Four photoacid generators such as triphenylsulfonium triflate and nonaflate, 4-tert-butylphenyl(diphenyl)sulfonium nonaflate and tris(4-tert-butylphenyl)sulfonium nonaflate were synthesized, and their spectral characteristics were investigated in the polymer matrix. The dependence of the photosensitivity of resist films on the efficiency of absorption of actinic radiation and the quantum yields of acid generation was found. Triphenylsulfonium triflate salt and tris(4-tert-butylphenyl)sulfonium nonaflate were shown to be promising photoacid generators with a resist sensitive to irradiation by ArF and KrF excimer lasers, respectively.

The addition of materials such as polysulfone as a modifier to epoxy binders has the potential to significantly improve the crack resistance of the material. In this work, the effect of the polyphenylene sulfone additive on the epoxy resin strength has been studied experimentally. Epoxy samples were cured at 160 and 200 ^∘C temperature. Under static conditions, the addition of 5 200 ^∘C leads to strength increase. Under dynamic loading, the spall strength decreased with increased polyphenylene sulfone addition in all epoxy resin samples. When the incoming pulse pressure is low, the spall strength of the samples cured at both temperatures is similar. The curing temperature effect begins to manifest itself at higher incoming pulse pressures in samples with 3–5

Hyperbranched polymers (HBPs) are widely applied nowadays as functional materials for biomedicine needs, nonlinear optics, organic semiconductors, etc. One of the effective and promising ways to synthesize HBPs is a polyaddition of AB2+A2+B4 monomers that is generated in the A2+CB2, AA′+B3, A2+B′B2, and A2+C2+B3 systems or using other approaches. It is clear that all the foundational features of HBPs that are manufactured by a polyaddition reaction are defined by the component composition of the monomer mixture. For this reason, we have designed a structural kinetic model of AB2+A2+B4 monomer mixture polyaddition which makes it possible to predict the impact of the monomer mixture’s composition on the molecular weight characteristics of hyperbranched polymers (number average (DPn) and weight average (DPw) degree of polymerization), as well as the degree of branching (DB) and gel point (pg). The suggested model also considers the possibility of a positive or negative substitution effect during polyaddition. The change in the macromolecule parameters of HBPs formed by polyaddition of AB2+A2+B4 monomers is described as an infinite system of kinetic equations. The solution for the equation system was found using the method of generating functions. The impact of both the component’s composition and the substitution effect during the polyaddition of AB2+A2+B4 monomers on structural and molecular weight HBP characteristics was investigated. The suggested model is fairly versatile; it makes it possible to describe every possible case of polyaddition with various monomer combinations, such as A2+AB2, AB2+B4, AB2, or A2+B4. The influence of each monomer type on the main characteristics of hyperbranched polymers that are obtained by the polyaddition of AB2+A2+B4 monomers has been investigated. Based on the results obtained, an empirical formula was proposed to estimate the pg = pA during the polyaddition of an AB2+A2+B4 monomer mixture: pg = pA = (−0.53([B]0/[A]0)1/2 + 0.78)υAB2 + (1/3)1/2([B]0/[A]0)1/2, where (1/3)1/2([B]0/[A]0)1/2 is the Flory equation for the A2+B4 polyaddition, [A]0 and [B]0 are the A and B group concentration from A2 and B4, respectively, and υAB2 is the mole fraction of the AB2 monomer in the mixture. The equation obtained allows us to accurately predict the pg value, with an AB2 monomer content of up to 80%.

