Highly efficient synthesis of benzopyranopyridines via ZrP2O7 nanoparticles catalyzed multicomponent reactions of salicylaldehydes with malononitrile and thiols

ZrP₂O₇ nanoparticles as an efficient catalyst have been used for the preparation of benzopyrano[2,3-b]pyridines from the four-component condensation reaction of salicylalde-hydes, thiols, and 2 equiv. of malononitrile under reflux conditions in ethanol in excellent yields and short reaction times.     

Optimization of Ozonation Process for a Composting Leachate-Contaminated Soils Treatment Using Response Surface Method

The ozonation process has become one of the most favorable processes among soil remediation technologies nowadays. Ozone, which has an oxidation potential of 2.07 V and acts as a powerful oxidizer, is capable of degrading organic pollutants of soil in a short period of time without producing any toxic residuals. In this study the capability of ozone, as an ex-situ method of soil treatment, in remediating the leachate-contaminated soil has been investigated. To maximize the removal efficiency of organic content of soil, design of experiments using the response surface method (RSM) and central composite design (CCD) have been employed. To select the range of effective parameters several experiments were performed at laboratory scale. Results showed a range of effective parameters on the ozonation process, including pH, humidity, and initial soil pollution. Present research shows that acid-washed ozone greatly enhanced the removal efficiency. According to the developed model, the maximum removal efficiency using acid-washed ozone was obtained by setting the parameters as pH = 10.8, humidity of 5% and initial organic content of soil to be 7720 mg/kg. Confirmation experiments showed that RSM could be effectively utilized for the optimization of the ozonation process. Analysis of variance also showed that pH was the most significant factor affecting removal efficiency.     

Synthesis and thermal stability of polystyrene and poly(vinyl chloride) coated with polythiophene and modified with Fe2O3 nanoparticles

In this study, polystyrene and poly(vinyl chloride) particles were coated successfully with polythiophene in aqueous media. These nanocomposites were prepared in situ by polymerization of thiophene in the presence of FeCl₃ as an oxidant and poly(vinyl pyrrolidone) as a surfactant. The effect of Fe₂O₃ nanoparticles on the characteristics of products such as thermal stability and morphology was investigated. The chemical structure, morphology, and thermal stability of these core‐shell nanocomposites were studied by Fourier‐transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, and thermogravimetric analysis. Thermal stability of the nanocomposites was compared and indicated that the thermal stability of polythiophene/polystyrene was better than the polythiophene/poly(vinyl chloride) nanocomposite. Also, the presence of Fe₂O₃ nanoparticles can drastically increase the thermal stability of polythiophene nanocomposites. J. VINYL ADDIT. TECHNOL. 20:212–217, 2014. © 2014 Society of Plastics Engineers     

Synthesis of biocompatible and degradable microspheres based on 2‐hydroxyethyl methacrylate via microfluidic method

Monodisperse poly(2‐hydroxyethyl methacrylate), p‐HEMA, microspheres in size ranging from 16 to 340 (μm) were synthesized by in situ emulsion photopolymerization of HEMA monomer with polyethylene glycol diacrylate (p‐EGDA) by means of a three‐dimensional microfluidic flow‐focusing device. An aqueous solution of HEMA, p‐EGDA as chain extender and UV‐photoinitiator serving as dispersed phase formed microdroplets in a continuous oil phase mainly consisting of n‐heptane. A downward coaxial orifices design in the device led to confinement of the reaction admixtures thread to central axis of the microchannels. This design strategy could solve the wetting problem of dispersed phase with the microchannels leading to a successful production of monodisperse microspheres with size variation of less than 4%. The effects of concentration of p‐EGDA, surfactant, and flow rate ratios on microsphere size were examined. It was observed that increasing the concentration of p‐EGDA slightly increases the size whereas increasing the flow rate ratios of continuous to dispersed phase effectively decreases the size of microspheres. The rapid continuous synthesis of p‐HEMA based microspheres via the microfluidic route with reliable control over size, size distribution, and composition opens new doors for mass production of biocompatible and degradable polymeric microspheres for enormous biotechnological applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40925.     

