Graft Copolymerization Of Methacrylic Acid Research Articles

Efficient removal of Cd2+ ions and methylene blue from aqueous solutions by polyanionic sodium alginate-derived hydrogel

Considering the purification technology based on the fabrication of efficient adsorbents for the effective removal of water contaminants, we developed a polyanionic superabsorbent hydrogel for its application in the adsorption of cadmium ions (Cd2+) and methylene blue (MB). The hydrogel was prepared by graft copolymerization of methacrylic acid, acrylamide, and 2-acrylamido-2-methyl-1-propanesulfonic acid onto sodium alginate. The hydrogel structure, thermal stability, surface morphology, and surface area were studied using FT-IR, SEM, EDX, TGA, and BET techniques.The hydrogel capacity to remove Cd2+ MB from aqueous solutions was investigated at different contact times, pH, sorbent dosage, contaminant concentrations, temperature salinity, and ion selectivity. To understand the hydrogel sorption behavior, different adsorption kinetics and isotherms models were employed. The hydrogel exhibited impressive efficacy in the removal of Cd2+ and MB ions, achieving removal efficiencies of up to 87% and 97.5%, respectively, under a sorbent dosage of 0.15 g/100 mL and a temperature of 25°C. Utilizing the Langmuir isotherm model, the maximum sorption capacities were determined to be 526 mg/g for cadmium ions and 131.5 mg/g for methylene blue. Regeneration experiments confirmed the reusability of the hydrogel, highlighting its potential as an effective adsorbent for Cd²⁺ and MB dye.

Optimization of synthesis conditions for graft copolymerization of methacrylic acid onto Garcinia kola pods and use in the sequestration of cationic dyes from simulated wastewaters

Optimization of synthesis conditions for graft copolymerization of methacrylic acid onto Garcinia kola pods and use in the sequestration of cationic dyes from simulated wastewaters

A porous fabric-based molecularly imprinted polymer for specific recognition of tetracycline by radiation-induced RAFT-mediated graft copolymerization

Despite technical and methodological advances, the selective separation of antibiotics from aqueous media remains a challenge. In this work, a novel molecularly imprinting polymer (MIP) with specific recognition sites was constructed by radiation-induced RAFT-mediated graft copolymerization of methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) from PE/PP nonwoven fabric for tetracycline hydrochloride (TC) removal. Binding isotherm and kinetics were found to follow Freundlich and pseudo-second-order model, respectively. The as-synthesized molecularly-imprinted fabric exhibited excellent binding performance towards TC, with the maximum adsorption capacity and imprinting factor of 46.7 mg g−1 and 3.6, respectively. Moreover, it removed approximately 95% of TC from the aqueous media, also performed well in real environmental samples. For comparison purposes, MIPs obtained with conventional grafting performed significantly lower than those attained by RAFT-mediated grafting. After ten consecutive adsorption and desorption cycles, the fabric-based molecularly-imprinted material retained excellent stability and reusability with a performance loss of only 3.6%, which could facilitate its potential application on an industrial scale.

Formulation and evaluation of interpenetrating polymeric network for controlled drug delivery

Novel Cytarabine-loaded agarose and fenugreek-based hydrogel were formulated via the crosslinking process. Graft copolymerization of methacrylic acid (MAA) on agarose and fenugreek was carried out by using methylene bisacrylamide (MBA) as a crosslinker and potassium persulfate as an initiator. The influence of different formulation ingredients (fenugreek, agarose, MBA, MAA) on swelling index, percentage drug release, and percentage gel content were investigated. It was observed that an increase in the concentration of fenugreek and agarose resulted in an increase in the swelling index (72.45–97.17%). However, an increase in the amount of MBA led to a decrease in the swelling index from 74.23% to 57.74%. A similar result tendency was noted in the case of drug release. FTIR was employed to elucidate effective grafting. The thermal behavior of hydrogel was evaluated through TGA and DSC analysis whereas surface morphology was elucidated through SEM. Release studies were performed at both acidic and basic pH, that is, 1.2 and 7.4. Hence, formulated biocompatible hydrogels proved to be a promising system for the controlled delivery of Cytarabine.

