Radiation-induced Grafting Of Glycidyl Methacrylate Research Articles

Radiation-induced grafting of glycidyl methacrylate onto natural cotton fibers and trimethylamine modification for p-nitrophenol adsorption

The pre-irradiation grafting procedure was employed to achieve the grafting of natural cotton fibers (Cot) with glycidyl methacrylate (GMA). It was found that the extent of grafting (DG) of GMA was influenced by the dose of radiation that was absorbed; increased doses led to larger DGs. Dose of 10 kGy was chosen for the preparation of the GMA grafted cotton (Cot-g-GMA); this provided a DG of 200%. Subsequently, (Cot-g-GMA) was modified using Trimethylamine (TMA). In order to describe the physiochemical qualities of the fibrous adsorbent, the fibrous adsorbent was characterized with the use of FTIR, FESEM, XRD, TG-DTG, and pHpzc. In addition, the designed TMA(Cot-g-GMA) adsorbent was utilized to examine the adsorption of p-nitrophenol from aqueous solution. An examination was made of the adsorption kinetics and isotherm in order to permit the elucidation of the adsorption of p-nitrophenol behavior. In accordance with the findings emerging from this work, p-nitrophenol adsorption was described with a pseudo-second order. Moreover, the fact that the Langmuir isotherm model was the best fit was determined by the isotherm analysis. In relation to adsorption capacity, the maximum capacity achieved was 180 mg/g at 298 K. The spontaneous and exothermic nature of adsorption was identified by thermodynamic analysis. Specifically, it is evident that adsorbent can be readily reproduced and recycled with no accompanying loss of adsorptive performance in the alkaline medium. These findings indicate the potential of the fibrous bio adsorbent as a means of eliminating p-nitrophenol from wastewater.

Highly selective adsorbent by gamma radiation-induced grafting of glycidyl methacrylate on polyacrylonitrile/polyurethane nanofiber: Evaluation of CO2 capture

In this paper, a new adsorbent was investigated for carbon dioxide adsorption from a combination of two polymers, industrial polyacrylic nitrile (PAN) and industrial polyurethane (PU). PAN/PU nanofibers were prepared by electrospinning and successfully bonded to Glycidyl methacrylate (GMA). After, amination was performed with ethanolamine (EA) to make a functional group. Dynamic CO2 adsorption experiments were performed in a fixed-bed column with a mixture of two CO2/N2 gases at a concentration of 5% CO2 at atmospheric pressure and ambient temperature. The results showed the highest adsorption capacity of 2.98 mmol/g for amination with ethanolamine (168.63% degree of amination, 30 kGy radiation dose and 167.92% degree of grafting). Satisfactory results were obtained by predicting and fitting the breakthrough curves of CO2 adsorption of experimental data with Bohart-Adams, Thomas, Yoon Nelson and Yan models. Also, four adsorption–desorption cycles at low temperatures have confirmed the applicability of this adsorbent.

Controlled Process of Radiation-Induced Grafting by Chemical Vapour Deposition for the Synthesis of Metal Adsorbent

Combination of high energy radiation and chemical vapour deposition in the grafting process for the synthesis of metal adsorbent was investigated. Radiation-induced grafting of glycidyl methacrylate onto kenaf fiber was performed in vapour phase to develop adsorbent for removal of aluminum from aqueous solution. Morphological changes of cross-section kenaf fiber was observed via scanning electron microscope and the thickness of co-monomer in the final graft co-polymer was determined. The comparison in cross-section morphology between ungrafted kenaf fibers and grafted kenaf fiber shows approximately 3.88 [μm] thick of additional grafted layer. The functionalization of the grafted fiber using imidazole was calculated grametrically and verified by elemental analysis. Imidazole has proven to be effective on the adsorption of aluminum ion. It was found that the adsorbent could remove more than 99% aluminum with the highest adsorption capacity of 4.93 [mg/g] at pH 4 and 60 minutes reaction time.

