KF/Al2O3 as an Efficient,Green, and Reusable Catalytic System for the Solvent-Free Synthesis of N-Alkyl Derivatives of Sulfonamides via Michael Reactions

KF/Al ₂ O ₃ efficiently catalyzes the microwave-assisted Michael addition of sulfonamides to α,β-unsaturated esters under solvent-free conditions to afford N-alkyl derivatives of sulfonamides as biologically interesting compounds in high yields and in short reaction times. In this reaction, N,N-dialkylsulfonamides are also produced, but in very low yields.     

SYNTHESIS AND CHARACTERIzATION OF TRIPHENYLANTIMONY (V) (O-ALKYL,O-CYCLOALKYL AND O-ARYLTRITHIOPHOSPHATES)

Triphenylantimony (V) (O-alkyl,O-cycloalkyl and O-aryltrithiophosphates) of the type Ph ₃ Sb[S ₂ (S)P(OR)] (R = Me, Et, Pr ⁿ , Pr ⁱ , Bu ⁿ , Bu ^s , Bu ⁱ , Am ⁱ , Ph and C.h. = cyclohexyl) have been synthesized for the first time by the reaction of triphenylantimony (V) dibromide with potassium trithiophosphates in 1:1 molar ratio in methanol. These new compounds have been characterized by elemental analysis, molecular weight determinations, and spectroscopic (IR,¹³C and ³¹P NMR) studies. On the basis of these data trigonal bipyramidal geometry has been proposed for these compounds.     

Preparation and characterization of conducting polyaniline layered magnetic nano composite polymer particles

Considering the application potentials of organic materials possessing both conducting and ferromagnetic functions in various electronic devices, an attempt was made to prepare conducting polyaniline (PANI) layered magnetic nano composite polymer particles. Two routes were used to modify magnetic Fe₃O₄ core particles. In one route, seeded emulsion polymerization of methyl methacrylate (MMA) was carried out in presence of nano‐sized Fe₃O₄ core particles. In another route, cross‐linker ethyleneglycol dimethacrylate (EGDM) was used in addition to MMA. The modified composite particles were named as Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM), respectively. Finally, seeded chemical oxidative polymerization of aniline was carried out in the presence of Fe₃O₄/PMMA and Fe₃O₄/P(MMA‐EGDM) composite seed particles to obtain Fe₃O₄/PMMA/PANI and Fe₃O₄/P(MMA‐EGDM)/PANI composite polymer particles. The modification of Fe₃O₄ core particles was confirmed by electron micrographs, FTIR, UV–visible spectra, X‐ray photoelectron spectra, X‐ray diffraction pattern and thermogravimetric analyses. A comparative study showed that crosslinking of intermediate shell improved the magnetic susceptibility and electrical conductivity of PANI layered magnetic nano composite particles. Copyright © 2013 John Wiley & Sons, Ltd.     

The Potential of O‐MMT as a Reinforcing Filler for Uncured and Dynamically Cured PVC/XNBR Composites

Organic montmorillonite modified with quaternary ammonium (O‐MMT) was compounded with uncured and dynamically cured poly(vinyl chloride)/carboxylated nitrile butadiene rubber (PVC/XNBR) composites, using a Brabender Plasticorder at 130°C and 50 rpm rotor speed. The reinforcing efficiency of the O‐MMT was investigated in the uncured PVC/XNBR composite and the dynamically cured PVC/XNBR counterpart. Mixing and dynamic curing of the composites were monitored by typical torque‐time curves derived from a Brabender internal mixer. The torque‐time curves revealed that the dynamic curing process was successful and the incorporation of O‐MMT has no adverse effect on the processibility of the composites. It has been found that the introduction of crosslinks within the rubbery phase in the presence of the O‐MMT has further improved the tensile properties. DMA studies revealed that dynamically cured composite with O‐MMT showed higher storage modulus than the composite without O‐MMT. Furthermore, a one‐step tensile modulus vs. temperature curve and a related one peak tensile loss modulus vs. temperature curve were obtained, consequently, both are characteristics of a miscible polymers system. Further evidence on the composite miscibility was purchased by thermal scans from DSC, which showed a single glass transition temperature of PVC/XNBR composites. This claim was further supported by ATR‐IR spectra which revealed that hydrogen bonding is extensively involved in PVC/XNBR composites. This evidence unveiled the exact nature of the specific interactions responsible for miscibility and hence, enhanced mechanical properties. Furthermore, we proved in our studies the reinforcing role played by layered clay due to better dispersion, as well as improved interactions.     

