Non-Gaussian elasticity of poly(2-acrylamido-2-methylpropane sulfonic acid) gels

Summary A series of strong polyelectrolyte hydrogels was prepared from the sodium salt of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) as the monomer and N,N-methylene(bis)acrylamide (BAAm) as a crosslinker. The hydrogels prepared between 9 and 50 mol % BAAm appeared homogeneous to eye but exhibited large spatial fluctuations of polymer concentration, as determined by the light scattering measurements. The elasticity tests show that the modulus of elasticity of gels increases with increasing degree of swelling, starting from the gel preparation state. Thus, the mechanical properties of the hydrogels are improved on their swelling in water. It was shown that the hydrogels even at a gel state just after their preparation are in the non-Gaussian regime due to the high degree of spatial gel inhomogeneity.     

Solvent-, ion- and pH-specific swelling of poly(2-acrylamido-2-methylpropane sulfonic acid) superabsorbing gels

Homopolymer hydrogel of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and its nanocomposite counterpart were prepared to study their swelling properties. The hydrogels showed ability to absorb and retain electrolytes as well as binary mixtures of water and organic solvents (i.e., methanol, ethanol, acetone, ethylene glycol (EG), polyethylene glycol, N-methyl-2-pyrrolidone (NMP), and dimethylsulfoxide (DMSO). The nanocomposite gel exhibited lower swelling in all solvent compositions in comparison with non-composite gel. Unlike conventional acrylic acid-based hydrogels, the poly(AMPS) gels showed superabsorbing capacity in pure ethanol, methanol, EG, DMSO and NMP. Meanwhile, swelling capacity of poly(AMPS) hydrogel in DMSO-water mixtures was surprisingly found to be even higher than that in water. This extraordinary superswelling behavior was explained based on the interactions involved in solvation as well as the solubility parameters. The gels showed pH-independent superabsorbency in a wide range of pH (3–11). Saline-induced swelling transitions were also investigated and the ionic interactions were confirmed by FTIR spectroscopy.     

AA/AMPS水凝胶的交联聚合反应动力学及其机理

Crosslink polymerization kinetics of poly(acrylic acid-co-2-acrylamido-2-methylpropane sulfonic acid),AA/AMPS hydrogels,was investigated by using dilatometry in the presence of sodium persulfate as initiator and N,N’-methylene bis(acrylamide) as crosslinker.It was found that the reaction for the crosslink polymerization of AA/AMPS hydrogels had orders of 0.58,1.14,and 0.86 with respect to the initiator,AMPS,and AA,respectively.From the Arrhenius plots,the activation energy of the crosslink polymerization was found to be about 140 and 89 kJ·mol-1 in the presence and absence of the crosslinker,respectively,in the temperature range from 45 to 65 °C.It was noted that the crosslinker had effects on the reaction order of the initiator and the activation energy due to the formation of cross-linked networks,which was verified by Fourier transfer infrared (FTIR) spectrum.To further confirm the influences of the cross-linked network structure on kinetic parameters of the crosslink polymerization,a mechanism was proposed,which highlights the different termination routes between free radical polymerization and crosslink polymerization.These results suggest that dilatometry provides a convenient tool for crosslink polymeri-zation study,and confirm that the cross-linked networks are formed in the crosslink polymerization.     

Copolymerization of 2-acrylamido-2-methylpropane sulfonic acid with 2-hydropropyl methacrylate

Summary Copolymerization of 2-acrylamido-2-methylpropane sulfonic acid (AMPS, monomer 1) with 2-hydropropyl methacrylate (monomer 2) was conducted in pure water at 80°C. The reactivity ratios estimated from the compositional data of the copolymers at low conversion are r₁=0.04±0.04 and r₂=6.30±0.48, and values of Q₁ and e₁ are 0.16 and 1.37, respectively. Copolymer microstructure predicted by statistical calculation shows mean sequence length of M_I shorter than 2. These results can be attributed to the strong repulsion between the ionized chain radical and charged monomer of AMPS.     

