Modification of leather properties by grafting. I. Effect of monomer chain on the physico‐mechanical properties of grafted leather

Although leather has a number of desirable properties such as thermal stability and fire retardancey, in addition to high toughness, it has a few drawbacks such as weight, high water absorption, poor soil and rot resistance, and nonuniformity. If these defects are overcome, leather's usefulness would be further enhanced and its competitive position with respect to synthetics would increase. This study reports the physical and mechanical properties of buffalo leather after chemical graft copolymerization with ethyl acrylate, butyl acrylate, and 2‐ethyl hexyl acrylate using benzoyl peroxide as an initiator. The optimum conditions for grafting (e.g., monomer and initiator concentrations, temperature and time of grafting, and solvent leather ratio) were extensively investigated. The study achieved outstanding properties for buffalo leather in reduction of water uptake after grafting, especially on using 2‐ethyl hexyl acrylate and butyl acrylate monomers. FT‐IR and solid ¹³C‐NMR for leather before and after grafting confirmed the grafting process.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1478–1483, 2003     

Functional properties of a protein product from Caryodendron orinocense (Barinas nut)

The functional properties of Caryodendron orinocense protein product were investigated and compared with those of soybean (Glycina maxima). The product protein content was 24.47 g/100 g (Nx6.25). Solubility increased at both sides of the isoelectric point (pH 4.0) and with increased NaCl concentration up to 0.5M. Compared with soybean flour (50% protein), the protein product exhibited higher water and oil absorption, but lower emulsifying activity, emulsion stability, foaming capacity, and foam stability, the last one increase at higher pH. Emulsifying activity, foaming capacity, and foam stability were ionic strength dependent. C. orinocense protein product increased its emulsifying activity steadily from 0.05M to 0.75M NaCl, while it remained almost constant for soybean flour. Foaming capacity increased drastically at pH 10. The minimum time and concentration to form a gel was 20% in 4 min and 10% in 8 min for the Caryodendron protein product and soybean flour, respectively. The bulk density was 0.5056+/-0.0041 g/mL.     

Grafting poly(t‐butyl acrylate) to poly(allylamine) by inverse microemulsion radical polymerization: From comb‐polymer to amphiphilic shell crosslinked polymer nanocapsule

An interfacial grafting radical polymerization method for amphiphilic comb copolymer and shell crosslinked polymer nanocapsules was reported. Macropolyradicals on a water soluble long chain polyamine were generated with hydrogen peroxide in the water phase and subsequent grafting radical polymerization of a vinylic monomer at the water/oil interface proceeded at 65°C. In the presence of a crosslinker, the resulting graft copolymer formed a defined core‐shell structure with hydrophilic aqueous core functionalized by the polyamine and a hydrophobic crosslinked polymer shell. The structure of the core‐shell material was characterized by NMR, FTIR, DSC, TGA, SEM, TEM, and the mechanism of the graft polymerization is proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1905–1911, 2007     

Inhibition effect of some polymers on the corrosion of cadmium in a hydrochloric acid solution

The effects of poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA), sodium polyacrylate (NaPA), poly(ethylene glycol) (PEG), pectin (P), and carboxymethyl cellulose (CMC) on the corrosion of cadmium in a 0.5M hydrochloric acid (HCl) solution were studied with both electrochemical impedance spectroscopy and Tafel plot techniques. Measurements were carried out at cathodic, open‐circuit, and anodic potentials. All the investigated polymers had inhibitory effects on both the cathodic (except for NaPA, P, and CMC) and anodic processes, with a predominant anodic inhibiting action. However, NaPA, P, and CMC exhibited a slight cathodic inhibiting action only at higher polymer concentrations. This behavior may be attributed to the very weak adsorbability of the polymers on the cathodic sites. Because PVA and PEG had hydroxy groups, there could be bridging between the polymer and the surface, resulting in an inhibiting effect in the HCl solution. However, PVA had much greater adsorbability on the surface than PEG at the anodic potential. The adsorption of most of the polymers obeyed a Temkin adsorption isotherm, and this indicated indicating that the main process of inhibition was adsorption. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 866–871, 2003     

Poly(p-tert-butoxycarbonyloxystyrene): a convenient precursor to p-hydroxystyrene resins

An efficient synthetic route to pure, high molecular weight poly(p-hydroxystyrene) is reported. The route involves synthesis of a new monomer, p-tert-butoxycarbonyloxystyrene, polymerization by radical initiation or by cationic initiation in liquid SO₂, followed by thermolysis or acidolysis of the tert-butoxycarbonyl protecting group. Porous, crosslinked resin beads containing the nucleophilic, phenol pendant group have been prepared in a similar fashion from the precursor terpolymer of p-tert-butoxycarbonyloxystyrene, styrene and divinylbenzene. The utility of this resin for solid-phase synthesis has been demonstrated.     

