Effect of irradiation on AMP based resins for cesium separation from HNO3 feed solutions: batch and column studies

Three different resins containing ammonium molybdophosphate (AMP), viz. PMMA (polymethylmethacrylate) resin, composite AMP resin and ALIX (a bisphenol based resin), were evaluated for their irradiation stability. The studies included batch as well as column studies and were carried out for cesium uptake behaviour at 3 M acidity. The resin beads were irradiated to varying dose viz., 0 MRad, 10 MRad, 20 MRad, 50 MRad and 100 MRad. The time taken to attain equilibrium was rather long and about 2–5 h were found to be required for attaining equilibrium in batch studies. Batch Cs(I) uptake studies revealed no significant effect on the K _d values in case of the PMMA resin while in case of the composite resin and ALIX resin, a decrease in the K _d was observed as a function of irradiation dose. The resin capacity indicated contrasting behaviour with irradiation dose for the resins. Column runs have been carried out for the uptake of radio cesium using both unirradiated and irradiated resins using feed solutions containing 3 MHNO₃. The loading capacities of the resins were found to be proportional to their Cs loading capacities observed in batch studies. Study revealed that the composite AMP had the maximum and PMMA has the least loading capacity. Results of these studies show that these AMP based resins can be used for cesium separation from acidic nuclear waste.     

Interacting blends of Styrenated unsaturated poly (ester–amide)s with commercial unsaturated polyester resin (o-phthalic anhydride based)

Unsaturated poly (ester–amide)s resins (UPEAs) were prepared by the reaction between an epoxy resin, namely diglycidyl ether of bisphenol-A (DGEBA) and unsaturated aliphatic bisamic acids (B_1–4) using a base catalyst. These UPEAs were then diluted by styrene and blended with commercial unsaturated polyester resin (o-phthalic anhydride based) to produce a homogeneous resin. The curing of these Styrenated UPEAs–UPR blends was carried out using Benzoyl peroxide (BPO) as a catalyst and N,N′-Dimethyl aniline (DMA) as a promoter. The glass fiber reinforced composites (i.e. laminates) of these Styrenated UPEAs–UPR (o-phthalic anhydride based) blends were fabricated. The mechanical and chemical resistance properties of the glass fiber composites have also been evaluated. The unreinforced cured samples of the Styrenated UPEAs–UPR (o-phthalic anhydride based) blends were also analyzed by thermogravimetry (TGA).     

Concentration and Separation of Ni2+, Cu2+ and Co2+ by Back Extraction Chromatography Using Lix 64N and Cationic Resins

Abstract

This paper describes the method for the concentration of Cu²⁺ by liquid-liquid extraction using Lix 64N solutions in kerosene, followed by back extraction chromatography.

It consists of a pass of the organic phase through columns filled with cationic resins (H⁺) which contains only the water surrounding the grains.

The effect of the pH of the aqueous film surrounding the resin grains on the capacity of Vionit CS-3 (-SO₃H) and Vionit CM-14 (-SH) has been established.

The loading curves of these resins have been drawn, as the optimum pH of the aqueous film and the resin capacities shown to increase in the order -SH < -SO₃H.

The effect of the flow-rate on the loading and the optimum elution conditions have been also determined.

A mechanism for the ion-exchange process is proposed.     

Synthesis of dimethyl carbonate (dmc) from co2, ethylene oxide and methanol using heterogeneous anion exchange resins as catalysts

Summary A two-step synthesis of dimethyl carbonate (DMC) from ethylene oxide (EO), carbon dioxide and methanol using heterogeneous anion exchange resins as catalysts is reported. The first step is the reaction of EO with CO₂ to form ethylene carbonate (EC), and the second one the transesterification of EC with methanol to yield DMC. Effect of various reaction parameters on the activity and selectivity of the catalysts used was investigated. After the first step, the crude mixture containing EC was directly reacted with methanol in the presence of a heterogeneous anion exchange resin catalyst to produce DMC in high yield and selectivity. Our process is highly economic.     