Removal of basic dyes from aqueous solutions by crosslinked‐acrylic acid/acrylamidopropane sulfonic acid hydrogels

In this study, Acrylic acid (AA)/2‐acrylamido‐2‐methlypropane sulfonic acid (AMPS) hydrogels were prepared by free radical polymerization in aqueous solutions of AA, AMPS, and N,N‐methylenebisacrylamide (NMBA) as crosslinker. Potassium persulfate (PPS)/potassium bisulfide (PBS) were used as initiator and accelerator pair. The water absorption capacities and dye adsorption properties of the hydrogels were investigated. Adsorption properties of the hydrogels were evaluated by depending on different adsorption conditions such as different initial dye concentration and contact time. The concentrations of the dyes were determined using UV/Vis Spectrophotometer at wavelength 530 nm for safranine T (ST) and 622 nm for brilliant cresyl blue (BCB). Adsorption kinetic studies showed that pseudo‐first order kinetic model is suitable to explain the adsorption kinetic data of the hydrogels. Langmuir and Freundlich isotherm models were used to describe adsorption data. The result revealed that the adsorption of basic dyes onto hydrogels fit very well both Langmuir and Freundlich isotherms. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Removal of methylene blue from aqueous solution by sorption on lignocellulose-g-poly(acrylic acid)/montmorillonite three-dimensional cross-linked polymeric network hydrogels

Batch lignocellulose-g-poly(acrylic acid)/montmorillonite (LNC-g-PAA/MMT) hydrogel nanocomposites were applied as adsorbents. The nanocomposites were characterized by FTIR, XRD, SEM, and TEM. The results showed that montmorillonite (MMT) could react with the monomers and change the structure of polymeric network of the traditional superabsorbent materials, an exfoliated structure was formed in the nanocomposites. The effect of process parameters such as MMT content (wt%), contact time (t), initial concentration of dye solution (C ₀), adsorption temperature (T), and pH value (pH) of the dye solution for the removal of methylene blue (MB) from aqueous solution were also studied. The results showed that the adsorption capacity for MB increased with increasing contact time, initial dye concentration, and pH value, but decreased with increasing MMT content and temperature. The adsorption kinetics were better described by the pseudo-second-order equation, and their adsorption isotherms were better fitted for the langmuir equation. By introducing 20 wt% MMT into LNC-g-PAA polymeric network, the obtaining hydrogel composite showed the high adsorption capacity 1994.38 mg/g and economic advantage for MB. The desorption studies revealed that the composite provided the potential for regeneration and reuse after MB dye adsorption, which implied that the composite could be regarded as a potential adsorbent for cationic dye MB removal in a wastewater treatment process.     

Removal of methylene blue from aqueous solutions by adsorption onto chemically activated halloysite nanotubes

This study examines the adsorption behavior of methylene blue (MB) from aqueous solutions onto chemically activated halloysite nanotubes. Adsorption of MB depends greatly on the adsorbent dose, pH, initial concentration, temperature and contact time. The Langmuir and Freundlich models were applied to describe the equilibrium isotherms and the Langmuir model agrees very well with experimental data. The maximum adsorption capacities for MB ranged from 91.32 to 103.63 mg·g⁻¹ between 298 and 318 K. A comparison of kinetic models applied to the adsorption data was evaluated for pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion equation. The results showed the adsorption process was well described by the pseudo-second-order and intra-particle diffusion mode. Thermodynamic parameters suggest that the adsorption is spontaneous and endothermic. The obtained results indicated that the product had the potential to be utilized as low-cost and effective alternative for dye removal in wastewater.     

Adsorption of phenazine dyes using poly(hydroxamic acid) hydrogels from aqueous solutions

Swelling and adsorption properties of poly(hydroxamic acid), (PHA) hydrogels in aqueous solutions of some phenazine dyes such as Neutral Red, Safranin T, and Janus Green have been investigated. PHA hydrogels containing N,N′ methylenebisacrylamide or ethyleneglycoldimethacrylate were used in experiments on swelling, diffusion and adsorption of the dyes. The equilibrium swelling (S_eq) values of PHA hydrogels in aqueous solutions of the phenazine dyes were calculated as 2.16–33.25 g g^?1. Swelling kinetic parameters such as initial swelling rate, swelling rate constant, and maximum swelling were found. Dye diffusion into hydrogels was found to be non‐Fickian in character. Diffusion coefficients are ranged 1.32 × 10^?6 cm² s^?1 ? 44.70 × 10^?6 cm² s^?1. Adsorption of the phenazine dyes onto PHA hydrogels was studied by batch technique. PHA hydrogels in the phenazine dye solutions showed the dark coloration. The data was found that Freundlich isotherm model fits. According the Freundlich constants, the adsorption isotherms are of S‐type in Giles classification. All swelling and binding parameters for PHA‐EGDMA were found to be higher than those for PHA‐NNMBA. The type of crosslinker influenced the swelling, binding, and sorption more than the type of dye. Finally, it can be said that PHA hydrogels may be used a sorbent for removal of dyes. POLYM. ENG. SCI., 58:310–318, 2018. © 2017 Society of Plastics Engineers     

