ampicillin. The cytotoxicity of these compounds against M-HeLa, FetMSC, and Vero cell lines was also studied. 2,4,6-trispropargyloxy-1,3,5-triazine does not show any cytotoxic effect (IC50 ≥ 280 µM). It was shown that the presence of an azide group in the compound directly affects the cytotoxic effect. Hyperbranched polymers have a less cytotoxic effect against M-HeLa (IC50 > 100) in comparison with monomers (IC50 = 90–99 µM). This makes it possible to use these polymers as the basis for biocompatible materials in biomedical applications.

The process of curing the acrylic oligomers for rapid thermal curing coatings in the presence of hexa(methoxymethyl)melamine (HMMM), tetra(butoxymethyl)glycoluril (TBMG), and tetra(methoxymethyl)glycoluril (TMMG) has been studied. When HMMM is used as a hardener, the content of hydroxyl groups in the terpolymer and also the crosslinking agent concentration have little effect on the initial cure rate. It has been established that during the curing of the TMMG composition, the amount of the network polymer and the initial curing rate decrease at short curing times only. It has also been revealed that the use of butoxy groups instead of methoxy groups as blocking agents leads both to a decrease in the initial cure rate and the gel fraction limiting value from 98 to 80%. When it comes to TBMG-containing compositions, a decrease in the part of hydroxyl groups in the copolymer leads to a significant fall in the initial curing rate and also in the gel fraction content. Regardless of the crosslinking agent used, an acceleration of the curing process is observed with an increase in the catalyst content in the compositions.

An efficient synthesis of the new star-shaped polymer with azido-containing oligomer rays is based on construsion of these rays on the β-cyclodextrin nitrate core employing 3,3-bis(azidomethyl)oxetane as the key reactant. The formation of star-shaped structure was proved. Thermal and optical properties of the synthesized polymers were assessed.

Eco-friendly waterborne polyurethanes (WPU) find wide application in agriculture as pesticide carriers, which enhances their efficiency. To provide better control of the retention time and capacity of pesticides, WPU can be modified by cyclodextrin derivatives able to form supramolecular assemblies with bioactive substances. Synthesis of WPU containing up to 15 wt.% of covalently bound β-cyclodextrin partial nitrate (CDPN) is reported in this work. Covalent bonding of CDPN to a polyurethane matrix has been proved by IR spectroscopy and size exclusion chromatography. The particle size and viscosity of the WPU dispersion have been determined. The introduction of CDPN affects molecular weight and thermal properties of WPU films. The presence of CDPN in WPU is shown to provide higher average molecular weight, wider molecular weight distribution, and larger average size of dispersed particles, compared with WPU reference samples containing 1,4-butanediol. The analysis of the rheological behavior of the obtained WPU dispersions shows that they can be classified as pseudoplastic liquids. The analysis of the thermal parameters of WPU films indicates that the introduction of 15.0 wt.% CDPN shifts the value of the glass transition temperature from −63 °C to −48 °C compared with reference samples. We believe that the results of the present study are sufficiently encouraging in terms of using CDPN-modified eco-friendly WPU as potential systems for developing the delivering agents of bioactive compounds. The application of such systems will allow the long-term contact of pesticides with the plant surface and minimize the possibility of their release into the environment.

The regularities of the formation, as well as the structure and properties of the epoxy nanocomposites synthesized via curing with 4,4′-diaminodiphenylmethane and triethylamine of the ED-20 epoxy binders modified by spherical small ( r ~ 2 nm) narrowly dispersed silver nanoparticles with oligostyrylmono-carboxylate ligands were studied by SEM, UV–Vis spectroscopy, and DSC methods. The limiting initial concentration of silver oligostyrylmonocarboxylate in the modified binder, which affords uniform distribution of the silver nanoparticles ( r ~ 8–20 nm) in the nanocomposites, was estimated at 2.5 wt %. The silver nanoparticles cause a slight decrease in the glass transition temperature and do not affect the mechanical characteristics of the epoxy nanocomposites. The thermophysical characteristics of the nanocomposites depend on the topology of the epoxy matrix.