Removal of Trace Contaminants from Water Using New Chelating Resins

Abstract

The modification of cross‐linked polyacrylamide (CPAAm) and incorporation of methyl thiourea (MeTU) or phenyl thiourea (PhTU) group were utilized in the preparation of two new chelating resins CPAAm‐EDA‐MeTU (resin I) and CPAAM‐EDA‐PhTU (resin II), [EDA=ethylenediamine]. The prepared resins were characterized by elemental analysis and IR spectroscopy. The sorption behaviors of Cd(II), Pb(II), and Zn(II) ions on the prepared resins were studied and the optimum sorption conditions for the tested metal ions were determined. The optimum pH value for the sorption of Cd(II) and Zn(II) ions on both resins I and II was ranged between 7–8. The prepared new resins show very little affinity towards Pb(II) ion. The maximum experimental sorption capacities of resin I towards Cd(II) and Zn(II) ions were 3.2 and 0.6 mmol g^?1, respectively, and that of resin II were and 0.6 mmol g^?1 in the same prescribed order. Langmuir and Freundlich isotherm constants and correlation coefficients for the present system were calculated and compared. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) for cadmium and zinc sorption on the prepared resins were also determined from the temperature dependence.     

Theoretical study on the interaction of sulfur‐ and aminopyridine‐containing chelating resins with Hg(II) and Pb(II)

The geometries and energetics of complexes of Hg(II) and Pb(II) with sulfur‐ and aminopyridine‐containing chelating resin including crosslinked polystyrene immobilizing 2‐aminopyridine via sulfur‐containing (PVBS‐AP), sulfoxide‐containing (PVBSO‐AP), and sulfone‐containing (PVBSO₂‐AP) spacer arms have been investigated theoretically, and thus interactions of the metal ions with chelating resins were evaluated. The results indicate that PVBS‐AP behaves as a tridentate ligand to coordinate with the metal ions by S and two N atoms to form chelating compounds with S atom playing a dominant role in the coordination, whereas PVBSO‐AP and PVBSO₂‐AP interact with metal cations, respectively, in a tricoordinate manner by O and two N atoms forming chelating complexes. Furthermore, it is revealed that O and N2 atoms of PVBSO‐AP are the main contributor of coordination to Hg(II), whereas N2 atom of PVBSO₂‐AP is mainly responsible for the coordination to Hg(II). For PVBSO‐AP‐Pb²⁺ and PVBSO₂‐AP‐Pb²⁺ complex, the coordination is dominated by the synergetic effect of N1, N2, and O atoms. Natural bond orbital and second‐order perturbation analyses suggest that the charge transfer from the chelating resins to metal ions is mainly dominated by the interactions of lone pair of electrons of the donor atoms with the unoccupied orbitals of metal ions. Hg(II) complexes exhibit larger binding energies than the corresponding Pb(II) complexes, implying the chelating resins exhibit higher affinity toward Hg(II), which is consistent with the experimental results. Combined the theoretical and experimental results, further understanding of the structural information of the complexes and the coordination mechanism was achieved. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Effect of alkylresorcinols on curing behaviour of phenol-formaldehyde resol resin

Thermal behaviour of cure-accelerated phenol-formaldehyde (PF) resins was studied using the addition of commercial mixture of water soluble oil shale alkylresorcinols (AR) to PF resin, 5-MR being as model compound. The acceleration effect of AR is based on the promotion of condensation of resin methylol groups and subsequent reaction of released formaldehyde with AR. Commercial PF resins SFŽ-3013VL and SFŽ-3014 from the Estonian factory VKG Resins have been used. The chemical structure of resins was characterised by ¹³C NMR spectroscopy. TG-DTA analysis was carried out using labsys^TM instrument Setaram. By TG-DTA measurements, the shift of exothermic and endothermic peaks and the changes of mass loss rate in the ranges of 1.5–10 g AR/100 g PF resin were studied. The effect of AR on the curing behaviour of PF resins was also followed by gel time. Testing of the plywood when using PF resin with 5 mass% of AR shows that the press time could be reduced by about 15%.     

A Comparison of the Syntheses of High Molar Mass Epoxy Resins on the Basis of two Groups of Modified Vegetable Oils

Application of epoxidized and hydroxylated natural oils as a new group of environmentally friendly and renewable raw materials for the synthesis of high molar mass epoxy resins is described. Selected vegetable oils were first oxidized and next reacted with mono and diethylene glycols. Obtained epoxidized soybean, rapeseed, linseed and sunflower oils were used together with Bisphenol A in the fusion process. Analogously, hydroxylated soybean and rapeseed oils were reacted with commercial grade Bisphenol A-based low molar mass epoxy resin. The fusion process was carried out in the presence of selected catalysts (i.e., lithium chloride, 2-methylimidazole, triphenylphosphine and triethanolamine) giving high molar mass epoxies. The relationship between type of modified oil used in the synthesis and reaction conditions and properties of synthesized resins (e.g., value and distribution of average molar mass, contents of epoxy groups and colour) is discussed.     

