Rhodium(I) complex catalyst immobilized on terpolymers of N‐vinylpyrrolidinone and 1‐vinylimidazole

The hydrosilylation of cyclohexanone and acetone with triethysilane and diphenysilane catalyzed by polymer‐supported Rh(I) complex has been investigated. Two terpolymers of styrene, divinylbenzene, and 1‐vinylimidazole (S/DVB/VI) or N‐vinylpyrrolidinone (S/DVB/NVP) were used as the catalysts supports. Physical characterization of these materials has involved the measurements of the structural parameters in the dry and swollen states by DSC, the nitrogen BET adsorption method and inverse steric exclusion chromatography ISEC. From these results it can be concluded that the original polymer structure has been changed during the complex attachment giving rise to materials of higher porosity. X‐ray photoelectron spectroscopy XPS, IR, and AAS spectroscopy were used to characterization of heterogeneous complexes before and after use. The effect of the morphology of the support on the catalytic properties of the polymer‐supported Rh(I) species was tested in the hydrosilylation of ketones and correlated with the reaction mechanism. It was demonstrated that the high selectivity of homogeneous rhodium complex toward the silyl ethers can be partially reversed to the dehydrogenative silylation products by a proper choice of polymer support with favorable microporous structure. Recycling tests demonstrated high stability of the supported catalysts during prolonged use. The constant selectivity of the supported catalysts demonstrated during recycling experiments showed that they could be useful for practical application. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Relation between microstructure and glass transition temperature of poly[(methyl methacrylate)‐co‐(ethyl acrylate)]

The glass transition temperature of a series of samples of the poly[(methyl methacrylate)‐co‐(ethyl acrylate)] copolymer, synthesized at low conversion, were calculated theoretically using the equations of Barton and Johnston. The values obtained are more precise when the probabilities of the compositional diads are derived from the ¹³C NMR data instead of the classical method utilizing reactivity ratios. This can be observed more clearly when the copolymer samples are synthesized at high conversion. Introduction of configuration (tacticity) at the diad level confirms the above observations and slightly improves the calculated values of T_g compared to the initial formulae which were only taking into account the compositional sequences of the copolymer. © 2001 Society of Chemical Industry     

Nafion‐115/aromatic poly(etherimide) with isopropylidene groups/imidazole membranes for polymer fuel cells

Proton exchange membrane fuel cells (PEMFCs) with Pt/C gas diffusion electrodes and graphite single‐serpentine monopolar plates were constructed based on an aromatic poly(etherimide) with isopropylidene groups (PI)/imidazole (Im) and a popular Nafion‐115 matrix. The electrochemical properties of PEMFCs were tested at 25 and 60°C. The maximum power density of 171 mW/cm² and the maximum current density of 484 mA/cm² were detected for Nafion‐115/PI membrane. For both constructed PEMFCs the efficiency at 0.6 V was found about 41%. Immersion of Nafion‐115 in PI or PI/Im increased the thermal stability and mechanical properties of membranes. Thermal, mechanical properties and morphology of membranes were characterized by TGA, and AFM techniques including force spectroscopy. Interactions between the components in composite membranes were established by FT‐IR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42436.     

Porosity effect on microstructure,mechanical, and fluid dynamic properties of Ti2AlC by direct foaming and gel‐casting

In this study, Ti₂AlC foams were fabricated by direct foaming and gel‐casting using agarose as gelling agent. Slurry viscosity, determined by the agarose content (at a fixed solids loading), as well as surfactant concentration and foaming time were the key parameters employed for controlling the foaming yield, and hence the foam porosity after sintering process. Fabricated foams having total porosity in the 62.5‐84.4 vol% range were systematically characterized to determine their pore size and morphology. The effect of the foam porosity on the room‐temperature compression strength and elastic modulus was also determined. Depending on the amount of porosity, the compression strength and Young's modulus were found to be in the range of 9‐91 MPa and 7‐52 GPa, respectively. Permeability to air flow at temperatures up to 700°C was investigated. Darcian (k₁) and non‐Darcian (k₂) permeability coefficients displayed values in the range 0.30‐93.44 × 10^?11 m² and 0.39‐345.54 × 10^?7 m, respectively. The amount of porosity is therefore a very useful microstructural parameter for tuning the mechanical and fluid dynamic properties of Ti₂AlC foams.     