Studies on Melamine Modified Polyesteramide as Anticorrosive Coatings from Linseed Oil: A Sustainable Resource

Melamine modified polyester amide (MPEA) was synthesized by the reaction of linseed oil fatty amide. The resin was further cured at room temperature by polystyrene co‐maleic anhydride (SMA) in different phr (30–80) to obtain MPEA coatings. The probable structure of MPEA was confirmed by FT‐IR, ¹H‐NMR and ¹³C‐NMR spectroscopic techniques. The physico‐chemical characterization of these resins viz. iodine value, saponification value, refractive index, inherent viscosity were carried out by standard methods. MPEA (40 wt%) solution in ethylene glycol monomethyl ether (EGME) was applied on a mild steel strip of standard sizes to study their physico‐mechanical and chemical resistance properties. It was found that coatings of MPEA with 60 parts per hundred of the resin (phr) of SMA showed the best performance in physico‐mechanical and alkali resistance properties. Thermal stability and curing behavior were studied by Thermo Gravimetric Analyses (TGA) and Differential Scanning Calorimetry (DSC), respectively.     

Synthesis,Electrical Conductivity,Spectral and Thermal Stability Studies on Poly(aniline-co-o-nitroaniline)

o-Nitroaniline units were incorporated in the polyaniline backbone through copolymerization with aniline. The copolymers were synthesized for 1:3 and 1:1 molar ratios of aniline and o-nitroaniline in acidic medium using potassium persulphate as oxidant and their properties were compared with that of polyaniline. The polymers showed less electrical conductivity than polyaniline. Unlike polyaniline, the presence of nitro group caused higher frequency dependence of electrical conductivity. Electronic spectra showed a blue shift in both the band of the copolymers due to the decrease in the extent of conjugation leading to lower conductivity, which could also be explained in terms of a decrease of delocalization of electron as evinced from electron para magnetic resonance (EPR) data. Thermo gravimetric analysis (TGA) revealed that copolymer derived from 1:1 molar ratio showed comparable thermal stability with polyaniline and the one derived from 1:3 molar ratios is thermally less stable than polyaniline. Activation energies for thermal degradation were estimated using Broido equation. The temperature dependence of electrical conductivity suggested charge transport is mainly through variable range hopping.     

Viscometric Estimation of Unperturbed Chain Dimensions of Polymers

A new expression is proposed to determine the unperturbed dimensions of coil-like polymers viscometrically by use of the Flory and Kratky expression. The unperturbed dimensions so estimated are compared with the results obtained by using different expressions available in the literature. The results are comparable even for stiff chain polymers. The data obtained under theta conditions also fit this expression very well. The effect of molecular weight, its distribution, and that of the solvent has also been studied. It is concluded that the unperturbed dimensions are independent of molecular weight and solvent but depend on the heterogeneity of the system.     

Synthesis,Electrical, Electronic and Charge Transport Properties of Poly(aniline‐co‐p‐toluidine)

Copolymers of aniline with p‐toluidine were synthesized for different molar ratios of the respective monomers in acid medium. The electrical conductivity, charge transport and spectral characteristics upon incorporation of p‐toluidine units into the polyaniline backbone were investigated. The electrical conductivity of the copolymers showed frequency dependence which became more prominent with an increase in the number of p‐toluidine units in the polyaniline backbone. A direct relationship between the frequency dependence and electron localization was observed in the copolymers. Electronic spectra showed blue shifts in the π→π*and benzenoid→quinoid transitions revealing a decrease in the extent of conjugation in the copolymers. The protonated forms of the copolymers were soluble in DMSO giving polaron band around 400 nm. The decrease in electrical conductivity was attributed to the greater electron localizations as revealed from the broader ESR signals. Temperature dependence of electrical conductivity showed that charge transport was mainly through variable range hopping though a mixed conduction behavior was observed at higher temperature range.