Evaluation of the Biocidal Capacity of Hypercrosslinked Resins Containing Dithiocarbamate Groups

Summary: In this study we report both the development of dithiocarbamate resins from the commercial hypercrosslinked resin MN-250 and the evaluation of the biocidal capacity of this material against E. coli ATCC25922 suspensions. The preparation of dithiocarbamate resins followed a synthetic pathway based on nitration of resins, reduction of nitro groups and reaction with CS₂ in an alkaline medium. The biocidal capacity was evaluated by means of elution of E. coli suspensions (10³–10⁷ cells/mL) through columns containing the resin and plating on LB nutrient medium solidified with Bacto agar. We can conclude that hypercrosslinked resins with dithiocarbamate groups have potential biocidal action.     

Curing of urea-formaldehyde resins on awood substrate

TG-DTA analysis method was used to study the curing behaviour of urea-formaldehyde (UF) adhesive resins in the presence of a wood substrate. The cure process was followed using a Setaram labsys^TM instrument in flowing nitrogen atmosphere by varying the ratio of resin and wood. Resin cure was catalysed with 2% of NH₄Cl. Curing tests were performed in the open standard platinum crucibles and in the sealed glass capsules. To characterise the reactivity of curing system, the peak temperatures in DTA curve and the mass loss values in TG curve were taken as the apparent indices. The main attention was paid to phenomena which actually take place in curing of UF resins during manufacturing of particleboards. Reactivity of the curing system depends mostly on methylol content of resin and can be adequetly evaluated by the maximum temperature of exothermic peak. The wood substrate has a substantial influence on the resin and water diffusion in system causing the changes in water/resin separation and water evaporation conditions. The water movement in curing adhesive joint was a confusing parameter in determining the peak positions. The rate of mass loss on a wood substrate is higher as compared to curing UF resin alone.     

Synthesis of phosphorus-modified poly(styrene-co-divinylbenzene) chelating resin and its adsorption properties of uranium(VI)

A new phosphorus-modified poly(styrene-co-divinylbenzene) chelating resin (PS–N–P) was synthesized by P,P-dichlorophenylphosphine oxide modified commercially available ammoniated polystyrene beads, and characterized by Fourier transform infrared spectroscopy and elemental analysis. The adsorption properties of PS–N–P toward U(VI) from aqueous solution were evaluated using batch adsorption method. The effects of the contact time, temperature, pH and initial uranium concentration on uranium(VI) uptake were investigated. The results show that the maximum adsorption capacity (97.60 mg/g) and the maximum adsorption rate (99.72 %) were observed at the pH 5.0 and 318 K with initial U(VI) concentration 100 mg/L and adsorbent dose 1 g/L. Adsorption equilibrium was achieved in approximately 4 h. Adsorption kinetics studied by pseudo second-order model stated that the adsorption was the rate-limiting step (chemisorption). U(VI) adsorption was found to barely decrease with the increase in ionic strength. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as ?G ₀, ?H ₀ and ?S ₀ were derived to predict the nature of adsorption. Adsorbed U(VI) ions on PS–N–P resin were desorbed effectively (about 99.39 %) by 5 % NaOH–10 % NaCl. The synthesized resin was suitable for repeated use.     

Synthesis and metal ion uptake studies of chelating resins derived from formaldehyde-furfuraldehyde condensed phenolic Schiff bases of 4,4'-diaminodiphenylether and o-hydroxyacetophenone

Two new chelating resins (o-HAP-DDE-HCHO and o-HAP-DDE-FFD), having multiple functional groups are synthesised by condensing the Schiff base of o-hydroxyacetophenone-4,4′-diaminodiphenylether (o-HAP-DDE) with formaldehyde and furfuraldehyde, respectively. The extent of loading of metal ions Cu(II) and Ni(II) was studied in both competitive and non-competitive conditions varying the time of contact, metal ion concentration and the pH of the reaction medium. Both the resins are able to preferentially remove Cu(II) from the mixture of Cu(II) and Ni(II) at a pH 5.89 in the batch operation, maximum % uptake being 76.8 and 84.1, respectively, for o-HAP-DDE-HCHO and o-HAP-DDE-FFD. The furfuraldehyde condensed resin was found to be more effective in removing Cu(II) ions than the formaldehyde condensed resins in batch technique. The resins exhibited little affinity for alkali and alkaline earth metal ions. Further, the furfuraldehyde condensed resin was utilised in column operation for removing Cu(II) ions. Elution study with HCl (>1.0 mol l⁻¹) resulted in removal of nearly 40–50% of loaded Cu(II) from the resin column.     