In this work, sodium tetrahydroxoborate (NaB(OH)4) that is the main product of the hydrolysis reaction of NaBH4 with a relatively small excess of water is studied in the reaction with sodium borohydride in the presence of a catalyst and without it. It was found, that mixtures consisting of NaB(OH)4 and NaBH4 begin to melt at 70 degrees C with the formation of a liquid phase without destroying the close coordination environment for both types of boron atoms. When a cobalt -based catalyst is added to mixtures, significant hydrogen evolution is observed. The resulting products are hydrogen and amorphous borates with a gross composition close to [NaBO2 & sdot;0.75H2O]. Carrying out the catalytic hydrolysis of borohydride in the system of initial composition H2O:NaBH4:catalyst under the conditions same to that the catalytic reaction of NaBH4 and NaB(OH)4 was observed is a promising way to produce H2 since it provides a high yield of hydrogen at small amounts of catalyst and atmospheric pressure. Catalytic hydrolysis carried out in the temperature range 80-120 degrees C with initial molar ratios H2O:NaBH4 = 3 and 2.7, and atmospheric pressure demonstrates a hydrogen yield of 8.3 wt% and NaBH4 conversion of 96 % at only 2.3 wt% of CoCl2 as catalyst. Since the resulting final composition of borates is close to [NaBO2 & sdot;0.66H2O], the potential mass yield of hydrogen in this process can reach 9.3 wt%.

The effect of input doses of 60Co gamma-radiation from 80 to 12,000 kGy on the thermophysical properties and thermal stability of samples of polypropylene granules and powder obtained by high temperature shear grinding of irradiated granules, as well as on the tensile strength properties of a plate made from irradiated granules and their corresponding powders, was studied. The thermophysical properties of the powder are determined by the changes introduced by radiation into the initial polymer granules. The effects of radiation in air (environments with oxygen) were studied. Grinding redistributes oxygen-containing functional groups from the surface layer of irradiated granules throughout the entire volume of the obtained powder leading to the destruction of polymer chains as there is a component due to thermal destruction of radiolyzed polymer chains. High-temperature shear grinding of irradiated granules has a significant effect on the product powder, reducing its thermal stability but increasing the tensile strength of plates pressed from it at low absorbed doses. The current work shows that radiation treatment coupled with high temperature shear grinding could be a method for modifying the properties of polymers so that polypropylene waste can be processed for other applications.

The study is about the thermal behavior of 6 s-triazine derivatives containing azide, propynyloxy, and propynylamino functional groups in the structure are analyzed, and a mechanism of thermal processes was proposed. The thermal decomposition of compounds was studied in the temperature range of 30 – 600 oC in a flow of helium by non-isothermal TGA and DSC methods, and high-temperature transformations were studied at elevated pressures in a nitrogen atmosphere in the Crawford bomb. For all compounds, the process of thermal decomposition occurs at several stages, including the formation of high-molecular compounds, thermal destruction of functional groups, and s-triazine framework. All compounds support the high-temperature transformation in an oxygen-free environment with adiabatic temperature in the range of 718 – 953 K. The behavior of both thermal processes depends on the number of azide groups in the molecule structure and their enthalpy of formation. With an increase in their number in the structure of the compound, the process of azido-acetylenic compounds of s-triazine becomes closer to explosive. The reduced products of the high-temperature transformation are analyzed.

The properties of azido-acetylenic derivatives of s -triazine containing various combinations of propynyloxy, propynylamino, N-methyl-propynylamino, and azido groups have been studied, and their enthalpy of formation in the condensed phase, density, and impact and friction sensitivities have been determined. Based on these data, the energy parameters of detonation, combustion, and adiabatic transformation for individual compounds and their compositions with the binder SKI-3 isoprene rubber have been calculated. The results of the integrated experimental and theoretical studies suggest a high heat of combustion of the investigated individual compounds and compositions based on them.

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.