Dual Function of Cellulose Triacetate–Graft–Polymethacrylic Acid Films for Dyes Removal and for High-Dose Radiation Dosimetry

Graft copolymerization of methacrylic acid (MAc) onto cellulose triacetate (CTA) films was conducted by gamma rays. The grafting conditions were optimized. The structure of grafted CTA films was characterized by Fourier transform infra red–attenuated total reflection, scanning electron microscopy, thermal gravimetric analysis, CHNS/O microanalyzer and, surface area and porosity analyzer. The grafted CTA films were exploited in adsorption of ethyl violet (EV) and phenol red (PR) dyes. The adsorption capacity of the grafted CTA films was investigated at various variables. The adsorption isotherms and kinetic study were examined. Further, the dyed grafted CTA films were used in measurements of high dose radiation. The results indicate that the useful dose range extents up to 440 and 300 kGy for EV and PR, respectively. The effects of relative humidity during irradiation, shelf-life, pre- and post-irradiation storage in dark and indirect daylight conditions on dosimeters performance were investigated.

Chemical Modification of Chitosan in order to Inverse Swelling Behavior: Comparison between Crosslinking, Michael Addition and Graft Copolymerization Reactions

In the present work, three methods were used to inverse chitosan swelling behavior including, conjugation of p-amino benzoic acid (PABA) on cross-linked chitosan in different condition, Michael addition reaction of acrylic acid (AA) on chitosan and finally graft copolymerization of methacrylic acid (MMA) on chitosan. We couldn’t inverse chitosan swelling behavior by the Michael addition reaction of acrylic acid, but conjugation of PABA on cross-linked chitosan inversed the chitosan swelling behavior. In addition, the graft copolymerization of MMA on chitosan was also successful. In general, the third method, among the above-mentioned modifications provided the best results.Bangladesh Pharmaceutical Journal 18(2): 110-117, 2015

Influence of Preparation Conditions on the Properties of Keratin-Based Polymer Hydrogel

In this study, a novel keratin-based polymer hydrogel (K-PmaH) was successfully prepared by graft-copolymerization of methacrylic acid onto keratin, cross-linked with N,N’-methylene-bis-acrylamide, then blended with agar. The influence of reaction temperature, dosage of reductant, initiator, and monomers on graft-copolymerization and that of heating methods on blending process was investigated. The results demonstrated that the dosage of DTT has prominent effects on the graft-copolymerization, and microwave radiation has significant effects on hydrogel properties. The swelling properties and in vitro degradation characteristic of K-PmaH also have been investigated, respectively. Determination results indicate that the K-PmaH has moderate swelling capacity in water and swelling–shrinkage behavior in saline solution. Moreover, K-PmaH reveals an excellent degradable characteristic in pepsin solution and trypsin solution. Consequently, the hydrogel K-PmaH is expected to be applied to the wounds and burns covering materials or bandages.

Positively charged functionalized silica nanoparticles as nontoxic carriers for triggered anticancer drug release

