Polyaniline‐supported acid catalyst: Esterification of cinnamic acid with alcohols

Polyaniline‐supported acid salts such as polyaniline‐hydrochloride, polyaniline‐sulfate, and polyaniline‐nitrate were prepared by oxidation of aniline using benzoyl peroxide and ammonium persulfate as oxidizing agents. Polyaniline salts were used as catalysts in the esterification of cinnamic acid with alcohols. Polyaniline‐sulfate salt was found to be the best catalyst for the esterification of cinnamic acid. The reusability, handling, and recovery of the catalyst were found to be good. The yield of the ester depended on the type of the polyaniline salt, amount of the catalyst, amount of alcohol, and both the time and the temperature of the reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1584–1590, 2005     

Melt rheology and morphology of PP/SEBS/PC ternary blend

Melt rheological properties of the ternary blend of isotactic polypropylene (PP), styreneethylene–butylene–styrene terpolymer (SEBS), and polycarbonate (PC), PP/SEBS/PC, are studied in a wide range of composition, such that PP is the matrix and SEBS and PC are the minor components, with the proportion of one varying from 0 to 30% at various fixed compositions of the other. The respective binary blends, PP/SEBS and PP/PC, studied as the reference systems for interpretation of results on the ternary blends yielded interesting new information about the morphology development and its correlation with melt rheological properties of these binary blends. The studies include the measurement of melt rheological properties on a capillary rheometer in the shear rate range 10¹–10⁴ s^?1 at a fixed temperature of 240°C. The data presented as conventional flow curves are analyzed for the effect of blend composition and shear rate on pseudoplasticity, melt viscosity, and melt elasticity, and role of each individual component is identified. Morphology of dispersed phases of these blends is studied through scanning electron microscopy of the cryogenically fractured and suitably etched surfaces. Variations of morphology with blend composition and shear rate showed interesting correlation with melt rheological properties, which are discussed in detail. An important finding of the morphological studies is that in the PP/SEBS/PC ternary blend the SEBS phase forms two types of morphologies depending on the blend composition and shear rate: (i) simple droplets and (ii) boundary layer at the surface of the PC droplets. © 1993 John Wiley & Sons, Inc.     

Explicit finite difference scheme for nonlinear convective problems

An explicit finite difference scheme is proposed for nonlinear convective problems. The procedure is applied to a nonlinear convective diffusion problem with a nonlinear boundary condition. It is shown that the nonlinear boundary condition may be treated directly without linearization which has to be carried out in the implicit method to avoid a nonlinear system of algebraic equations. The explicit procedure is more direct and less cumbersome than the implicit procedure and the answers are in excellent agreement with those of the implicit method.     

An electrochemically regenerative hydrogen-chlorine energy storage system: electrode kinetics and cell performance

The electrochemical oxidation and reduction of hydrogen and chlorine in hydrochloric acid has been investigated on graphite, ruthenized titanium and platinum electrodes. Both steady state and potentiostatic pulse methods were used. Cell studies were also carried out in cells with flow-by and flow-through chlorine electrodes. Results indicate that the electrode kinetics are fast and the electrolysis and fuel cell reactions can be carried out in the same cell with electric-to-electric efficiencies in excess of 75% at current densities of 300 mA cm^–2. Mass transfer limitations at the chlorine electrode during discharge can be eliminated by cell pressurization and the use of flow-through electrodes.This study was carried out under the auspices of the US Department of Energy.in the summers of 1976 and 1977     

Poly(ethyl acrylate) in dilute solution

Poly(ethyl acrylate) (PEA), solution polymerized in methyl ethyl ketone by free radical initiation, was fractionated and the fractions were characterized by light scattering, viscometry and osmometry. Fractions obtained were in the molecular weight range of 0·3 × 10⁶ to 1·6 × 10⁶ with a polydispersity of 1.40. The following Mark-Houwink relations were established:

$\text{[η]}{}^{\mathrm{<mtext>35°</mtext><mtext>C</mtext>}}{}_{\mathrm{<mtext>acetone</mtext>}}\text{=4·15×10}{}^{\mathrm{?2}}\text{M}{}^{\mathrm{0?61}}{}_{\mathrm{W}}$

$\text{[η]}{}^{\mathrm{<mtext>35°</mtext><mtext>C</mtext>}}{}_{\mathrm{<mtext>MEK</mtext>}}\text{=2·03×10}{}^{\mathrm{?2}}\text{M}{}^{\mathrm{0?66}}{}_{\mathrm{W}}$

$\text{[η]}{}^{\mathrm{<mtext>39.5°</mtext><mtext>C</mtext>}}{}_{\mathrm{<mtext>n-propanal</mtext>}}\text{=7·89×10}{}^{\mathrm{?2}}\text{M}{}^{\mathrm{0?50}}{}_{\mathrm{W}}$

It was found that n-propanol at 39.5°C was a theta solvent for poly(ethyl acrylate) and that acetone was a poor solvent compared to methyl ethyl ketone. A relation between the molecular dimension and the molecular weight was established. It was observed that the chain dimensions of poly(ethyl acrylate) and poly(butyl acrylate) were considerably larger than poly(ethyl methacrylate) and poly(butyl methacrylate) respectively. The validity of various extrapolation procedures that have been proposed for calculating the unperturbed dimensions have been examined. The steric factor for PEA was 2·16 compared to 2·10 for poly(ethyl methacrylate). Root mean square end-to-end distances were calculated from the Debye-Bueche and Kirkwood-Riseman methods and compared with the experimental values.     