An efficient and reusable quaternary ammonium fabric adsorbent prepared by radiation grafting for removal of Cr(VI) from wastewater.

A novel quaternary ammonium polyethylene nonwoven fabric for removing chromium ions from water was prepared via radiation-induced grafting of glycidyl methacrylate and further modification with N,N'-dimethylethylenediamine. The structural and morphological characteristics of the adsorbent were analyzed using Fourier transform infrared spectroscopy (FTIR), thermogravimetry and differential thermogravimetry (TG/DTG), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The influences of several principal factors, including pH value, initial Cr(VI) concentration, contact time, and coexisting anions (including SO42-, CO32-, NO3-, PO43-, and Cl-), on adsorption performance were investigated via batch tests. The results showed that the optimum removal efficiency was 99.2% at pH 3 and the maximum adsorption quantity for Cr(VI) at 25°C was 336mg/g. The adsorption kinetic parameters were better fitted with the pseudo-second-order kinetic model, and the equilibrium data were described very well by the Freundlich isotherm model. Furthermore, the as-synthesized adsorbent exhibited excellent regeneration and recyclability while maintaining high adsorption performance after five adsorption/desorption cycles.

Synthesis and Characterization of Cation-Exchange Fibers with Radiation-Induced Grafting of Glycidyl Methacrylate onto Cotton Cellulose

Conventional ion exchange beads are used for purification and demineralization of water and for various other applications in the chemical synthesis, hydrometallurgy, and agricultural industries. However, there are some disadvantages associated with ion exchange beads, such as distillation causing porosity during solvent removal, pre-swelling of beads to allow for core functionalization, and pre-swelling of beads overnight prior to end use. Fibrous ion exchange materials have advantages over the conventional ion exchange beads, including simplification of the overall preparation. In this study, a cation-exchange fiber was prepared by a radiation-induced grafting method. Glycidyl methacrylate (GMA) was grafted onto cotton cellulose using a pre-irradiation method by electronbeam irradiation. Sequential treatment with sulfonic acid was performed to react with the cation pollutants. The degree of grafting increased up to 812% with the increase of absorbed dose, reaction time and monomer concentration. It was found that the sulfonation reaction occurred smoothly with 10% sodium sulfite solution, and a high 2.0 meq/g ion exchange capacity was obtained from 140% GMA-grafted non-woven cotton fabric.

Gamma radiation-induced grafting of glycidyl methacrylate (GMA) onto water hyacinth fibers

Water hyacinth fibers (Eichhornia crassipes) were functionalized using radiation-induced graft polymerization of glycidyl methacrylate by γ-rays from 60Co source. The simultaneous grafting technique was employed wherein the water hyacinth fibers were irradiated in nitrogen atmosphere in the presence of glycidyl methacrylate dissolved in water/methanol solvent. The effects of different grafting parameters to the grafting yield were evaluated. The optimal values of solvent, absorbed dose, dose rate, and concentration of monomer were found to be 1:3 (volume/volume) water–methanol solvent, 10kGy, 8kGyh−1 dose rate and 5% volume/volume glycidyl methacrylate, respectively. Using the optimum conditions, degree of grafting of approximately 58% was achieved. The grafted water hyacinth fibers were characterized using Attenuated Total Reflectance-Fourier Transformed Infrared Spectroscopy (ATR-FTIR), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDX). The results of these tests confirmed the successful grafting of glycidyl methacrylate onto water hyacinth fibers.

Radiation-induced grafting of glycidyl methacrylate onto cotton fabric waste and its modification for anchoring hazardous wastes from their solutions

Ion exchange adsorbents based on cellulosic fabric wastes carrying sulfonic acid and amine functional groups were synthesized by radiation-induced graft polymerization of glycidyl methacrylate (GMA) with subsequent chemical modification of the epoxy groups of poly-GMA graft chains with sodium sulfite/H 2SO 4 and triethylamine, respectively. The conversion of epoxy groups into the functional groups was investigated. Factors affecting on grafting process such as radiation dose, monomer concentration and solvent were studied. The synthesized adsorbent and its applications in the removal of different types of hazardous pollutants e.g. acidic dye, cobalt, dichromate and phenols from aqueous solution were also studied.