Branched polyacrylonitrile has been synthesized via anionic polymerization with the 1,4-diazabicyclo[2.2.2]octane–ethylene oxide initiating system. The degree of branching has been determined by means of NMR spectroscopy and indirectly confirmed by viscometry of the dilute solutions. Solutions of binary mixtures of the branched PAN with the industrial linear polymer in dimethyl sulfoxide with different ratio of the components have been prepared; their rheological behavior has been investigated. It has been shown that the introduction of the branched polymer in a solution of linear PAN allows significant decrease in the mixed solutions viscosity at equal total fraction of the polymer. The addition of branched PAN in a solution of the linear PAN has increased the total concentration of the polymer in the system favoring the increase in the viscosity of the mixed solution, but the viscosity has been significantly lower than this of the equally concentrated solution of the linear polymer. Investigation of the frequency dependences of the components of complex shear modulus of these solutions has revealed that the increase in the viscoelastic properties is mainly due to the increase in the elasticity modulus. Exponent of the frequency dependence of the loss modulus in the terminal zone has not been changed, whereas this of the elasticity modulus has been decreased to 0.4 over the entire range of the ratio between the branched and linear PAN. The specific relaxation time has been decreased with the increase in the fraction of linear PAN. Thermal behavior of linear and branched PAN has been investigated by means of DSC. The performed study has revealed the possibility of preparation of the mixed films and fibers based on linear and branched polyacrylonitrile.

The structure of α-, β- and γ-cyclodextrin nitrates was analyzed by X-ray diffraction. It has been established that with an increase in the number of nitrate groups in β- and γ-cyclodextrin nitrates, the structure changes from crystalline at a degree of substitution of hydroxyl group 9–12% to amorphous at that of more than 40%, which is a consequence of steric factors and different degrees of polarity of functional groups (OH) and (ONO2). In the case of α-cyclodextrin nitrates, with an increase in the degree of substitution of OH group, the tendency to amorphization of the substance, which is characteristic of β- and γ-cyclodextrin nitrates, remains. However, at a degree of substitution of 98–100% the appearance of a new crystalline phase is observed. Probably, the molecules of α-cyclodextrin nitrates, which have only 6 glucopyranose units in their composition, undergo structural changes due to steric effects, resulting in the formation of a new molecular crystal structure with a more stable configuration.

The polymerization of acrylonitrile under the action of the new initiating system 1.4-diazabicyclo[2.2.2]octane–ethylene oxide is studied. The polymerization initiated by this system is accompanied by the occurrence of intra- and intermolecular chain transfer to the polymer. It is found that cyclic ethers, such as ethylene oxide and tetrahydrofuran, facilitate the reaction of chain transfer, acting as catalysts, as confirmed by quantum chemical calculations. The study of the thermal behavior of the synthesized hyperbranched polyacrylonitrile samples in the temperature range of 175–350°C shows that heat release for these samples begins at lower temperatures and proceeds in a wider temperature range and with a lower intensity compared to a linear polymer.

Anionic copolymerization of acrylonitrile with methyl acrylate under the action of the 1,4-diazabicyclo[2.2.2]octane–ethylene oxide initiating system was studied. Similarly to the anionic homopolymerization of acrylonitrile, the copolymerization is accompanied by the intra- and intermolecular chain transfer to the polymer. The influence of the copolymerization conditions on the intensity of the chain transfer leading to the formation of highly branched and hyperbranched copolymers was examined. The acrylonitrile–methyl acrylate copolymerization constants were determined: r1 = 1.25 ± 0.06 and r2 = 0.18 ± 0.07. Quantum-chemical calculations of the thermodynamic parameters of the copolymerization were made.