Effect of nonprotein polymers on water‐uptake properties of fish protein‐based hydrogel

The effects of nonprotein polymers on the water‐swelling properties of fish protein‐based hydrogel were studied. Inclusion of carboxymethyl cellulose (CMC), poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA), or guar gum at a 2.5% (w/w) level in an 80% ethylenediaminetetraacetic dianhydide (EDTAD)‐modified fish protein hydrogel (10% monomer concentration) significantly decreased the extent of water uptake of the hydrogel. Among these polymers, PVA exhibited the greatest inhibitory effect. The inhibitory effect of these polymers on the water uptake of fish protein hydrogel was apparently due to the thermodynamic incompatibility of these polymers with the fish protein gel network and the consequent effect on the extent of relaxation of the crosslinked polypeptide network. In contrast, inclusion of 60% EDTAD‐modified soy protein up to a level of 40% of the total protein in the gel did not affect the extent of the equilibrium water uptake of the gel. At higher levels, however, soy protein also decreased the amount of water uptake by the gel. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 45–51, 2002     

Lyso platelet activating factor (LysoPAF) and its enantiomer. Total synthesis and carbon-13 NMR spectroscopy

Described is a reaction sequence for the total synthesis of lyso platelet activating factor (lysoPAF; 1-O-alkyl-sn-glycero-3-phosphocholine) and its enantiomer. The procedure is versatile and yields optically pure isomers of defined chain length. The synthesis is equally suited for the preparation of lysoPAF analogues and its enantiomers with unsaturation in the long aliphatic chain. First,rac-1(3)-O-alkylglycerol is prepared by alkylation ofrac-isopropylideneglycerol with alkyl methanesulfonate followed by acid-catalyzed removal of the ketal group. The primary hydroxy group of alkylglycerol is then protected by tritylation, the secondary hydroxy group is acylated, and the protective trityl group is removed under mild acidic conditions with boric acid on silicic acid, essentially without acyl migration. Condensation of the diradylglycerol with bromoethyl dichlorophosphate in diethyl ether, hydrolysis of the resulting chloride, and nucleophilic displacement of the bromine with trimethylamine givesrac-1-O-alkyl-2-acylglycero-3-phosphocholine in good overall yield. The racemic alkylacylglycerophosphocholine is finally treated with snake venom phospholipase A₂ (Ophiophagus hannah) which affords 1-O-alkyl-sn-glycero-3-phosphocholine (lysoPAF) of natural configuration in optically pure form. The “unnatural” 3-O-alkyl-2-O-acyl-sn-glycerol-1-phosphocholine enantiomer, which is not susceptible to phospholipase A₂ cleavage, gives 3-O-alkyl-sn-glycero-1-phosphocholine upon deacylation with methanolic sodium hydroxide. Homogeneity and structure of the intermediates and final products were ascertained by carbon-13 nuclear magnetic resonance spectroscopy on monomeric solutions.     

Grafting of methyl methacrylate to nitrocellulose by ceric ions

Studies were carried out on grafting of various vinyl monomers to nitrocellulose by ceric ions. It was observed that graft copolymerization occurred only with methyl methacrylate (MMA) and methyl acrylate monomer. The variables such as initiator concentration, monomer concentration, time of grafting, and nitrocellulose content on grafting of MMA are discussed. By hydrolyzing away the nitrocellulose backbone, the grafted poly(methyl methacrylate) branches were isolated and the >c?o peak at 1740 cm^?1 in the infrared spectra of these isolated branches gave definite evidence of grafting. The molecular weight of isolated branches has been determined by viscometry. The probable mechanism of grafting may be at the α-carbon atom of primary alcohol or at a C₂-C₃ glycol group of the anhydro glucose unit or at the hemiacetal group of the end unit of nitrocellulose, as nitrocellulose is formed by the partial nitration of cotton cellulose.     

Effects of ring substituents on the protective properties of self-assembled benzenethiols on copper

The self-assembled monolayers (SAMs) of a series of substituted benzenethiol (BT) molecules, X-C₆H₄-SH (where X = meta-NH₂, ortho-NH₂, para-NH₂, para-NHCOCH₃, para-F, para-CH₃ and para-CH(CH₃)₂), have been prepared by adsorption from a solution onto a fresh copper (Cu) surface pretreated by a nitric acid etch. The corrosion inhibition efficiency of the modified Cu surfaces in a sulfuric acid solution was investigated by electrochemical characterization. The protection afforded by the substituted functional groups on BT is strongly influenced by the type and the position of the substituent on the benzene ring. BT molecules without any substituent group on the ring are ineffective corrosion inhibitors, indicating that the chemical configuration is the key factor in determining the efficacy of the SAMs as barriers to electrochemically corrosive ions. It is further proposed that the steric hindrance offered by the substituted group in the SAMs plays a very important role in determining its barrier properties.