Electrospun fibers of poly(l‐lactic acid) containing lovastatin with potential applications in drug delivery

Lovastatin (Merck's Mevacor) is a statin drug designed to lower cholesterol, and reduce the risk of heart attack and stroke. We use electrospinning to combine the biomedical properties of lovastatin with the advantages of electrospun fibers to prepare a composite biomaterial for lovastatin delivery. Poly(l ‐lactic acid) (PLLA), a biodegradable and biocompatible polymer, was co‐spun with lovastatin. Incorporation of lovastatin at 5 or 10 wt % improved fiber alignment and surface smoothness, and increased fiber diameter. Influence of lovastatin on the phase structure (crystal, mobile amorphous, and rigid amorphous fractions) was investigated using scanning calorimetry and synchrotron X‐ray scattering. Addition of lovastatin resulted in increased crystallinity and reduced mobile amorphous fraction. PLLA fibers were characterized in terms of their drug release kinetics in comparison to PLLA film. High drug entrapment efficiency (ranging from 72% to 82%) and appropriate release profiles were achieved. In vitro drug release studies demonstrated that release occurred in two stages: an initial rapid release over the first day and a slower second stage of release which approached a plateau after 7 days. PLLA fibers have a higher release rate than comparable film. Electrospun biomaterial fibers of PLLA provide a promising new release strategy for delivery of lovastatin. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45287.     

Melt fracture and rheology of linear low density polyethylene ‐ calcium carbonate composites

Rheological behavior and melt fracture of linear low‐density polyethylene (LLDPE) calcium carbonate (CaCO₃) composites were investigated. Two types of commercial inorganic fillers were used, unmodified and modified with stearic acid. Rheological capillary studies were conducted to assess the influence of inorganic filler incorporation as well as chemical treatment on the rheological properties and instability sequence of polyethylene‐based composites. Strong suppression of melt flow instabilities was observed for both types of composites. Mooney analysis was applied to examine the influence of mineral filler addition and stearic acid modification on the wall slip. Moreover, chemical treatment of calcium carbonate allows to obtain better dispersion of the inorganic filler in a polymeric matrix. POLYM. ENG. SCI., 57:998–1004, 2017. © 2016 Society of Plastics Engineers     

Antibacterial modification of nylon-6 nanofibers: structure,properties and antibacterial activity.

Antibacterial nylon 6 (PA6) nanofibers have been prepared in one-step procedure using Nanospider technology. Chlorhexidine (CHX), 1-dodecyltrimethylamonium bromide (DTAB) and benzyltrimethylamonium bromide (BTAB) have been used as antibacterial agents. Samples were characterized by a series of analytical and testing methods to investigate the surface chemistry, zeta potential, structure, morphology, phase composition, mechanical properties and antibacterial activity. Experimental characterization has been combined with molecular modeling to analyze the interaction of nanofibers with modifying molecules for better understanding the effect of nanofibers modification on their properties. Antibacterial modification of PA6 led to significant changes of zeta potential (from -31 mV for PA 6 up to -49 mV for PA6/BTAB), changes in phase composition (decrease of alpha phase content and increase of gamma phase content for PA6/BTAB and PA6/CHX) and to significant increase of fiber diameter for PA6/BTAB. Antibacterial modification resulted in the straightening of nanofibers and to higher permeability of nanofiber textile for all investigated samples. Tensile tests showed the the increase of Young modulus for all the investigated samples. All the modified samples: PA6/DTAB, PA6/BTAB and PA6/CHX exhibit good antibacterial activity.     

Decomposition of allantoin in the presence of Cu(II) ions resulting in the formation of a coordination polymer containing oxalate species

A novel Cu(II) coordination polymer, [Cu(ox)(DMSO)₂]_n (1) (ox-oxalate dianion, DMSO-dimethyl sulphoxide) has been prepared in the reaction of copper nitrate dihydrate and allantoin (5-ureidohydantoin) in DMSO/water solution. Compound (1) crystallizes in the monoclinic, space group P121/c1 with a = 5.1785(7), b = 13.6311(18), c = 8.5386(12) Å, β = 107.524(12)°, V = 574,76(14) Å³, Z = 4, D_cal = 1779 mg/m³, R₁ = 0.0449. The metal ion coordinates through four oxygen atoms belonging to two bidentate bridging oxalate ligands, and two oxygen atoms from two DMSO ligands forming an elongated octahedron. The crystal structure was confirmed by FT-IR and Uv–vis spectroscopic data.