In der vorliegenden Arbeit wurde die Synthese von ABO3-Perowskiten durch Sprayflammensynthese (SFS) untersucht. Das im Fokus stehende Materialsystem war das Perowskit BaTiO3 (BTO), bei dem die A-Position im Gitter von Ba und die B-Position von Ti besetzt sind. Bisher berichten nur wenige Literaturquellen uber die SFS von BaTiO3, daher wurden im Rahmen dieser Doktorarbeit geeignete Losungsmittel, Prakursoren und Syntheseparameter (Konzentration der Prakursoren, Gasflusse, Reak-tordruck) untersucht, um die optimalen Synthesebedingungen zu ermitteln. Die hergestellten Materia-lien wurden ex situ bezuglich ihrer physiko-chemischen Eigenschaften untersucht. Bei den hergestellten Materialien handelt es sich um nanokristalline BaTiO3-Pulver, die neben einer Mischung von Materialien mit kubischer und tetragonaler Kristallstruktur auch eine zusatzliche uner-wunschte hexagonale Phase aufweisen. Die hexagonale Phase tritt in allen hergestellten Proben auf. Ihre Entstehung wird auf das Schnelle Abkuhlen des austretenden Partikelstroms durch Vermischen mit Quenchgas zuruckgefuhrt. Die Substituierung der A-Position mit Sr und der B-Position mit Zr hat gezeigt, dass die Herstellung von Materialien je nach Konzentration des substituierten Stoffes ohne die hexagonale Phase moglich ist. Untersuchungen der gebildeten Materialien mit IR-Spektroskopie zeigen, dass die Oberflachen der Materialien mit organischen Spezies verunreinigt sind, die durch unvollstandige Verbrennung der Losungsmittel und Prakursoren entstehen. Eine thermische Nachbehandlung der Pulver nach der Synthese fuhrt zu Materialien mit saubereren Oberflachen und hoher Kristallinitat mit einem verringerten Anteil der hexagonalen Phase, wahrend die mittlere Partikelgrose auf der Nanoskala bleibt. Die erzeugten Materialien wurden hinsichtlich ihrer Eigenschaften bezuglich photokatalytischer Was-serspaltung mit UV-Licht (BST, Ba1–xSrxTiO3) und kapazitiver Energiespeicherung (BTZ, BaTi1–xZrxO3) getestet. Die photokatalytische Aktivitat von BTO- und BST-Proben mit und ohne Warmebehandlungen wurde mit denen einer kommerziellen BaTiO3-Probe verglichen. Die Ergebnisse zeigen, dass die durch SFS hergestellten Materialien eine zur kommerziellen Probe ahnliche Aktivitat aufweisen. Bei der pho-tokatalytischen Aktivitat wurde kein nennenswerter Unterschied zwischen warmebehandelten und nicht warmebehandelten Proben beobachtet. Um die Energiespeichereigenschaften der Materialien abschat-zen zu konnen, wurden dielektrische Tests an kompaktierten und gesinterten BTZ-Pulvern durchgefuhrt. Niedrige Zr-Konzentrationen (x = 0–0.15) liefern dabei eine gute Kombination aus Dielektrizitats-konstante und von dielektrischen Verlusten (tan δ). Die Ergebnisse wurden stark von den relativ kleinen Dichten der erzeugten Materialien beeinflusst, die den niedrigeren Sintertemperaturen und Sinterzeiten im Vergleich zu konventionellen Herstellungsmethoden von Keramiken zugeschrieben wurden. Die vorliegende Arbeit hat gezeigt, dass die Herstellung von komplexen und hochqualitativen Materia-lien wie Perowskiten durch Sprayflammensynthese moglich ist. Die Flexibilitat der Herstellungsme-thode wurde durch die gezielte Herstellung variabel (0 < x < 1) substituierter Materialien mit den Zu-sammensetzungen Ba1–xSrxTiO3 und BaTi1–xZrxO3 nachgewiesen.

