Transesterification in poly(ethylene terephthalate) and poly(ethylene naphthalate 2,6-dicarboxylate) blends: model compounds study

Kinetics of transesterification reaction in poly(ethylene terephthalate)-poly(ethylene naphthalate 2,6-dicarboxylate), PET-PEN, blends resulting from melt processing was simulated using model compounds of ethylene dibenzoate (BEB) and ethylene dinaphthoate (NEN). The exchange reaction between BEB and NEN was followed by ¹H NMR spectroscopy using signals from the aliphatic protons of ethylene glycol moieties at 4.66 and 4.78 ppm, respectively. The first-order kinetics was established under pseudo-first-order conditions for both reactants. Thus, the overall transesterification reaction was second order reversible. The reversibility was confirmed experimentally by heating a mixed sequence of 1-benzoate 2-naphthoate ethylene (BEN) under similar conditions. Both forward reaction of the equimolar amounts of the reagents and reverse reaction came to equilibrium at the same molar ratio of the reactants and reaction products of roughly 0.25:0.50:0.25 for BEB, BEN, and NEN, respectively. The rate equation for the transesterification reaction in the model system was modified using half-concentration of BEN, which is the only effective in the intermolecular exchange. Direct ester-ester exchange was deduced as a prevailing mechanism for the transesterification reaction under the conditions studied, and the values of equilibrium and rate constants, as well as other basic thermodynamic and kinetic parameters were determined. The use of Zn(OAc)₂ as a catalyst resulted in a significant decrease in the activation enthalpy of transesterification, which might be due to the partial switch of the reaction mechanism from primarily pseudo-homolytic to more heterolytic where Zn^II acts as a Lewis base which binds to the ester carbonyl oxygen.     

Plasma polymerization of random polyaniline–polypyrrole– iodine copolymers

This work presents the synthesis by plasma and the characterization of polypyrrole–polyaniline–iodine copolymer thin films. The objective was to study the conditions to randomly copolymerize different and noncombinable monomers to create new copolymers with enhanced selective properties. The study was focused on the influence of the monomer mass ratio r on the structure of the copolymers. The monomer ratio r is important since it represents the contribution of each monomer to the structure and to the properties of the copolymer. The mainstream techniques used to characterize the plasma polymers were infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The electric conductivity was studied as a function of the relative humidity. The results indicated that the copolymers with iodine have better conductive properties at lower relative humidity and that the copolymers without iodine are more stable at moderately high temperatures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 263–270, 2002     

Cover Image,Volume 141, Issue 17

The cover image by Lizandra Viana Maurat da Rocha highlights one of our innovative biodegradable films, which incorporated molybdenum trioxide and zinc oxide into the poly(butylene adipate-co-terephthalate) matrix through casting. The photo emphasizes its partial transparency and homogeneity. Some analytical results reported as FTIR, TD-NMR, XRD and TGA validates nanomaterial's exceptional mechanical and chemical properties. Icons below underscore its potential as an eco-friendly food packaging,with bacteriostatic features and no formation of microplastics after disposal. DOI: 10.1002/app.55294

     

Comparison of the time-temperature curing dependence of industrial and dry blend modified plastisols

In this work PVC plastisol rotational molding formulations were characterized as a function of processing conditions. Temperature sweep runs in the 60 to 220°C range suggest the presence of different stages in the solidification process, marked by the crossover of storage (G′) and loss (G″) moduli. Viscoelastic properties as a function of time were measured at different processing temperatures (in the 80 to 220°C range). Ultimate strength, ultimate elongation, and solvent resistance of the formulations after processing were also measured to evaluate performance.     

Biodegradability Study of the Biosurfactant Contained in a Crude Extract from Corn Steep Water

Over the last few years, the global biosurfactant market has raised due to the increasing awareness among consumers, for the use of biological or bio-based products. Because of their composition, it can be speculated that these are more biocompatible and more biodegradable than their chemical homologous. However, at the moment, no studies exist in the literature about the biodegradability of biosurfactants. In this work, a biosurfactant contained in a crude extract, obtained from a corn wet-milling industry stream that ferments spontaneously in the presence of lactic acid bacteria, was subjected to a biodegradation study, without addition of external microbial biomass, under different conditions of temperature (5–45 °C), biodegradation time (15–55 days), and pH (5–7). For that, a Box–Behnken factorial design was applied, which allowed to predict the percentage of biodegradation for the biosurfactant contained in the crude extract, between the range of the independent variables selected in the study, obtaining biodegradation values between 3 and 80%. The percentage of biodegradation for the biosurfactant was calculated based on the increase in the surface tension of samples of the crude extract. Furthermore, it was also possible to predict the variation in t_1/2 for the biosurfactant (time to achieve the 50% of biodegradation) under different conditions.     