Removal of nitrite ions from aqueous solutions by poly(N,N‐dimethylamino ethylmethacrylate) hydrogels

Removal of nitrite ions from aqueous solutions by protonated poly(N,N‐dimethylamino ethylmethacrylate) hydrogels (P(DMAEMA)) was investigated. We have shown that polycationic and pendant secondary amine group containing P(DMAEMA) hydogels is very efficient and highly selective for the removal of nitrite ions from aqueous solutions at even in very high concentrations. Adsorption studies have shown that pH of the nitrite solution has influence on the nitrite ion uptake capacity of P(DMAEMA) hydrogels. The adsorption capacity of hydrogels had been increased up to 3100 mg NO/g dry gel, by changing pH of the solution. The results of the adsorption studies showed that the interaction between nitrite ions and quaternized amine groups agree with the Langmuir‐type isotherm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6023–6027, 2006     

N-vinylpyrrolidone/acrylic acid/2-acrylamido-2-methylpropane sulfonic acid based hydrogels: Synthesis,characterization and their application in the removal of heavy metals

In this work, the synthesis of N-vinylpyrrolidone/acrylic acid/2-acrylamido-2-methylpropane sulfonic acid (NVP/AAc/AMPS) based hydrogels by UV-curing technique was studied and their swelling behavior, heavy metal ion recovery capabilities were investigated. The structures of hydrogels were characterized by FT-IR analysis and the results were consistent with the expected structures. Thermal gravimetric analysis of hydrogels showed that the thermal stability of hydrogel decreases slightly with incorporation of AMPS units into the structure. In addition, the morphology of the dry hydrogel sample was examined by SEM. According to swelling experiments, hydrogels with higher AMPS content gave relatively higher swelling ratio compared to neat hydrogel. These hydrogels were used for the separation of Cd(II), Cu(II) and Fe(III) ions from their aqueous solutions. The influence of the uptake conditions such as pH, time and initial feed concentration on the metal ion binding capacity of hydrogel was also tested. The selectivity of the hydrogel towards the different metal ions tested was Cd(II) > Cu(II) > Fe(III). It was observed that the specific interaction between metal ions and ionic co-monomers in the hydrogel affected the metal binding capacity of the hydrogel. The recovery of metal ions was also investigated in acid media.     

Removal of cobalt ions from aqueous solutions by using poly(N,N‐dimethylaminopropyl methacrylamide/itaconic acid) hydrogels

In this study, N,N‐dimethylaminopropyl methacrylamide (DMAPMAm) homopolymer and DMAPMAm/itaconic acid (DMAPMAm/IA) copolymers were obtained from ⁶⁰Co‐γ radiation polymerization. Gel fraction and percentage of swelling values were calculated through gravimetrical calculations. In order to increase the swelling of the hydrogel, the amount of IA in initial copolymer composition was gradually increased, but it was observed that gelation values were low. The structural and morphological assessments of homopolymer and copolymers were made by means of several techniques including Fourier Transform Infrared Spectroscopy (FT‐IR), Scanning Electron Microscopy (SEM), and Energy‐Dispersive X‐ray Spectroscopy (EDS). The cobalt ion (Co²⁺) removal capacities of hydrogel were investigated by taking into account of the initial metal ion concentration and pH of aqueous medium. When it came to the maximum capacity of values obtained from adsorption experiments by using Co²⁺ solutions at pH 5, they changed between 220 and 245 mg Co²⁺/g dry hydrogel. FT‐IR, SEM, EDS, and XRD analyses were carried out for enlightening the mechanism of Co²⁺ removal by hydrogels after the completion of adsorption. Also, desorption studies were conducted using ethylenediaminetetraacetic acid (EDTA). Finally, within approximately 5 days, all adsorbed Co²⁺ ions were released from hydrogels at pH 5 using 0.1M EDTA solution. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39569.     

Study on the inverse emulsion copolymerization of microgels based on acrylamide/2-acrylamido-2-methylpropane sulfonic acid

Inverse emulsion copolymerization of acrylamide and AMPS was conducted, and the effects of cross-linker concentration, initiator type, and reaction temperature on particle size distribution, equilibrium swelling and thermal properties were studied. Fourier transform infrared spectrophotometry (FTIR) and differential scanning calorimetry (DSC) results were used to confirm the copolymerization of the monomers. In this study, relatively high amounts of AMPS comonomer were used successfully to synthesize AAm/AMPS based microgels. Thermal properties were determined using thermogravimetric analysis (TGA) and it was found that degradation threshold shifted to higher temperatures with increasing cross-linking. There was a good agreement between the DSC and TGA thermograms depicting the different stages of microgel degradation including the departure of amide and sulphonic acid groups. Dynamic light scattering (DLS) demonstrated that higher cross-link densities resulted in the formation of smaller particles with narrower distribution and lower swelling capacity. The results of scanning electron microscopy (SEM) showed that the more hydrophobicity of the initiator led to the decrease in particle size and swelling capability. Swelling ratio reached its maximum value at about 50 °C. Interestingly, mean particle size had a close relation with equilibrium swelling as samples with lower mean particle diameters exhibited lower swelling capacities.     