The aim of this study is the synthesis of pH-responsive cationic silica nanoparticles (NPs) by pyridinium-based ionic liquid for the improved sustained release formulations of methotrexate (MTX) as an anionic anticancer drug. Fanctionalized cationic silica NPs were successfully prepared via graft copolymerization of methacrylic acid (MAA) onto vinyl-bond-modified silica NPs. The prepared NPs were characterized using the scanning electron microscopy (SEM), the infrared spectroscopy (IR), and the thermogravimetric analysis. The resultant NPs were uniform spherical NPs with a mean diameter of approximately 160 ± 20 nm. We explored the ionic interaction of MTX NPs in order to generate pH-responsive controlled release system. The cumulative release of MTX-loaded composite microspheres shows a highly desirable precise pH-responsive drug release performance, i.e. loaded drug would not leak in physiological pH (7.4), but would release in a sustained way, where the pH value is lower (4). The protonation of carboxyl groups at mildly acidic condition resulted in a faster dissociation of copolymer/MTX complex, leading to an accelerated release of MTX at pH 4. Thus, complexation of MTX with NPs yielded a drug delivery system affording a pH-triggered release of MTX in an acidic environment. The in vitro cytotoxicity test by MTT assay against breast cancer cells, MCF7 indicates that NPs are nontoxic and suitable to use as drug carriers. Antitumor activity of the MTX-loaded nanocomposites against the cells was kept over the whole experiment process. The results showed that the MTX could be released from the nanocomposites without losing cytotoxicity.

Synthesis And Characterization Of Graft copolymers Of Methacrylic Acid Onto Gelatinized potato Starch Using Chromic Acid Initiator In Presence Of Air

The graft copolymerization of methacrylic acid onto gelatinized potato starch has been carried out at 70 0 C using chromic acid as initiator. The different reaction parameters such as effect of temperature, initiator and monomer concentrations were optimized to determine the maximum percentage grafting. The maximum grafting efficiency of 87.5% was optimized at reaction temperature (60 0 C), monomer concentration (0.81molL -1 ) and initiator concentration (0.02 mmol.L -1 ). The grafted samples were evaluated for other physico-chemical properties such as swelling behavior, moisture absorption and chemical resistance. The grafted samples were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA) techniques. The additional peaks observed in FTIR spectra of grafted samples confirmed the grafting of monomer onto gelatinized starch. The grafted co-polymers have been successfully used for the removal metal ions and organic dyes from aqueous system.

Crosslinked Graft Copolymer of Methacrylic Acid and Gelatin as a Novel Hydrogel with pH-Responsiveness Properties.

In this paper, a novel gelatin-based hydrogel was synthesized through crosslinking graft copolymerization of methacrylic acid (MAA) onto gelatin, using ammonium persulfate (APS) as a free radical initiator in the presence of methylenebisacrylamide (MBA) as a crosslinker. A proposed mechanism for hydrogel formation was suggested and the structure of the product was established using FTIR spectroscopy and gravimetric analysis of the products. Moreover, morphology of the samples was examined by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA/DTG). The effect of reaction variables such as concentration of APS and MBA were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. The gelatin-g-PMAA hydrogel exhibited a pH-responsiveness character so that a swelling-deswelling pulsatile behavior was recorded at pHs 2 and 8. This on-off switching behavior makes the hydrogel as a good candidate for controlled delivery of bioactive agents.

Tuning of the vinyl groups’ spacing at surface of modified silica in preparation of high density imprinted layer-coated silica nanoparticles: A dispersive solid-phase extraction materials for chlorpyrifos

This paper reports the preparation of high density imprinted layer-coated silica nanoparticles toward selective recognition and fast enrichment of chlorpyrifos (CP) from complicated matrices. The molecularly imprinted polymers (MIPs) were successfully coated at the surface of modified silica through using the chemical immovable vinyl groups at the nanoparticles' surface, followed by the graft copolymerization of methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) in the presence of templates CP. It has been demonstrated that the space of end vinyl groups at the surface of silica can be controlled by changing the condition of chemical modification, regulating the thickness of imprinted shells and the density of efficient imprinted sites. After removal of templates by solvent extraction, the recognition sites of CP were created in the polymer coating layer. The CP-imprinted nanoparticles exhibited high recognition selectivity and binding affinity to CP analyte. When the CP-imprinted nanoparticles were used as dispersive solid-phase extraction (dSPE) materials, the high recovery yields of 76.1-93.5% from various spiked samples with only 1microg/mL analyte were achieved by one-step extraction. These results reported herein provide the possibility for the separation and enrichment of CP from complicated matrices by the molecular imprinting modification at the surface of common silica nanoparticles.