The work addresses complex thermal behavior of two triazine-based azide-alkyne monomers: 2-azido-4,6-bis (prop-2-yn-1-yloxy)-1,3,5-triazine (ABPOT) and 2,4-diazido-6-(prop-2-yn-1-yloxy)-1,3,5-triazine (DAPOT). Despite the similarity of the two AB2-type structures, the isothermal aging kinetics of DAPOT occurs significantly faster than that of ABPOT. During storage at room temperature, the chemical transformation starts in the crystalline state via topochemical reactions. Calorimetry, along with X-ray diffraction, makes it possible to probe transformations in isolated microcrystals including melting, oligomerization, polymerization and decomposition. The thermal behavior of microparticles can strongly differ from that of the same material in bulk due to enhanced contribution of the monomer evaporation at the particle surface at extremely high heating rates. The isothermal melting caused by the topochemical reaction and subsequent polymerization during long-term storage can be modeled using the correlated two-stage Avrami equation. The Avrami parameter corresponding to the amorphization process is close to unity while that of the polymerization is approximately 0.5. Consequently, both processes can likely be viewed as one-dimensional, with diffusion control dominating the polymerization process. The observed impact of long-term storage on the polymerization capability of the monomers may prove beneficial in synthesizing hyperbranched polymers through "green" topochemical methods.

We report a simple and convenient approach to the one-pot synthesis of hyperbranched polyurethane-triazoles with desirable properties. This method is based on in situ generation of an AB2 + A2 + B4 azide-acetylene monomer mixture of known composition, due to quantitative reactions of urethane formation between isophorone diisocyanate (IPDI), 1,3-diazidopropanol-2 (DAPOL) (in the first stage) and propargyl alcohol (in the second stage). The obtained monomer mixture can be involved in step-growth polymerization by azide-alkyne cycloaddition without additional purification (in the third stage). The properties of the resulting polymers should depend on the composition of the monomer mixture. Therefore, first the model revealing the correlation between the monomer composition and the ratio and reactivity of the IPDI and DAPOL active groups is developed and proven. In addition, the newly developed structural kinetic model considering the substitution effect at polyaddition of the complex mixture of monomers allows the prediction of the degree of branching of the target polymer. Based on our calculations, the hyperbranched polyurethane-triazoles were synthesized under found conditions. All products were characterized by 1H NMR, FTIR, SEC, DLS, DSC, TGA and viscometry methods. It was shown that the degree of branching, molecular weight, intrinsic viscosity, and hydrodynamic radius of the final hyperbranched polymers can be specified at the first stage of one-pot synthesis. The obtained hyperbranched polyurethane-triazoles showed a degree of branching from 0.21 to 0.44 (calculated DB-0.25 and 0.45, respectively).

In this work sodium tetrahydroxoborate (NaB(OH)4) that is the main product of NaBH4 hydrolysis reaction if water excess is relatively small has been examined in reaction with sodium borohydride with and without a catalyst. It was found that mixtures consist of NaB(OH)4 and NaBH4 start to melt at 70°C producing liquid phase with no destruction of close coordination environment for both types of boron atoms. But if Co-based catalyst is added to the mixtures the significant hydrogen evolution is observed. Obtained products are hydrogen and amorphous borates with gross-composition close to [NaBO2×0.75H2O].Carrying out catalytic hydrolysis with molar ratios 3≥H2O:NaBH4≥2 during which liquid water is used instead of the tetrahydroxoborate is a promising way for H2 production with high mass yield at mild temperature, small quantities of a catalyst, and atmospheric pressure. The catalytic hydrolysis caring out at the temperature range 80-120ºC, initial molar ratios H2O:NaBH4=3 and 2.7 and atmospheric pressure demonstrates hydrogen yield 8.2Wt% and 97% of NaBH4 conversion at only 2.3Wt% of a Co-based catalyst. Taking into account that the obtained final borate gross composition is close to [NaBO2×0.66H2O], the potential mass yield of hydrogen in this process could reach 9.3Wt% for all the reactants including the catalyst.

The kinetics of photodissociation of ferrocene in bisphenol A dicyanate oligomer is studied using photospectroscopy. Thermograms of bisphenol A dicyanate oligomer polymerization in the presence of photodissociated ferrocene are obtained. Kinetic calculations and analysis of the thermograms lead to the conclusion that systems based on bisphenol A dicyanate oligomer and ferrocene may find application in 3D printing.