Polyurethane hydrogels containing polyethylene glycol as a linear fragment and incomplete β-cyclodextrin nitrate as a cross-linking agent were synthesized. The polyols were cross-linked with 1,6-hexamethylene diisocyanate. The hydrogel swelling ratio was studied as a function of the content of partially nitrated β-cyclodextrin in the hydrogel, molecular mass of polyethylene glycol, and degree of substitution of hydroxy groups by nitrate groups in incomplete β-cyclodextrin nitrates. As the cyclodextrin nitrate content is increased from 13 to 44 wt %, the swelling ratio relative to the dry substance weight decreases from 9.5 to 2.3. An increase in the molecular mass of polyethylene glycol from 0.4 to 20 kDa leads to an increase in the swelling ratio from 1.6 to 5.1 for weakly cross-linked polyurethane hydrogels and from 1.2 to 2.8 for the thickly cross-linked hydrogels. The ability of the synthesized compounds to absorb Methylene Blue, Methyl Orange, and phenol was studied. Polyurethane hydrogels do not absorb Methylene Blue. The absorption of Methyl Orange and phenol depends both on the content of incomplete β-cyclodextrin nitrate and on the hydrogel swelling ratio. The synthesized polyurethane hydrogels are biologically compatible.

An IR spectroscopic method for estimating individually the degree of substitution of hydroxyl groups by nitrates in the 2-, 3-, and 6-positions of the glucopyranose ring in partial cyclodextrin nitrates was devised. Calibration curves were constructed and molar extinction coefficients were obtained for ONO2 groups in each position. The primary error sources affecting the accuracy of determining the functional group locations in β-cyclodextrin were analyzed. The relative error of the measured amounts of nitrates in the cyclodextrin glucopyranose ring 2- and 3-positions was 10%; in the 6-position, 20%.

A complex analysis of the crumbed rubber produced by the explosive circulation method has been performed by the methods of AFM, X-ray diffraction, gas chromatography, mass spectrometry, and gel-permeation chromatography (GPC). The results of the small- and wide-angle X-ray diffraction study have revealed an amorphous structure of the samples without supramolecular ordering at a distance scale of ~1–40 nm. Globular formations of a size of 5–20 nm on the crumb surface combined into clusters of various shapes and sizes in the range 100–1000 nm have been found by means of the AFM method. Individual nanoglobules and small and large clusters of these nanoglobules appeared to be randomly covering the surface of the examined samples. It has been established that the nanoglobules partially consist of saturated and unsaturated hydrocarbons of low-molecular weight, which belonging to classes of linear, cyclic, and aromatic compounds. Most of the nanoglobules are represented by oligomeric products having 3–5 units, as well as compounds of higher molecular weight. All of the above compounds provide better adhesion of the regenerate to different matrices than that produced by other methods. The composition of the nanoscaled globules includes secondary products of reactions of low-molecular hydrocarbons formed from rubber tires at their explosive circulation grinding.

Few-layer graphene structures synthesized by the plasma electrochemical method are used as modifiers of epoxy binders. It is shown that the obtained structures have the maximum positive effect on the strength characteristics of a cured epoxy–amine composition at a concentration of 0.2 wt %.

Influence of small additives of fullerene, graphene oxide, and their combinations in the ratio of 85:15 on the structure and mechanical properties of cross-linked polyurethanes under static and dynamic loads has been investigated. Nanocomposite structures have been studied by X-ray diffraction analysis and scanning electron microscopy. It is shown that the presence of carbon nanoparticles in the composite reduces its strength under both static and shock-wave loads. The synergistic effect of the mixture of carbon nanoparticles manifests itself as an increase in the elastic modulus by a factor of 1.25 in comparison with the initial polymer.

An IR spectroscopy-based method was devised for estimating the degree of substitution of hydroxyl groups with nitrate groups into the positions 2, 3 and 6 of the glucopyranose ring individually in cyclodextrin partial nitrates. Gauge dependencies as well as the values of molar extinction coefficient were obtained for groups in each position. Primary sources of errors affecting the accuracy of determining the localization of functional groups in β-cyclodextrin were analyzed. Relative error of the evaluation of the number of nitrate groups in positions 2 and 3 of cyclodextrin glucopyranose ring is 10 % and 20 % for position 6.