Modification of κ‐carrageenan by graft copolymerization of methacrylic acid: Synthesis and applications

AbstractIn this article, the synthesis of κ‐carrageenan‐g‐methacrylic acid has been reported by free radical polymerization initiated by Potassium peroxymonosulphate/glycolic acid redox pair under nitrogen atmosphere. The reaction conditions have been optimized by varying the reaction conditions, including the concentration of monomer, peroxymonosulphate, glycolic acid, sulphuric acid, κ‐carrageenan along with reaction time and temperature. It has been observed that the maximum yield has been obtained at time 120 min, temperature 40°C, at 20 × 10−2 mol dm−3 concentration of methacrylic acid, 1.0 g dm−3 concentration of κ‐carrageenan and 16 × 10−3 mol dm−3 concentration of peroxymonosulphate. The graft copolymer is characterized by Forier Transform Infrared Spectroscopy and Thermal analysis. Water swelling capacity of graft copolymer has been determined. Intrinsic viscosity has been obtained for both grafted and ungrafted κ‐carrageenan. Metal ion sorption and flocculation performance of synthesized graft copolymer has been studied with respect to the ungrafted substrate. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Studies of adsorption of alkaline trypsin by poly(methacrylic acid) brushes on chitosan membranes

AbstractPoly(methacrylic acid)‐grafted chitosan membranes (chitosan‐g‐poly(MAA)) were prepared in two sequential steps: in the first step, chitosan membranes were prepared by phase‐inversion technique and then epichlorohydrin was used as crosslinking agent to increase its chemical stability in acidic media; in the second step, the graftcopolymerization of methacrylic acid onto the chitosan membranes was initiated by ammonium persulfate (APS) under nitrogen atmosphere. The chitosan‐g‐poly(MAA) membranes were first used as an ion‐exchange support for adsorption of trypsin from aqueous solution. The influence of pH, equilibrium time, ionic strength, and initial trypsin concentration on the adsorption capacity of the chitosan‐g‐poly(MAA) membranes have been investigated in a batch system. Maximum trypsin adsorption onto chitosan‐g‐poly(MAA) membrane was found to be 92.86 mg mL−1 at pH 7.0. The experimental equilibrium data obtained for trypsin adsorption onto chitosan‐g‐poly(MAA) membranes fitted well to the Langmuir isotherm model. The adsorption data was analyzed using the first‐ and second‐order kinetic models, and the experimental data was well described by the second‐order equation. More than 97% of the adsorbed trypsin was desorbed using glutamic acid solution (0.5M, pH 4.0). In addition, the chitosan‐g‐ poly(MAA) membrane prepared in this work showed promising potential for various biotechnological applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Chromium(III) removal from water and wastewater using a carboxylate-functionalized cation exchanger prepared from a lignocellulosic residue

This study concerns with the development of a new cation exchanger (SDGPMA SP COOH) carrying spacer (SP) group [ CONH (CH 2) 2 NHCO(CH 2) 2 ] and carboxylate functional group at the chain end. The preparation process was carried out through graft copolymerization of methacrylic acid onto sawdust, SD (a lignocellulosic residue) using ceric ammonium nitrate as an initiator. The poly(methacrylic acid) grafted SD (SDGPMA) was subsequently treated with thionyl chloride followed by ethylenediamine (transmidation) and succinic anhydride (carboxyfunctionalization) treatments. Infrared spectroscopy and potentiometric titrations were used to confirm graft copolymer formation and carboxylate functionalization. The effectiveness of the SDGPMA SP COOH in removing Cr(III) from water and wastewater was evaluated by the batch technique. The influence of different experimental parameters such as solution pH, contact time, absorbent dose, Cr(III) concentration and temperature on removal process was evaluated. The maximum Cr(III) removal was observed at the initial pH of 7.0. The Cr(III) was removed by SDGPMA SP COOH up to 99.3 and 92.6% from an initial concentration of 10 and 25 mg/L, respectively, at pH 7.0. Equilibrium time was reached within 4 h. Kinetic data were analyzed using the pseudo-first-order, pseudo-second-order and Elovich equations. The data fitted very well to the pseudo-second-order rate expression. The Langmuir, Freundlich and Temkin equations were applied to the experimental isotherm data and the Langmuir model was found to be in better correlation with the experimental data. The monolayer adsorption capacity for Cr(III) removal was found to be 36.63 mg/g. The adsorption efficiency towards Cr(III) removal was tested using simulated tannery wastewater. The adsorbed Cr(III) on SDGPMA SP COOH can be recovered by treating with 0.1 M HCl. Four adsorption/desorption cycles were performed without significant decrease in removal capacity. The results showed that SDGPMA SP COOH developed in this study exhibited considerable adsorption potential for application in removal of Cr(III) from water and wastewaters.