Adsorption behavior of urokinase by polypropylene film modified with amino acids as affinity groups

In order to prepare a new-type adsorbent with an affinity ligand, polypropylene films modified with amino acid groups such as l-phenylalanine (Phe), d, l-Phe, l-cysteine (Cys), and d, l-tryptophane (Try), were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) films and subsequent amination of poly-GMA graft chains. The physical and chemical properties of the GMA-grafted PP film and the PP film modified with amino acid groups were investigated by IR and XPS. The adsorption of urokinase for the PP films modified with four kinds of amino acid groups were examined under various conditions, such as the contents of the amino acid group and pH value. The adsorption of urokinase increased with the increasing content of the amino acid group. The adsorption of the PP film modified with four kinds of amino acid groups was in the following order: l-Phe> d, l-Phe> d, l-Try> l-Cys. The adsorption amounts of urokinase by the PP film modified with four kinds of amino acid groups at pH 7.4 was higher than that at pH 9.0.

Desalination by electrodialysis with the ion-exchange membrane prepared by radiation-induced graft polymerization

Ion-exchange membranes modified with the triethylamine [–N(CH 2CH 3) 3] and phosphoric acid (–PO 3 H) groups were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto the polyolefin nonwavon fabric (PNF) and subsequent chemical modification of poly(GMA) graft chains. The physical and chemical properties of the GMA-grafted PNF and the PNF modified with ion-exchange groups were investigated by SEM, XPS, TGA, and DSC. Furthermore, electrochemical properties such as specific electric resistance, transport number of K +, and desalination were examined. The grafting yield increased with increasing reaction time and reaction temperature. The maximum grafting yield was obtained with 40% (vol.%) monomer concentration in dioxane at 60°C. The content of the cation- and anion-exchange group increased with increasing grafting yield. Electrical resistance of the PNF modified with TEA and –PO 3 H group decreased, while the water uptake (%) increased with increasing ion-exchange group capacities. Transport number of the PNF modified with ion-exchange group were the range of ca. 0.82–0.92. The graft-type ion-exchange membranes prepared by radiation-induced graft copolymerization were successfully applied as separators for electrodialysis.

Adsorption behavior of Urokinase by the polypropylene film with amine, hydroxylamine and polyol groups

For the purpose of the recovery of urokinase, the polypropylene (PP) films were modified by radiation-induced grafting of glycidylmethacrylate (GMA) and subsequent chemical modification of epoxy group of poly-GMA graft chains. The physical and chemical properties of the irradiated PP film, GMA-grafted PP film and the PP films modified with trimethylamine (TMA), hydroxylamine (HA), diethanolamine (DEA), and tri(hydroxymethyl)aminomethane (THMAM) were investigated by IR, SEM, and XPS. The adsorption of urokinase for the PP films modified with TMA, HA, DEA, and THMAM group were examined under various conditions of the functional group content, pH value and salt. It increased with increasing the content of functional group. The adsorption behavior of the PP films modified for different functional groups was in the following order: TMA>DEA>THMAM>HA. The adsorption of urokinase by the PP films with various functional groups at pH=7.4 were higher than that at pH=9.0. In TMA, DEA, and THMAM groups, the adsorption of urokinase without salts was also higher than those with salts.

Electrochemical properties of polyethylene membrane modified with sulfonic and phosphonic acid groups

Ion-exchange membranes modified with sulfonic (-SO3H) and phosphonic acid (-PO3H) groups were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polyethylene (PE) films and sub-sequent sulfonation and phosphonation of poly(GMA) graft chains. The surface area, thickness and volume of grafted PE film increased with increasing grafting yield. The specific electrical resistance of PE membrane modified with the -PO3H and -SO3H groups decreased with increasing the ion-exchange capacity. The PE membrane modified with -PO3H group had a lower specific electrical resistance than that of PE membrane modified with -SO3H group.