POLYESTERIMIDE-MODIFIED BISMALEIMIDE RESINS. I. EFFECT OF POLYESTERIMI DE CONTENT

ABSTRACT

A novel polyesterimide (PEsI-M) was used to improve toughness of bismaleimide (BMI) resin composed of bis(4-maleimidediphenyl) methane (BDM) and O,O′-diallyl bisphenol A (DBA). Morphologies of modified resins changed from spherical particles to inverted phase structures, depending on PEsI-M's content based on the observation of scanning electronic microscopy (SEM). PEsI-M was an effective morphology modifier so that loading of 12 pbw resulted in a diverted phase structure. Dynamic mechanical analysis (DMA), rheometrics mechanical spectroscopy (RMS) and differential scanning calorimetry (DSC) were respectively used to investigate the dynamic mechanical behavior, and the gelation time and the curing extent of unmodified and modified BMI resins. The fairly uniform morphology in 15 pbw PEsI-M modified system cured at 180°C suggests that the phase separation might take place via a spinodal decomposition mechanism. The fracture energy (G _IC ) increased with the increase of PEsI-M content in the modified system. G _IC of 15 pbw PEsI-M modified system was 0.63 times larger than that of the unmodified BMI resin.     

Poly(vinylbenzyl Pyridinium Salts) as Novel Sorbents for Hazardous Metals Ions Removal

Novel efficient complexing resins—poly(vinylbenzyl pyridinium salts) fabricated through poly(vinylbenzyl halogene-co-divinylbenzene) quaternization of N-decyloxy-1-(pyridin-3-yl)ethaneimine and N-decyloxy-1-(pyridin-4-yl)ethaneimine—were tested as adsorbents of Pb(II), Cd(II), Cu(II), Zn(II), and Ni(II) from aqueous solutions. The structure of these materials was established by ¹³C CP-MAS NMR, X-ray photoelectron spectroscopy, elemental analysis, and Fourier transform infrared spectroscopy, as well as thermogravimetric and differential thermal analyses. The textural properties were determined using scanning electron microscopy and low-temperature N₂ sorption. Based on the conducted sorption studies, it was shown that the uptake behavior of the metal ions towards novel resins depended on the type of functionalities, contact time, pH, metal concentrations, and the resin dosage. The Langmuir model was investigated to be the best one for fitting isothermal adsorption equilibrium data, and the corresponding adsorption capacities were predicted to be 296.4, 201.8, 83.8, 38.1, and 39.3 mg/g for Pb(II), Zn(II), Cd(II), Cu(II), and Ni(II), respectively. These results confirmed that owing to the presence of the functional pyridinium groups, the resins demonstrated proficient metal ion removal capacities. Furthermore, VBBr-D4EI could be successfully used for the selective uptake of Pb(II) from wastewater. It was also shown that the novel resins can be regenerated without significant loss of their sorption capacity.     

Solvent-Impregnated Resins Based on the Mixture of (2-Diphenylphosphoryl)-4-ethylphenoxy)methyl) diphenylphosphine Oxide and Ionic Liquid for Nd(III) Recovery from Nitric Acid Media

Novel solvent-impregnated resins (SIRs) were prepared by treatment of styrene–divinylbenzene copolymer (LPS-500) with mixtures of the promising polydentante extractant (2-diphenylphosphoryl)-4-ethylphenoxy)methyl)diphenylphosphine oxide (L) and an ionic liquid [C₄mim]⁺[Tf₂N]⁻for the extraction chromatography recovery of Nd(III) from nitric acid solutions. It was shown that introduction of the ionic liquid into the SIR composition results in considerable enhancement of the Nd(III) recovery efficiency compared with resin impregnated only by L in slightly acidic media. The influence of the L: ionic liquid molar ratio in the SIRs composition, their percentages, concentration of metal and HNO₃ in the eluent, and acid type on the value of synergistic effect and adsorption efficiency of Nd(III) recovery was studied. The SIR containing 40% of mixture of L and [C₄mim]⁺[Tf₂N]⁻ with molar ratio 2:1 turned out to be the most efficient. The selectivity of Nd(III) separation from light and heavy rare-earth elements was studied and the optimal conditions of Nd(III) adsorption recovery and stripping by this SIR were chosen. It was found that in recovery efficiency of Nd(III) developed SIR exceeded the SIR containing Cyanex 923 (a mixture of monodentate trialkylphosphine oxides) and [C₄mim]⁺[Tf₂N]⁻.     

