Grafting vinyl monomers onto silk fibers: Graft copolymerization of methyl methacrylate onto silk using acetylacetonate Mn(III) complex

The graft copolymerization of methyl methacrylate onto Mulberry silk fibers was studied in aqueous solution using Mn(acac)₃ as initiator. Perchloric acid was found to catalyze the reaction. The rate of grafting was investigated by varying the concentration of the monomer and the complex, acidity of the medium, the solvent composition of the reaction medium, the surfactants, and the inhibitors. The graft yield increases with increasing concentration of Mn(acac)₃ up to 0.01 mol/L, decreasing thereafter. Increase of MMA concentration up to 0.56 mol/L increases graft yield, and thereafter it decreases. Among the various vinyl monomers studied, MMA was found to be most suitable for grafting. Grafting increases up to 7.5 × 10^?3 mol/L of HClO₄ concentration, and thereafter it decreases. A suitable reaction scheme has been proposed and a rate equation has been derived. The energy of activation has been calculated from the Arrhenius plot. The chain transfer constants for various chain transfer solvents have been evaluated from the average molecular weight (M?) of grafted poly(methyl methacrylate).     

Grafting vinyl monomers onto silk fibers. II. Graft copolymerization of methyl methacrylate onto silk by hexavalent chromium ion

The feasibility of chromium(VI) to induce graft polymerization of methyl methacrylate onto silk was investigated. The rate of grafting was determined by varying monomer concentration, chromium(VI) concentration, temperature, acidity of the medium, nature of the silk, reaction medium, and redox system. The graft yield increased with increasing monomer concentration up to 0.65M, and with further increase of monomer the graft yield decreased. The graft yield increased with increasing chromium(VI) concentration. The grafting is considerably influenced by chemical modification of silk prior to grafting. The graft yield is influenced by thiourea concentration, decreasing with increasing thiourea concentration. The effect of certain inorganic salts and anionic surfactants on the rate of grafting was investigated.     

Field Validation of DNDC Model for Methane and Nitrous Oxide Emissions from Rice-based Production Systems of India

The DNDC (DeNitrification and DeComposition) model was tested against experimental data on CH₄ and N₂O emissions from rice fields at different geographical locations in India. There was a good agreement between the simulated and observed values of CH₄ and N₂O emissions. The difference between observed and simulated CH₄ emissions in all sites ranged from −11.6 to 62.5 kg C ha⁻¹ season⁻¹. Most discrepancies between simulated and observed seasonal fluxes were less than 20% of the field estimate of the seasonal flux. The relative deviation between observed and simulated cumulative N₂O emissions ranged from −237.8 to 28.6%. However, some discrepancies existed between observed and simulated seasonal patterns of CH₄ and N₂O emissions. The model simulated zero N₂O emissions from continuously flooded rice fields and poorly simulated CH₄ emissions from Allahabad site. For all other simulated cases, the model satisfactorily simulated the seasonal variations in greenhouse gas emission from paddy fields with different land management. The model also simulated the C and N balances in all the sites, including other gas fluxes, viz. CO₂, NO, NO₂, N₂ and NH₃ emissions. Sensitivity tests for CH₄ indicate that soil texture and pH significantly influenced the CH₄ emission. Changes in organic C content had a moderate influence on CH₄ emission on these sites. Introducing the mid-season drainage reduced CH₄ emissions significantly. Process-based biogeochemical modeling, as with DNDC, can help in identifying strategies for optimizing resource use, increasing productivity, closing yield gaps and reducing adverse environmental impacts.     

Grafting of vinyl monomers onto silk fibers: Trivalent-manganese-initiated graft copolymerization of acrylamide onto silk fibers

Graft copolymerization of acrylamide (AM) onto silk fibers, using Mn(III)–sulphate as initiator, has been investigated, in aqueous sulphuric acid in the temperature range of 30–55°C. Grafting reaction has been studied by varying the concentration of monomer, Mn(III), sulphuric acid, temperature, and also with the modified silk. The graft yield increases significantly with increase of monomer concentrations to the extent of 0.85M, after which the rate falls. With increase in Mn(III) concentration and H⁺ ion concentration the graft yield increases, but after an optimum concentration a depression in the graft yield is noticed. The rate of the reaction is temperature-dependent; with increase of temperature the graft-on increases. Among the solvent composition studied a solvent/water mixture containing 10% of the solvent seems to constitute the most favorable medium for grafting, and a further increase of solvent composition decreases the graft yield. The effect of various additives such as transition metal salts, aromatic and heterocyclic amines on grafting reaction has been studied. A suitable mechanism for grafting has been proposed. Finally physical characterization such as thermal analysis (TGA) of the grafted samples has been carried out in order to ensure grafting and to study the change in the properties of the fibers.     

