Transformation of Specific Dispersion Interactions between Cellulose and Polyacrylonitrile in Solutions into Covalent Interactions in Fibers.

Morphological transformations in emulsions of cellulose and polyacrylonitrile (PAN) ternary copolymers containing acrylonitrile, methyl acrylate, and methylsulfonate comonomers in N-methylmorpholine-N-oxide were studied over the entire range of concentrations depending on temperature and intensity of the deformation action. Based on the morphological and rheological features of the system, the temperature-concentration range of spinnability of mixed solutions was determined, and composite fibers were spun. The fibers are characterized by a heterogeneous fibrillar texture. Studies of the structure of the fibers, carried out using X-ray diffraction analysis, revealed a decrease in cellulose crystallinity with an increase in the content of PAN. The study of the thermal properties of the obtained fibers, carried out using DSC, and chemical transformations in them in a wide temperature range by high-temperature diffuse reflection IR spectroscopy made it possible to reveal a new intense exothermic peak on the thermograms at 360 °C, which according to the IR spectra corresponds to the transformation of intermacromolecular physical interactions of the PAN and cellulose into covalent bonds between polymers. In addition, the ester groups found during the thermal treatment of the PAN part of the composite fibers in the pyrolysis zone can have a key effect on the process of their further carbonization.

Membranes Based on Cellulose and Copolymers of Acrylonitrile Prepared from Joint Solutions.

Cellulose and copolymers of acrylonitrile (PAN) are characterized by their chemical resistance to several conventional solvents. Therefore, these polymers are often used to obtain membranes for the recovery of such solvents. In this work, for the first time, composite membranes formed from highly concentrated mixed solutions based on cellulose and PAN are considered (the total content of polymers is 18 wt.%). For mixed solutions, the morphology and rheological behavior were evaluated. It is shown that the resulting solutions are two-phase, and their morphology depends on the components' ratio and the system's history. The non-monotonous change in the viscosity with the PAN content indicates a specific interaction of cellulose and PAN in N-methylmorpholine-N-oxide solutions. The rheological behavior of mixed solutions allows for their processing in conditions identical to those of cellulose solutions. The introduction of PAN into the cellulose matrix promotes a decrease in the structural order in the system, affecting the membranes' transport properties. For composite membranes, it was found that with an increase in the content of the PAN phase, the retention of Remazol and Orange decreases, while the observed values are several times higher than those for cellulose membranes. The permeability of ethanol increases with increasing terpolymer content.

Polyacrylonitrile Fibers with a Gradient Silica Distribution as Precursors of Carbon-Silicon-Carbide Fibers.

This study presents preparing and characterization of polyacrylonitrile (PAN) fibers containing various content of tetraethoxysilane (TEOS) incorporated via mutual spinning solution or emulsion using wet and mechanotropic spinning methods. It was shown that the presence of TEOS in dopes does not affect their rheological properties. The coagulation kinetics of complex PAN solution was investigated by optical methods on the solution drop. It was shown that during the interdiffusion process phase separation occurs and TEOS droplets form and move in the middle of the dope's drop. Mechanotropic spinning induces the TEOS droplets to move to the fiber periphery. The morphology and structure of the fibers obtained were investigated by scanning and transmission electron microscopy, as well as X-ray diffraction methods. It was shown that during fiber spinning stages the transformation of the TEOS drops into solid silica particles takes place as a result of hydrolytic polycondensation. This process can be characterized as the sol-gel synthesis. The formation of nano-sized (3-30 nm) silica particles proceeds without particles aggregation, but in a mode of the distribution gradient along the fiber cross-section leading to the accumulation of the silica particles either in the fiber center (wet spinning) or in the fiber periphery (mechanotropic spinning). The prepared composite fibers were carbonized and according to XRD analysis of carbon fibers, the clear peaks corresponding to SiC were observed. These findings indicate the useful role of TEOS as a precursor agent for both, silica in PAN fibers and silicon carbide in carbon fibers that has potential applications in some advanced materials with high thermal properties.