Syndiotactic Polystyrene/Organoclay Nanocomposites: Synthesis via In Situ Coordination‐Insertion Polymerization and Preliminary Characterization

Summary: Syndiotactic polystyrene (sPS)/organophilic clay nanocomposites were obtained by in situ coordination‐insertion polymerization of styrene. Two cationic surfactants (alkylammonium and alkylphosphonium) were used for the intercalation of montmorillonite (MMT). For each organically modified clay, three protocols were performed using an MAO‐activated hemi‐metallocene catalyst, in order to compare the influence of experimental conditions on the composite microstructure and on its thermal stability. The microstructures of nanocomposites were investigated by wide angle X‐ray scattering and DSC. Partially exfoliated or intercalated materials were obtained in all cases and a decrease of crystallinity is observed. Thermal properties were also studied by DSC and thermogravimetric analysis. The presence of clay does not have a strong influence on the sPS thermal transitions but the thermal decomposition process of the material was slowed down in the presence of few organoclay percents, particularly in the degradation beginning. The influence of these two organically modified clays on the thermal stability of the material is discussed.

Gel and suspension formed from the combination of cloisite with toluene (left) and styrene (right), respectively.     

Kinetic modelling of the catalytic conversion of synthesis gas

A kinetic study for the one-step conversion of synthesis gas to gasoline on a ZnO–Cr₂O₃–ZSM-5 catalyst is described. On this catalyst, three reactions are involved in the overall transformation of synthesis gas: the methanol synthesis, the conversion of methanol to hydrocarbons and the water–gas shift reaction. Under the operating conditions selected for the study, it was found that the water–gas shift was at equilibrium and the methanol was completely converted to hydrocarbons. Consequently, it was postulated that the kinetics of the limiting reaction step, the methanol synthesis on the ZnO–Cr₂O₃ component, was the one that controls the overall reaction rate. Three kinetic model equations describing the rate of synthesis gas conversion on the bifunctional catalyst, were considered to fit the data of the experimental runs performed in a Berty well-mixed reactor. Those equations were derived under very special conditions where the methanol decomposition term could be neglected. It was also observed that in the kinetic equations a term involving the fugacity of CO₂ was required to predict the rate properly. The catalyst deactivation was also taken into account in the analysis.     

Lignin‐based polycondensation resins for wood adhesives

Lignin‐based wood adhesives are obtained that satisfy the requirements of relevant international standards for the manufacture of exterior‐grade wood particleboard. Formulations based on low molecular mass lignin and presenting an increase in the relative proportion of reactive points yield better results than the higher molecular mass lignin used in the past. These lignins allow a higher proportion of hydroxymethylation during preparation of methylolated lignins. These lignin‐based adhesives also yield acceptable results at particleboard pressing times that are sufficiently low to be of industrial significance. Lignin‐based wood adhesives, in which a nonvolatile nontoxic aldehyde (glyoxal) is substituted for formaldehyde in their preparation, are prepared and tested for application to wood panels such as particleboard. The adhesives yield good internal bond strength results for the panels, which are good enough to comfortably pass relevant international standard specifications for exterior‐grade panels. The adhesives also show sufficient reactivity to yield panels in press times comparable to that of formaldehyde‐based commercial adhesives. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1690–1699, 2007     

Recycling of pharmaceutical waste gelatin for controlled‐release applications. I. A 2,4‐dicholorphenoxy acetic acid based system

Gelatin is a natural macromolecular protein. It contains a wide variety of amino acids in its polymer structure, and it is colorless to yellowish, water‐soluble, and tasteless. It is used as a dispersing agent, sizing medium, and coating for photographic films and in pharmaceutical formulations. In this study, biodegradable mulching, based on waste gelatin from pharmaceutical gelatin scraps (derived from pharmaceutical soft gelatin capsule production), was formulated via the casting of water solutions or suspensions into flexible and consistent films. Gelatin was blended with synthetic materials such as poly(vinyl alcohol) and other natural wastes such as sugar cane bagasse and sawdust. To all formulations, 2,4‐dichlorophenoxy acetic acid (2,4‐D) was added as a herbicide. The morphology and mechanical properties of the samples were investigated with scanning electron microscopy and tensile testing, respectively. The results showed that the produced films had controlled‐release properties. The effects of various additives and crosslinking on the films and the release of the herbicide 2,4‐D from the films were also investigated. The introduction of synthetic and natural additives reduced the release rate of 2,4‐D. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2313–2319, 2004     

Credal classification rule for uncertain data based on belief functions

In this paper we present a new credal classification rule (CCR) based on belief functions to deal with the uncertain data. CCR allows the objects to belong (with different masses of belief) not only to the specific classes, but also to the sets of classes called meta-classes which correspond to the disjunction of several specific classes. Each specific class is characterized by a class center (i.e. prototype), and consists of all the objects that are sufficiently close to the center. The belief of the assignment of a given object to classify with a specific class is determined from the Mahalanobis distance between the object and the center of the corresponding class. The meta-classes are used to capture the imprecision in the classification of the objects when they are difficult to correctly classify because of the poor quality of available attributes. The selection of meta-classes depends on the application and the context, and a measure of the degree of indistinguishability between classes is introduced. In this new CCR approach, the objects assigned to a meta-class should be close to the center of this meta-class having similar distances to all the involved specific classes? centers, and the objects too far from the others will be considered as outliers (noise). CCR provides robust credal classification results with a relatively low computational burden. Several experiments using both artificial and real data sets are presented at the end of this paper to evaluate and compare the performances of this CCR method with respect to other classification methods.