Polymers from renewable resources. VIII. Thermal properties of the interpenetrating polymer networks derived from castor oil–isophorone diisocyanate–polyacrylamides

Castor oil was reacted with isophorone diisocyanate varying the isocyanate/hydroxyl ratio to produce a number of polyurethanes (PUs). All the PUs were reacted with acrylamide and methacrylamide using ethylene glycol dimethacrylate as the crosslinker and benzoyl peroxide as the initiator. Thermogravimetric analysis of the polymers was conducted using a computer analysis method for assigning the kinetic mechanism. The degradation steps have been discussed in the light of the kinetic parameters. © 1995 John Wiley & Sons, Inc.     

Grafting vinyl monomers onto wool fibers: Graft copolymerization of methyl methacrylate onto wool fibers using vanadyl acetyl acetonate complex

The graft copolymerization of methyl methacrylate (MMA) onto native and reduced Indian Chokla wool fibers was studied in aqueous solution using the acetylacetonate oxovanadium (IV) complex. The rate of grafting was investigated by varying the concentration of the monomer and the complex, acidity of the medium, and the solvent composition of the reaction medium. The graft yield increases with increasing concentration of the initiator up to 8.75 × 10^?5 mol/L, of the monomer up to 0.5634 mol/L, and thereafter it decreases. MMA was found to be the most active monomer when compared to other vinyl monomers. Grafting increases with increasing concentration of HClO₄ and with increasing temperature. Reduced and oxidized wools were found to be better substrates than untreated, esterified, crosslinked, and trinitrophenylated wools. The extent of grafting was mostly dependent upon the concentration of ? SH groups in case of reduced wool. A suitable reaction scheme has been proposed and the activation energy was calculated from Arrhenius plot.     

Grafting vinyl monomers into nylon-6. II. Graft copolymerization of methyl methacrylate onto nylon-6 by hexavalent chromium ion

The feasibility of chromium(VI) to induce graft copolymerization of methyl methacrylate onto nylon-6 was investigated in the presence of nitrogen. The rate of grafting was determined by varying monomer concentration, chromium(VI) concentration, temperature, acidity of the medium, solvents, inorganic salts, and redox system. The graft yield increases significantly by increasing the monomer concentration. The graft yield increases with increase of [Cr(VI)] up to 0.025 mole/liter. With further increase of [Cr(VI)], the graft yield decreases. The increase of acid concentration up to 0.395 mole/liter results the increase in graft yield. Beyond this concentration the graft yield decreases. The graft yield increases with increase in temperature up to 55°C and thereafter it decreases. The graft yield is medium dependent. The graft yield increases with increasing thiourea concentration upto 0.0025 mole/liter but beyond this concentration, the percentage graft yield decreases. A suitable kinetic scheme has been proposed and the rate equation has been evaluated.     

Sorption/diffusion of aqueous mixtures of 1,4‐dioxane/tetrahydrofuran through blend membranes of poly(vinyl alcohol) and sodium alginate: Their compatibility and pervaporation separation studies

Blend membranes of poly(vinyl alcohol) (PVA) and sodium alginate (NaAlg) were prepared by solution casting and crosslinked with glutaraldehyde (GA). Polymer blend compatibility was studied in water by measuring solution viscosity at 30°C. From the viscosity data, interaction parameters were determined to find the blend compatibility. Thickness of the membranes ranged between 35 and 40 μm. Circular disc‐shaped samples were cut from the thin membranes to perform gravimetric sorption experiments in water + 1,4‐dioxane and water + tetrahydrofuran mixtures at 30°C. Diffusion coefficients were calculated using Fick's equation. Concentration profiles of liquids were computed by solving Fick's equation under suitable boundary conditions. Diffusion coefficients show a dependence on the composition of the blends as well as composition of binary mixtures. A correlation was attempted between concentration profiles and diffusion coefficients of the transporting liquids. Degree of swelling and sorption coefficients were calculated from the gravimetric sorption data. Sorption kinetics was studied using an empirical equation to understand the nature of sorption–diffusion anomalies. Membrane selectivity for water + 1,4‐dioxane and water + tetrahydrofuran mixtures were calculated from the pervaporation experiments. A correlation between sorption and membrane selectivity was attempted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 178–188, 2005