Removal of Hg(II) from acid aqueous solutions by poly(N‐vinylimidazole) hydrogel

Caption of Hg(II) from acid aqueous solution by immersed poly(N‐vinylimidazole) hydrogel particles was studied as a function of pH, counterion, and cation concentration. Fitting parameters to several sorption isotherms have been determined. Their values depend mostly on pH and less, on temperature and counterion, and suggest a large affinity of imidazole groups in the gel and mercury cations. Practically total removal (94.4%) of Hg(II) is achieved at pH = 2, with 10 g of dry gel per liter of solution, when cation concentration was as large as 15,000 ppm (0.075 M). Polymer protonation decreases about fourfold the cation affinity, supporting competitive protonation‐complexation mechanisms. By its side, metal uptake decreases polymer protonation. Thermal stability of loaded gels decreases with respect to metal free hydrogels. Scanning electron micrographs reveal no changes in the gel morphology upon cation binding, but T_g increases significantly with the Hg(II) content of loaded gels and swelling decreases moderately, indicating the role of the cation as ionic crosslinker. Practically total elution of Hg(II) is achieved with 1 M HNO₃ in consecutive loading‐elution cycles. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1467–1475, 2001     

Removal of methylene blue from aqueous solution by a carbon-microsilica composite adsorbent

Microsilica, one kind of industrial solid waste material, was utilized firstly to prepare a carbon-microsilica composite adsorbent (CMS). The prepared adsorbent was characterized with XPS, SEM and Gas sorption experiments. The results indicated the SO₃H groups, which are very effective in capturing cationic organic dye, were introduced onto the surface of CMS; the Brunauer-Emmett-Teller (BET) surface area (S _BET ) and total pore volume (V _total ) of CMS reach 51m²/g and 0.045 cm³/g, respectively. Meanwhile, the possibility of the utilization of the adsorbent for removal of methylene blue (MB) from aqueous solution was investigated. The effect of pH, contact time and initial MB concentration for MB removal were studied. Equilibrium data were modeled using the Langmuir, Freundlich and Dubinin-Radushkevich equations to describe the equilibrium isotherms. It was found that data fit to the Langmuir equation better than the Freundlich equation. Maximum monolayer adsorption capacity was calculated at different temperatures (298, 308, and 318 K) reach 251.81, 283.76 and 309.70 mg/g, respectively. It was observed that adsorption kinetics obeys the pseudo-first-order equation.     

Thermal stability of polymers based on acrylamide and 2-acrylamido-2-methylpropane sulfonic acid in different temperature and salinity conditions

Partially hydrolyzed polyacrylamide (PHPA) is the most widely used polymer in enhanced oil recovery (EOR) applications. However, under conditions of high temperature and salinity, the PHPA molecules become hydrolyzed, causing a drastic reduction of the viscosity of the polymer solution due to the presence of negative charges, making the molecules more susceptible to interactions with cations. In this sense, in order to increase the stability of these polymers, an anionic monomer more resistant to cations such as 2-acrylamido-2-methylpropane sulfonic acid (AMPS) has been incorporated into the HPAM molecules. This work evaluated the thermal stability of a copolymer (acrylamide and AMPS - AN125) and a terpolymer (acrylamide, acrylate, and AMPS-FP5115) in the time course of 360 days. The tests were carried out in typical conditions of Brazilian offshore reservoirs, such as absence of oxygen, high temperature, and high salt concentration. The test method involved measurements of intrinsic viscosity in function of time and determination of the hydrolysis degree of the polymers by elemental analysis. The copolymer AN125 was more stable under the test conditions than the terpolymer FP 5115 due to the presence of a higher concentration of AMPS in the copolymer. The AMPS group was hydrolyzed to AA at a temperature of 100 °C, however, the increase in salt concentration delayed the onset of this degradation. The tests indicated that the presence of a higher AMPS content in the copolymer does not prevent the polymer from undergoing hydrolysis, but delays the polymer precipitation step in the solution.     