Adsorption of Pb2+, Cu2+ and Co2+ by polypropylene fabric and polyethylene hollow fiber modified by radiation-induced graft copolymerization

Cation-exchange adsorbents were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) fabric and polyethylene (PE) hollow fiber and subsequent phosphonation of epoxy groups of poly(GMA) graft chains. The adsorption characteristics of Pb2+, Cu2+ and Co2+ for the two cation-exchange adsorbents were studied. In the grafting of GMA onto PP fabric, the degree of grafting (%) increased with an increase in reaction time, reaction temperature, and pre-irradiation dose. The maximum grafting yield was observed around 60% GMA concentration. In 50, 130 and 250% GMA-grafted PP fabric, the content of phosphoric acid was 1.52, 3.40 and 4.50 mmol/g at 80 °C in the 85 % phosphoric acid aqueous solution for 24 h, respectively. The adsorption of Pb2+, Cu2+ and Co2+ by PP fabric adsorbent was enhanced with an increased phosphoric acid content The order of adsorption capacity of the PP fabric adsorbent was Pb2+>Co2+>Cu2+. In adsorption of Pb2+, Cu2+ and Co2+ by PE hollow fiber, the amount of Pb2+ adsorbed by the PE hollow fiber adsorbent containing 1.21 mmol/g of -PO3H wasca. 54.4 g per kg. The adsorption amount of Cu2+ and Co2+ in the same PE hollow fiber wasca. 21.0 g per kg andca. 32.1 g per kg, respectively. The order of adsorption of the PE hollow fiber adsorbent was Pb2+>Co2+>Cu2+.

Adsorption of Co2+ and Cs1+ by polyethylene membrane with iminodiacetic acid and sulfonic acid modified by radiation-induced graft copolymerization

Two modified hollow fiber membranes, the chelating hollow fiber membrane with iminodiacetic acid and the cation-exchange hollow fiber membrane with sulfonic acid group (SO3H), were prepared by radiation-induced grafting of glycidyl methacrylate onto polyethylene hollow fiber membrane and its subsequent iminodiacetation and sulfonation. The adsorption characteristics of Co2+ and Cs1+ for the 2 hollow fiber membranes were examined when the solutions of Co2+ and Cs1+ permeate across the 2 membranes, respectively. Without regard to the chelating membrane with iminodiacetic acid group and the cation-exchange membrane with sulfonic acid group (SO3H), 2 membranes were observed to adsorb Co2+ higher than Cs1+. The adsorption curves of Co2+ by IDA group-chelating fiber membrane in the presence of Na1+ and Ca2+ showed that the chelating hollow was found to have a very high selectivity for Co2+, even though there is a high concentration of Na1+ and Ca2+ in the inlet solution. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 999–1006, 1999

Adsorption of Pb2+ and Pd2+ on polyethylene membrane with amino group modified by radiation-induced graft copolymerization

Six chelating hollow fiber membranes were prepared by radiation-induced grafting of glycidyl methacrylate onto a polyethylene hollow fiber membrane and its subsequent amination. The adsorption characteristics of Pb2+ and Pd2+ for the chelating hollow fiber membranes were presented when the solution of Pb2+ and Pd2+ permeates across the chelating membrane, respectively. The degree of grafting for glycidyl methacrylate increases with increasing monomer concentration, reaction temperature, and preirradiation dose. The adsorption of Pd2+ by chelating hollow fiber membranes modified with five kinds of amines was in the following order: diethylene triamine > hexamethyl diamine > ethylene diamine > dimethyl amine > trimethyl amine. The chelating hollow fiber membrane modified with iminodiacetic acid adsorbed Pb2+ ions much more than Pd2+. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 643–650, 1999

Comparison of BSA adsorption and Fe sorption to the diol group and tannin immobilized onto a microfiltration membrane