Preparation of ion-exchange beads based on poly(methacrylic acid) brush grafted chitosan beads: Isolation of lysozyme from egg white in batch system

Poly(methacrylic acid) brush grafted crosslinked-chitosan (chitosan- g-poly(MAA)) beads were prepared in two sequential steps: in the first step, chitosan beads were prepared by phase-inversion technique and then were crosslinked with epichlorohydrin under alkaline condition; in the second step, the graft copolymerization of methacrylic acid onto the chitosan beads was initiated by ammonium persulfate (APS) under nitrogen atmosphere. The chitosan- g-poly(MAA) beads were first used as an ion exchange support for adsorption of lysozyme (LYZ) from aqueous solution. The influence of pH, equilibrium time, ionic strength and initial LYZ concentration on the adsorption capacity of the chitosan- g-poly(MAA) ion-exchange beads has been investigated in a batch system. Maximum LYZ adsorption onto chitosan- g-poly(MAA) beads was found to be 65.7 mg/g at pH 6.0. The experimental equilibrium data obtained LYZ adsorption onto chitosan- g-poly(MAA) ion-exchange beads fitted well to the Langmuir isotherm model. Kinetics parameters of this adsorption system were also analyzed by using the equilibrium experimental data. The result of kinetic analyzed for LYZ adsorption onto ion-exchange beads showed that the second order rate equation was favourable. Finally, the chitosan- g-poly(MAA) ion-exchange beads were used for the purification of LYZ from egg white in batch system and the purity of the eluted LYZ from ion-exchange chitosan- g-poly(MAA) beads was determined as 94% by HPLC from single step purification.

Poly (methacrylic acid) modified biomass for enhancement adsorption of Pb2+, Cd2+ and Cu2+

AbstractIn this study, the graft copolymerization of methacrylic acid onto the biomass of baker's yeast was carried out in aqueous medium using potassium persulfate (PPS) as initiator. The poly (methacrylic acid) modified biomass obtained was characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS) and microscopic analyses. The number of functional groups was determined by potentiometric titration. The adsorption capacity of the modified biomass for Pb2+, Cd2+ and Cu2+ showed a significant increase compared with the pristine biomass, due to the presence of a large number of functional groups. According to the Langmuir equation, the maximum uptake capacities (qm) for Pb2+, Cd2+ and Cu2+ were 243.9, 108.7 and 73.5 mg g−1, respectively. Adsorption kinetics study showed that completion of the adsorption process needed only 30 min. The loaded biosorbent was regenerated using EDTA solution and used repeatedly three times with little loss of uptake capacity. Good results were obtained when the modified biomass was used to treat simulated wastewater containing Pb2+, Cd2+ and Cu2+. Copyright © 2007 Society of Chemical Industry

Graft copolymerization of methacrylic acid onto xanthan gum by Fe2+/H2O2 redox initiator