New Type of Catalyst for Efficient Aerobic Oxidative Desulfurization Based On Tungsten Carbide Synthesized by the Microwave Method.

Herein, we present a new type of high-performance catalyst for aerobic oxidation of organosulfur compounds based on tungsten carbide. The synthesis of tungsten carbide was performed via microwave irradiation of the precursors, which makes it possible to obtain a catalyst in just 15 min. The synthesized catalyst was investigated by a variety of physicochemical methods: X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, electron microscopy, and N2 adsorption/desorption. It was shown that active centers containing tungsten in the transition oxidation state (+4) play a key role in the activation of oxygen. The main factors influencing the conversion of dibenzothiophene (DBT) were investigated. It should be noted that 100% conversion of DBT can be achieved under relatively mild conditions: 120 °C, 3 h, 6 bar, and 0.5% wt catalyst. The catalyst retained its activity for at least six oxidation/regeneration cycles. The simplicity and speed of synthesis of the proposed catalyst in combination with its high activity and stability open broad prospects for its further use both for oxidative desulfurization and for other reactions of aerobic oxidation of organic substrates.

Structure, Morphology, and Permeability of Cellulose Films.

The work is focused on the study of the influence of the cellulose type and processing parameters on the structure, morphology, and permeability of cellulose films. The free volume of the cellulose films was evaluated by the sorption of n-decane, which is a non-solvent for cellulose. The structural features of the membranes and their morphology were studied using X-ray diffraction, IR spectroscopy, SEM, and AFM methods. The characteristic features of the porous structure and properties of cellulose films regenerated from cellulose solutions in the N-methylmorpholine-N-oxide (NMMO) and cellophane films were compared. Generally, cellulose films obtained from solutions in NMMO have a higher permeability and a lower rejection (as measured using Orange II dye) as compared to cellophane films. It was also found that the cellulose films have a higher ultimate strength and modulus, whereas the cellophane films are characterized by higher elongation at break.

Multiblock Copolymers of Norbornene and Cyclododecene: Chain Structure and Properties.

We investigate the structure-property relations of the multiblock copolymers of norbornene with cyclododecene synthesized via the macromolecular cross-metathesis reaction between amorphous polynorbornene and semicrystalline polydodecenamer in the presence of the first-generation Grubbs catalyst. By adjusting the reaction time, catalyst amount, and composition of the initial system, we obtain a set of statistical multiblock copolymers that differ in the composition and average length of norbornene and dodecenylene unit sequences. Structural, thermal, and mechanical characterization of the copolymers with NMR, XRD, DSC (including thermal fractionation by successive self-nucleation and annealing), and rotational rheology allows us to relate the reaction conditions to the average length of crystallizable unit sequences, thicknesses of corresponding lamellas, and temperatures of their melting. We demonstrate that isolated dodecenylene units can be incorporated into crystalline lamellas so that even nearly random copolymers should retain crystallinity. Weak high-temperature endotherms observed in the multiblock copolymers of norbornene with cyclododecene and other cycloolefins could indicate that the corresponding systems are microphase-separated in the melt state.

Features of the Gas-Permeable Crystalline Phase of Poly-2,6-dimethylphenylene Oxide.

Poly-2,6-dimethylphenylene oxide (PPO) film samples with varying degrees of crystallinity (from 0 to 69%) were obtained by means of different techniques. The films were studied by various physicochemical methods (Fourier-transform infrared spectroscopy, positron annihilation lifetime spectroscopy, X-ray diffraction, and 1H nuclear magnetic resonance relaxation). Solubility coefficients of gases in the PPO samples were measured via sorption isotherms of gases by volumetric technique with chromatographic detection. The apparent activation energy of permeation and the activation energy of diffusion of all gases were estimated based on temperature dependences of gas permeability and diffusivity for amorphous and semi-crystalline PPO in the range of 20-50 °C. The peculiarities of free volume, density, and thermal properties of gas transport confirm the nanoporosity of the gas-permeable crystalline phase of PPO. So, the PPO can be included in the group of organic molecular sieves.