2－丙烯酰胺－2－甲基丙磺酸的研究开发

介绍了２－丙烯酰胺－２－甲基丙横酸（ＡＭＰＳ）的制备、应用以及在我国的开发前景。     

Adsorption of methylene blue from aqueous solutions by modified expanded graphite powder

The modified expanded graphite (MEG) powder was used as a porous adsorbent for the removal of the cationic dye, methylene blue (MB), from aqueous solutions. The dye adsorption experiments were carried out with the bath procedure. Experimental results showed that the basic pH, increasing initial dye concentration and high temperature favored the adsorption. The dye adsorption equilibrium was attained rapidly after 5 min of contact time. Experimental data related to the adsorption of MB on the MEG under different conditions were applied to the pseudo-first-order equation, the pseudo-second-order equation and the intraparticle diffusion equation, and the rate constants of first-order adsorption (k₁), the rate constants of second-order adsorption (k₂) and intraparticle diffusion rate constants (k_int) were calculated, respectively. The experimental data fitted very well in the pseudo-second-order kinetic model. The thermodynamic parameters of activation such as Gibbs free energy, enthalpy, and entropy were also evaluated. The results indicated that the MEG powder could be employed as an efficient adsorbent for the removal of textile dyes from effluents.     

Adsorption of methylene blue from aqueous solutions by synthetic montmorillonites of different compositions

The sorption capacity of synthetic montmorillonites of the composition Na_2x (Al_2(1–x),Mg_2x )Si₄O₁₀(OH)₂ · nH₂O (where 0 < x < 1) in relation to the methylene blue dye has been investigated. The obtained results from the data for natural samples of montmorillonite (K10) and activated carbon have been compared. The effect of the montmorillonite composition and the medium acidity on the degree of dye adsorption has been studied. The chemical composition of montmorillonite, which is optimal for solving tasks in the field of ecology and medicine, has been determined. The character of the interaction of montmorillonites with the adsorbed substance from the point of view of the physical-chemical sorption models has also been studied.     

Removal of Cu2+ and Pb2+ ions from aqueous solutions by starch-graft-acrylic acid/montmorillonite superabsorbent nanocomposite hydrogels

In this study, the removal of copper(II) and lead(II) ions from aqueous solutions by Starch-graft-acrylic acid/montmorillonite (S-g-AA/MMT) nanocomposite hydrogels was investigated. For this purpose, various factors affecting the removal of heavy metal ions, such as treatment time with the solution, initial pH of the solution, initial metal ion concentration, and MMT content were investigated. The metal ion removal capacities of copolymers increased with increasing pH, and pH 4 was found to be the optimal pH value for maximum metal removal capacity. Adsorption data of the nanocomposite hydrogels were modeled by the pseudo-second-order kinetic equation in order to investigate heavy metal ions adsorption mechanism. The observed affinity order in competitive removal of heavy metals was found Cu²⁺ > Pb²⁺. The Freundlich equations were used to fit the equilibrium isotherms. The Freundlich adsorption law was applicable to be adsorption of metal ions onto nanocomposite hydrogel.     

Preparation of poly(acrylamide-co-2-acrylamido-2-methylpropan sulfonic acid)-g-Carboxymethyl cellulose/Titanium dioxide hydrogels and modeling of their swelling capacity and mechanic strength behaviors by response surface method technique

It is very important that new generation, unique, high mechanical strength, and biocompatible hydrogel composites are developed due to their potential to be used as biomaterials in the biomedical field. Modeling of the swelling capacity and mechanical strength behavior of hydrogels is a domain of steadily increasing academic and industrial importance. These behaviors are difficult to model accurately due to hydrogels show very complex behavior depending on the content. In this study, a series of poly(acrylamide-co-2-acrylamido-2-methylpropan sulfonic acid)-g-carboxymethyl cellulose/TiO₂ (poly(AAm-co-AMPS)-g-CMC/TiO₂) superabsorbent hydrogel composites were prepared by free-radical graft copolymerization in aqueous solution. Structural and surface morphology characterizations were conducted by using Fourier-transform infrared spectroscopy and scanning electron microscope analysis techniques. For modeling the equilibrium swelling capacity and fracture strength behaviors of hydrogels, the composition parameters (such as mole ratio of AMPS/AAm, wt% of CMC, and wt% of TiO₂) was proposed by response surface method (RSM) Design Expert-10 software. Statistical parameters showed that the RSM model has good performance in modeling the swelling capacity and mechanic fracture strength behaviors of poly(AAm-co-AMPS)-g-CMC/TiO₂ hydrogel composites. According to the RSM model results, the maximum swelling capacity and fracture strength values were calculated as 270.39 g water/g polymer and 159.23 kPa, respectively.