Kinetic study of styrene atom transfer radical polymerization from hydroxyl groups of graphene nanoplatelets: Heterogeneities in chains and graft densities

Confinement effect of graphene nanoplatelets on the kinetics of styrene atom transfer radical polymerization was studied by a “grafting from” reaction. Graphene oxide was modified by different amounts of (3‐aminopropyl) triethoxysilane and then alpha‐bromoisobutyryl bromide from the hydroxyl groups. Polymerization of styrene in the presence of modified graphene and free initiator, ethyl alpha‐bromoisobutyrate, was accomplished at 110°C. Then, effect of various graft densities and different graphene loadings on the heterogeneous graft and free polystyrene chains characteristics and also kinetics of polymerization was studied by gas and gel permeation chromatographies. Efficiency of grafting reactions along with the graft contents was studied by X‐ray photoelectron spectroscopy, elemental analysis, and thermogravimetric analysis. Confinement effects of graphene on the relaxation behavior of polystyrene chains and also morphology of the graphenes were studied by differential scanning calorimetry and transmission electron microscopy, respectively. POLYM. ENG. SCI., 55:1720–1732, 2015. © 2014 Society of Plastics Engineers     

Evolution of vinyl chloride conversion below critical micelle concentration: A response surface analysis

Utilizing response surface methodology, the conversion of vinyl chloride monomer (VCM) was monitored when the polymerization temperature, the type of surfactant, and the weight ratio of water‐to‐monomer (W/M) were taken as the emulsion polymerization variables. Because the homogeneous nucleation was found to be the dominant mechanism in VCM emulsion polymerization, irrespective of the surfactant concentration, the whole experiments have been carried out below critical micelle concentration of the used surfactants. Among all the studied variables, the polymerization temperature appeared as the most effective parameter; moreover, its interactive effect with W/M caused different trends in the alteration of final conversion being observed. Also, depending on the reaction temperature, the VCM conversion would be affected by the type of the surfactant used. Contrarily, simultaneous change in the type of surfactant and W/M revealed an insignificant effect on the evolution of VCM conversion. The optimization of final conversion of VCM was also accessible through contour plots of response surface methodology. It is worth noting that, taking a conventional approach into consideration, the alteration of VCM conversion seemed to be a monotonic function of temperature. J. VINYL ADDIT. TECHNOL., 21:157–165, 2015. © 2014 Society of Plastics Engineers     

Supertough (Polyamide 6)/(acrylonitrile butadiene rubber) nano alloy through in situ polymerization of caprolactam in the presence of acrylonitrile butadiene rubber nanophase

In this work, polymerization of caprolactam (CL) was carried out in the presence of acrylonitrile butadiene rubber (NBR) during the reactive melt‐mixing process. During shear mixing, NBR particles swelled and dissolved in the molten CL, which led to separation and distribution of rubber particles to nanoscale in the dissolution stage. Then, in an internal mixer, supertough Polyamide 6 was prepared via melt polymerization of CL/NBR mixture, sodium caprolactam as a catalyst, and hexamethylene diisocyanate as an activator. The effects of various concentrations of catalyst and activator on the initiation time of the reaction were determined. Physical and mechanical properties of different formulations prepared via reactive melt blending were determined by tensile and impact measurements, differential scanning calorimetry, Fourier‐transform infrared spectroscopy, X‐ray scattering techniques, transmission electron microscopy, and dynamic mechanical thermal analysis. Experimental results showed that a recipe with 3% nitrile rubber in a CL/NBR mixture enhances the physical and mechanical properties the best, compared with other formulations. This condition led to the formation of NBR nanospheres during melt polymerization of Polyamide 6 as well. J. VINYL ADDIT. TECHNOL., 21:116–121, 2015. © 2014 Society of Plastics Engineers     

Investigation of Magnesium Incorporation within Gelatin/Calcium Phosphate Nanocomposite Scaffold for Bone Tissue Engineering

In this study, diffusional method was used to prepare a calcium phosphate/gelatin nanocomposite as a scaffold for bone tissue repair. Incorporation of magnesium (Mg) into mineral phase of the scaffold was also investigated. Addition of Mg ions to the synthesis process caused formation of magnesium phosphate (MgP) and hydroxyapatite (HAp). However, analyses data for the sample lacking Mg showed that the mineral formed within GEL had a low crystalline nature, consisting of HAp and octacalcium phosphate (OCP). With addition of Mg within the structure of precipitated minerals, morphology of minerals was dramatically changed toward being irregular and less ordered.     

Effect of different modified nanoclays on the kinetics of preparation and properties of polymer-based nanocomposites

Polymer-clay nanocomposites have been prepared by free radical and RAFT polymerizations. To investigate the effects of nanoclay content and its modification system on the kinetics of polymerization, two different commercial grades of clay including Na-MMT and Cloisite 30B have been used and a method has been developed for further modification of Na-MMT with two commercial modifiers containing either a long organic chain or a vinyl group. Also, kinetics of free radical and RAFT polymerizations of both styrene and methyl methacrylate in the presence of these nanoclays was studied. Morphology of the nanocomposites has been studied by XRD and the results have been assessed with TEM observations. Exfoliated structure was obtained for the nanocomposites with 1?wt.% of vinyl-containing clays. Thermogravimetric behavior of the nanocomposites has been studied by TGA. Incorporation of clays has resulted in an evident increase in thermal stability of both polymers.