Adsorption of UO2+2 by polyethylene adsorbents with amidoxime,carboxyl, and amidoxime/carboxyl group

The polyethylene (PE) adsorbents were prepared by a radiation-induced grafting of acrylonitrile (AN), acrylic acid (AA), and the mixture of AN/AA onto PE film, and by subsequent amidoximation of cyano groups of poly-AN graft chains. With an increase of AA composition in AN/AA monomer mixture, the water uptake of the grafted polyethylene film increased. In AN/AA mixture, the maximum adsorption of UO²⁺₂ was observed in the adsorbent with a ratio of AN/AA (50/50, mol%) in copolymer. The amidoxime, carboxyl, and amidoxime/carboxyl groups onto PE acted as a chelating site for the selected UO²⁺₂. The complex structure of polyethylene with three functional groups and UO²⁺₂ was confirmed by Fourier Transform Infrared (FTIR) spectroscopy.     

Fabrication of New Cellulose-Based Sorbents for Fast and Efficient Removal of Hazardous Al(III) Ions from Their Aqueous Solutions

Cellulose was used as a base polymer in two prepared resins when it was grafted by glycidyl methacrylate (GMA) then immobilized with 8-hydroxyquinoline by two different procedures. The resulting resins were characterized by infrared (IR) spectroscopy, thermogravimetric analysis (TGA), and nitrogen surface area measurements (BET). The two resins were used in the removal of hazardous Al(III) from their aqueous solutions. The present work discussed the preparation and the effect of spacer arms length used in the functionalization steps on the adsorption process. The resin with longer spacer arm showed faster kinetics compared with the other one toward Al(III) ion adsorption. Fast and efficient adsorption of hazardous Al(III) ions from drinking water by these resins indicates their applicability in water treatment applied field. Thermodynamic parameters were calculated for the studied resins and showed that they possess spontaneous exothermic nature. The regeneration efficiencies reached 90 ± 0.5% over three cycles using a mixture of 2 M HCl and 0.5 M HNO₃.     

Novel flame‐retardant thermosets: Phosphine oxide‐containing diglycidylether as curing agent of phenolic novolac resins

Phosphorus‐containing novolac–epoxy systems were prepared from novolac resins and isobutyl bis(glycidylpropylether) phosphine oxide (IHPOGly) as crosslinking agent. Their curing behavior was studied and the thermal, thermomechanical, and flame‐retardant properties of the cured materials were measured. The T_g and decomposition temperatures of the resulting thermosets are moderate and decrease when the phosphorous content increases. Whereas the phosphorous species decrease the thermal stability, at higher temperatures the degradation rates are lower than the degradation rate of the phosphorous‐free resin. V‐O materials were obtained when the resins were tested for ignition resistance with the UL‐94 test. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3516–3526, 2004     

Adsorption of Uranium (VI) Ions on Hydrazinyl Amine and 1,3,4-Thiadiazol-2(3 H)-thion Chelating Resins

Nitrogenous compounds are the most widely used in solid phase extraction due to its low cost, easy convertible to many functional groups. These have large adsorptive capacity toward heavy metal ions as rare earth elements (REEs) and uranium with ability for recovering from low concentrate solutions. Synthesis of resins were carried out by polymerization of acrylonitrile with divinyl benzene as crosslinker. Treatment of the resulted precipitate with hydrazine hydrate in ethanol produce hydrazinyl methyl amine which has high chelating capacity toward uranyl ions. 1,3,4-Thiadiazol-2(3H)-thion derivative was yielded by reaction of hydrazinyl amine with carbon disulfide in methanol. This reaction carried out in the presence of methyl benzoate and dioctyl phthalate as pore producing solvent which used to improve physical properties and adsorptive character of the resins. Optimization on the two resins during loading and elution were carried out using solution with different concentrations. The optimum factors during adsorption and elution were recognized.     

Application of thermodynamics in a specific force field to the adsorption of Al ions on the chelating resins Ostsorb Oxin, Ostsorb Salicyl, Spheron Oxin, and Spheron Salicyl: Mathematical analysis of sorption isotherms using nonlinear mean square software

The sorption mechanism of Al³⁺ on chelating resins by means of mathematical analysis of sorption isotherms using nonlinear mean square software was studied. This method should yield more detailed information than classical thermodynamics and should be more flexible than the statistical-mechanical method, so that it would make it possible to obtain fairly easily relations directly applicable in practice. This model defined the specific potential Φ_Al^R for the ion in a resin (which depends on properties of resin and ion). On the basis of this model, N and PO isotherms were derived. To study the sorption mechanism, the Freundlich, Langmuir, N and PO equations (models) of isotherms were used. It was estimated that the functional groups (8-hydroxyquinoline and salicylate) in the studied chelating resins influence Φ_Al^R and thus their mechanism and sorption capacity.