Enthalpies of formation in gas phase of three series of energetic derivatives of triazido-s-triazine containing propynyloxy, propynylamine and methylpropynylamine groups were calculated using G4 method. Contributions of each group to the enthalpy of formation of the discussed compounds were estimated in order to apply the increment method for quick estimation of this thermodynamic parameter for substituted s-triazines.

An original synthesis of a new non-symmetric energetic ABB' type monomer, 2-azido-4-propargylamino-6- propargyloxy-s-triazine, with a total yield of 40% involves the sequential introduction of propargylamino, propargyloxy and azido groups into s-triazine. DFT investigation of azide- Cl alkyne cycloaddition mechanism at M06-2X/6-311++G(d,p) level of theory for this monomer predicts that the regioselectivity of polycycloaddition reaction should increase with the number of propargylamino groups in the monomer structure due to the stabilization of the transition state, leading to 1,5-triazole regioisomer.

Core/shell pigments allow for the combination of the active anti-corrosion effect of the shell and the barrier effect of the core. This makes it possible to obtain anti-corrosion pigments, with a high-protective effect and low toxicity. Thus, the need for a comprehensive study of the properties of these pigments grows more urgent, before their application to paints and varnishes. The hiding power of core/shell pigments comes close to the one of pure polyaniline (PANi), when the PANi content in the pigment reaches 50 wt.%, with sulfuric and phosphoric acids used as dopants. This paper, also, shows that the blackness value of core/shell pigments with 10 wt.% PANi is around 35 and constant; for pure PANi, their blackness value is 40. When PANi content is 5 wt.%, kaolin-based pigment shows the lowest blackness, which happens due to a generally higher whiteness of kaolin. However, when the PANi content surpasses 10 wt.%, there seems to be no influence on the blackness of the core/shell pigments. The core/shell pigment with a 20 wt.% PANi is, optically, identical to a black-iron-oxide pigment. An increase in the PANi content of the core/shell pigment leads to an increase in the oil absorption of the samples. It was found that the dispersion process would be the most energy efficient for core/shell pigments, containing kaolin and talc as a core.

The kinetic studies of photodissociation of ferrocene in the oligomer of bisphenol A dicyanate were done using photospectroscopy. Thermograms of polymerization of the bisphenol A dicyanate oligomer in the presence of photodissociated ferrocene were also obtained. Based on kinetic calculations and analysis of thermograms, conclusion has been made regarding the possibility and promising use of a system based on the oligomer bisphenol A dicyanate and ferrocene for 3D printing.

Thermal transformations of 2,4,6-tris(2,2,2-trinitroethylnitramino)-1,3,5-triazine ( I ) are studied in the temperature range 22–300°C with the use of methods of differential thermal analysis, powder X-ray diffractometry, and IR spectroscopy. At 120°C, the polymorphic transformation α- I → β- I , which is preceded by a sharp increase in the volume of the unit cell and amorphization of I , is recorded. The polymorphic transformation is accompanied by a significant increase in the rate of thermal decomposition of the compound I . Under normal conditions, the phase β- I is stable, but a reverse polymorphic transformation with the formation of a defect phase α- I can be realized at a pressure of 5 kbar.

Efficient methods for the synthesis of novel azidopropargylamino-substituted 1,3,5-triazines were developed. 4,6-Diazido-N-(prop-2-yn-1-yl)-1,3,5-triazin-2-amine was obtained by the method of sequential nucleophilic substitution of chlorine atoms in cyanuric chloride by amino and azido groups or by the method of selective substitution of the azido group in triazidotriazine with propargylamine. 6-Azido-N-2,N-4-dimethyl-N-2,N-4-di(prop-2-yn-1-yl)-1,3,5-triazine-2,4-diamine was obtained by nitrosation of the corresponding 6-hydrazinyl-N-2,N-4-dimethyl-N-2,N-4-di(prop-2-yn-1-yl)-1,3,5-triazine-2,4-diamine. Monomers with a lower melting point were obtained by N-methylation of azidopropargylamino-substituted 1,3,5-triazines.