A diol group and tannin were immobilized on a polyethylene microfiltration (MF) membrane by radiation-induced grafting of glycidyl methacrylate (GMA) and subsequent chemical modifications. A quantitative hydrolysis of the GMA-grafted membrane with sulfuric acid provided a diol group density of 7.7 mol per kg of the starting MF membrane. Coupling of the GMA-grafted membrane with tannin resulted in a 4% molar conversion of the epoxide group. Breakthrough curves of bovine serum albumin (BSA) and ferrous ions during permeation of their solution across the modified membrane were compared. The breakthrough curves resulting from BSA adsorption onto the grafted polymer branches containing the diol group and tannin were insensitive to the residence time of the solution across the membranes, whereas, the breakthrough curve of the ferrous ions was dependent on the residence time because of their lower binding rate to the tannin immobilized on the grafted polymer branches.

放射線グラフト重合法によるアフィニティ膜の開発

Membrane-based affinity chromatography has advantages over conventional bead-based chromatography for the following two reasons : (1) the module charged with hollow fibers requires a much lower operating pressure than a bead-packed bed ; and (2) as the biomolecule can be transported by convection to the ligand immobilized on the inner surface of the microporous membrane, faster adsorption onto the affinity membrane can be attained. Hollow-fiber affinity membranes containing phenylalanine and tryptophan as ligands were prepared by the radiation-induced grafting of glycidyl methacrylate onto a porous polyethylene hollow fiber, followed by coupling of the epoxide group produced with Phe and Trp. The remaining epoxide group is quantitatively converted into a diol group. The diol group renders the polymer surface hydrophilic and prevents nonselective adsorption. To evaluate the adsorption behavior of the membrane, the gamma-globulin-containing buffer solution was permeated from the inside to the outside of the Trp-containing hollow-fiber affinity membrane. The breakthrough curves as a function of effluent volume coincided irrespective of the flow-rate, i. e., the residence time of the solution across the membrane, as a result of negligible diffusional mass transfer resistance.

Protein adsorption capacity of a porous phenylalanine-containing membrane based on a polyethylene matrix

A porous hollow-fibre membrane containing l-phenylalanine as a pseudo-biospecific ligand has been prepared by radiation-induced grafting of glycidyl methacrylate onto polyethylene microfiltration hollow fibre, followed by coupling of the produced epoxide group with l- phenylalanine. The remaining epoxide group was hydrolysed into a diol group with sulphuric acid. The l-phenylalanine and the diol group acted in a complementary way as a pseudo-biospecific ligand and a hydrophilic group, respectively. The adsorption capacity of bovine gamma globulin on the resulting porous adsorbent could be determined by the specific surface area of the adsorbent when the ligand was in excess over the protein.

Adsorption and elution of bovine γ-globulin using an affinity membrane containing hydrophobic amino acids as ligands

A hollow-fibre affinity membrane containing hydrophobic amino acids as ligands was prepared by the radiation-induced grafting of glycidyl methacrylate onto a porous polyethylene hollow fibre and subsequent coupling with phenylalanine (Phe) or tryptophan (Trp). The densities of the Phe and Trp ligand of the resulting affinity membrane were 0.4 and 0.4 mol/kg, respectively. The Trp-containing affinity membrane exhibited a higher amount of adsorbed bovine γ-globulin (BGG) than the Phe-containing membrane. To evaluate the adsorption behaviour of the membrane, the BGG-containing buffer solution was permeated from the inside to the outside of the Trp-containing hollow-fibre affinity membrane through the ligand-immobilized pores. The breakthrough curves as a function of effluent volume coincided irrespective of the flow-rate, i.e. the residence time (55–220 s) of the solution across the membrane (thickness 0.83 mm), as a result of negligible mass transfer resistance. A series of chromatographic procedures, (adsorption—washing—elution) was repeated twice and a satisfactory quantitative elution was attained. The reproducible profile of the flux and the protein concentration assured a quantitative cycle of chromatography using the affinity membrane containing Trp as a ligand.