AbstractThe graft copolymer of xanthan gum with methacrylic acid was synthesized in inert atmosphere by using Fentos reagent as a redox initiator. The effect of reaction conditions on grafting parameters [G(%), E(%), C(%), A(%), H(%), and Rg] was investigated. Similar trend was observed on increasing the concentration of ferrous ion and hydrogen peroxide from 4.0 to 20.0 × 10−3 mol dm−3 and 2.5 to 10 × 10−3 mol dm−3 respectively, i.e., initially grafting parameters increased and after a certain range of concentration grafting parameters showed decreasing trend. Hydrogen ion shows influenced result i.e., small increment of concentration in hydrogen ion presents much increment in percent of grafting. It was observed that the [G(%), E(%), C(%), A(%), and Rg] increased upto 6.67 × 10−2 mol dm−3 concentration of methacylic acid after that it decreased. Maximum G(%) was obtained at minimum concentration of xanthan gum i.e., at 40 × 10−2 g dm−3. The optimum temperature and time duration of reaction for maximum percentage of grafting were found to be 45°C and 150 min respectively. Thermogravimetric analysis showed that the xanthan gum‐g‐methacrylic acid is thermally more stable than pure gum. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

Preparation and application of chitosan/poly(methacrylic acid) graft copolymer

2,2-Azobis(2-methylpropionitrile) (AMPN) was investigated as initiator for the graft copolymerization of methacrylic acid (MAA) onto chitosan. A number of variables in the grafting reaction were investigated, including AMPN and monomer concentration, material to liquor ratio, duration, and temperature of polymerization reaction. The graft copolymers were evaluated in terms of graft yield, homopolymer, monomer conversion percent, and grafting efficiency. The apparent viscosity of the resultant polymerization product was measured at different rates of shear. The optimum conditions for grafting of MAA onto chitosan are: AMPN; 0.125%, material-to-liquor ratio 1:30, and reaction temperature; 80 °C. The resultant product was used for preparation of crosslinked chitosan/poly(MAA) graft copolymer (CCPMAAGC) by its reaction with epichlorohydrin in alkaline medium. The result obtained reflects the feasibility for using CCPMAAGC as adsorbent for both Cu 2+ ions and hepatit A virus.

Ce(IV)‐induced graft copolymerization of methacrylic acid on electrospun polysulphone nonwoven fiber membrane

AbstractCe(IV)‐induced graft copolymerization of methacrylic acid (MAA) on polysulphone (PSU) surface is studied. After pretreatment either by formaldehyde solution or by air glow discharge plasma, the PSU fiber membrane was immersed in MAA solution with Ce(IV) and heated under 80°C under N2 protection. The MAA was induced by the Ce(IV) redox initiation system to polymerize on the PSU fiber membrane surface. It was found that the pretreatment of the membrane is a very necessary condition for the graft copolymerization to obtain high graft degree. For both the formaldehyde and the air glow discharge plasma pretreated membrane, the graft degree increase with the reaction time. To study the reaction mechanism, control experiments were carried out. Membrane surfaces were characterized by ATR‐FTIR and XPS. The reaction mechanism of the graft copolymerization was discussed based on the experimental data. The effect of the graft copolymerization on the membrane's structure and water permeability was finally studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3835–3841, 2006

Graft copolymerization of methacrylic acid onto guar gum, using potassium persulfate as an initiator

AbstractGraft copolymerization of methacrylic acid (MAA) onto guar gum (GG) was carried out by free radical initiation mechanism by using potassium persulfate (PPS) as an initiator. It was found that % grafting, grafting efficiency, and % conversion were all dependent on the concentration of PPS, MAA, reaction temperature, and reaction time. Using PPS, the maximum % grafting was ascertained to be 241 at the optimum conditions of 60°C reaction temperature, 3 h of reaction time, 1.1 mmol of PPS, and 0.058 mol of MAA. Plausible mechanism for grafting reaction was suggested. The graft copolymer formed was characterized by Fourier transform infrared and differential scanning calorimetry. The graft copolymer formed could find applications in drug delivery. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 618–623, 2006