Evaluation of Transport Phenomena for Removing Vanadium from Petrochemical Industry Solid Waste

Transport phenomena are investigated which are involved in the electrokinetic remediation process used for removing vanadium from deactivated catalysts from oil catalytic cracking that are currently allotted to cement plants and class-I landfills. Variables such as the concentration of electrolyte, electric potential, and applied electric current were evaluated in order to determine the effects produced by electroosmosis, diffusion, hydraulic gradient, and electromigration on the removal of vanadium from the catalyst. It was observed that migration is the most relevant phenomenon in the remediation tests, and for the best remediation condition, the migratory flow accounted for about 87 % of the vanadium removal.     

Caffeine selectivity of divinylbenzene crosslinked polymers in aqueous media

The selective binding of caffeine to polymers is of interest in developing caffeine-specific sensors. The influence of the nature and quantity of crosslinking agents and functional monomers on the selectivity and binding affinity of a polymer to caffeine is reported. A high binding affinity and selectivity of divinylbenzene (DVB) crosslinked polymers toward caffeine was exhibited by the binding competition of caffeine with several dimethylated and chlorinated xanthines and N-methylated uric acids in aqueous media. To understand the nature of the caffeine–polymer interaction, we performed binding studies with solvents of different polarities and ionic strengths. The binding properties of DVB-based polymers containing different functional monomers were compared with Amberlite^® XAD resins. Analytes with hydrophilic and electron-withdrawing groups lowered their binding affinity with the polymer in comparison with caffeine and its dimethylated derivatives. The caffeine–polymer interaction appeared to be predominantly a hydrophobic π–π interaction but partly due to the presence of caffeine-specific sites. The reversibility of the caffeine–polymer binding was investigated, and the dissociation constants were approximated to be 27 and 6 mM. Dipole moments of caffeine and related molecules were estimated theoretically and were correlated with their corresponding B/T ratio, which is defined as the fraction of caffeine bound to the polymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 195–205, 2001     

Development of composite membrane PBAT: Zeolite Y for application as rhynchophorol release system

Composite membranes consisting of biodegradable poly(butylene adipate‐co‐terephthalate (PBAT) and zeolite Y (0–10 wt %) were produced by extrusion. Zeolite Y is well dispersed in the membrane up to 5 wt %, but tends to agglomerate at higher contents. The presence of zeolite Y in the composite resulted in an improvement of the thermal stability, mechanical properties, and increased the barrier properties. The interaction of the composite membranes with rhynchophorol was investigated by different techniques, showing that the semiochemical progressively lixiviates PBAT monomers, causing thermal and mechanical properties to decrease. However, no interaction seemed to occur between the rhynchophorol and the zeolite. Studies of diffusion of pheromone through membranes have shown that the addition of the zeolite Y has not contributed significantly to a decrease in the release rate of rhynchophorol, but the presence of the zeolite Y helps to increase chemical, mechanical, and thermal stabilities of the membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45757.     

Amperometric urea biosensors based on the entrapment of urease in polypyrrole films

Urease (Urs) was immobilized in electrochemically prepared polypyrrole (PPy) and the resulting films were characterized by cyclic voltammetry, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and ultraviolet visible spectroscopy (UV-VIS). The enzymatic activity of Urs entrapped in the PPy matrix was confirmed by the catalytic conversion of urea into carbon dioxide and ammonia, when urea was detected amperometrically at different concentrations in standard samples and commercial fertilizers. The PPy/Urs biosensors exhibited selectivity, a relatively high efficiency at urea concentrations below 3.0 mmol L⁻¹, and a sensitivity to urea of 2.41 μA cm⁻² mmol⁻¹ L.