Effect of intercalated hydrotalcite on swelling and mechanical behavior for poly(acrylic acid‐co‐N‐isopropylacrylamide)/hydrotalcite nanocomposite hydrogels

A series of nanocomposite hydrogels were prepared from acrylic acid (AA), N‐isopropylacrylamide (NIPAAm), and intercalated hydrotalcite (IHT) by photopolymerization. The influence of the intercalating content of 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) in HT on the swelling and mechanical properties for poly(AA‐co‐NIPAAm)/IHT nanocomposite hydrogels was investigated. The results showed that the higher the content of the AMPS‐HT was, the higher the swelling ratio of the gels and the higher the content of the intercalating agent was, the lower swelling ratio. It was also demonstrated that the swelling ratio of the gel was not affected by the counterion in HT. The gel strength and crosslinking density were not enhanced by adding AMPS‐HT into the gel composition, but the maximum effective crosslink density and shear modulus of the nanocomposite hydrogels were increased with an increase of the content of the intercalating agent in HT. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1572–1580, 2005     

Super alcohol-absorbent gels of sulfonic acid-contained poly(acrylic acid)

Alcohol-specific superabsorbing gels (super-alcogels) based on non-neutralized acrylic acid (AA, 60–94 mol%) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) were prepared via solution polymerization in water. Polyethylene glycol dimethacrylate and potassium persulfate were used as crosslinker and initiator, respectively. Characterization of samples was performed using FTIR, ¹H-NMR and thermomechanical analyses. Glass transition temperature and modulus of dried samples were found to be directly changed with their AA content. The gels exhibited enormous ability for absorbing and retaining a variety of mono- and poly-hydric alcohols. For example, in lieu of one gram of a typical sample composing 25 mol% AMPS, its absorption capacity was measured to be 53.0 g methanol, 42.1 g ethanol, 12.1 g n-propanol, 3.4 g iso-propanol, 41.2 g ethylene glycol, 20.7 g propylene glycol, 37.8 g 1,3-propanediol and 32.9 g glycerol. The absorbencies were superior to those of a known commercial poly(AA) sample, Carbopol. The alcohol absorbency was improved with increase of AMPS incorporated. It was recognized to be dependant on the alcohol characteristics such as H-bonding ability, OH/C ratio, electronic features (e.g. dielectric constant), steric hindrance of the neighboring groups of the solvent OH group, as well as the solvent viscosity. Normal phase transitions were observed in the gel swelling behavior in the alcohol-water binary mixtures. Rheological measurements of the water-swollen gel showed that more AMPS content resulted in gels with inferior storage modulus. All the empirical observations were discussed based on the related physicochemical principles.     

Preparation and Controlled Drug Release Characteristics of Thermoresponsive PEG/Poly (NIPAM-co-AMPS) Hydrogels

Thermosensitive hydrogels were prepared by free radical polymerization of N-isopropylacrylamide (NIPAM) and 2-acrylamido-2-methylpropanesulphonic acid (AMPS) in presence of polyethylene glycol (PEG) as macroinitiator. The incorporation of functional monomer in the hydrogel was confirmed by infrared spectroscopy. The equilibrium swelling ratio (ESR), deswelling rate, volume transition temperature, and surface morphology of synthesized hydrogels are found to be dependent on concentration of AMPS monomer in the feed composition. The equilibrium swelling ratio (ESR) and water retention properties increase with increasing AMPS concentration in hydrogels and decrease with increasing salt concentration in external medium. The hydrogel with high dose of AMPS has high loading efficiency of theophylline drug, whereas the in-vitro release of the drug is delayed for a prolonged period in swollen gels above LCST of PNIPAM.     

Chitosan‐modified nanoclay–poly(AMPS) nanocomposite hydrogels with improved gel strength

BACKGROUND: Making (nano)composite structures is one of the efficient approaches for strengthening hydrogels extended in recent years. The present paper deals with the synthesis and properties of novel nanocomposite hydrogels based on 2‐acrylamido‐2‐methylpropane‐1‐sulfonic acid (AMPS). Initially, a bio‐modified clay, chitosan‐intercalated montmorillonite (chitoMMT), was prepared. Then, this was incorporated into the polymerization of AMPS in the presence of a macro‐crosslinker, i.e. poly(ethylene glycol) dimethacrylate, to yield super‐swelling nanocomposite hydrogels. The swelling capacity as well as some structural, rheological and thermomechanical properties of the hydrogels were studied and compared with those of the clay‐free counterpart. RESULTS: ChitoMMT exhibited no toxicity, which was confirmed using cell‐culture testing. A chitoMMT content of ca 6% was found to be the most favourable content of the bio‐modified clay for achieving a product with improved properties (i.e. the highest gel content, the highest gel strength and optimal thermal stability). Based on a dynamic mechanical thermal analysis study, an increased glass transition temperature (98.2 °C) and improved rubbery modulus (up to 238% higher than that of the clay‐free counterpart) were recorded. Thermogravimetric analysis verified that the thermal stability of nanocomposite samples was higher than that of clay‐free samples. CONCLUSION: Owing to the non‐toxicity of the incorporated chitoMMT, the strengthened hydrogels may be considered as potential candidates for bio‐applications. Copyright © 2009 Society of Chemical Industry     

Removal of hazardous by radiation‐synthesized copolymer hydrogels based on 2‐acrylamido‐2‐methylpropanesulfonic acid and 2‐dimethyaminoethyl methacrylate monomers

Superabsorbent copolymer hydrogels were prepared by gamma irradiation of aqueous solutions of 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) and 2‐dimethyaminoethyl methacrylate (DEMA) monomers mixtures. The thermal stability of hydrogels was evaluated by thermogravimetric analysis. The ability to adsorb Cu²⁺ ions and dyes by the prepared hydrogels from aqueous solutions was investigated. The swelling study, in water, showed that the hydrogels based on pure AMPS monomer and AMPS/DEMA copolymers reached the equilibrium state after 6 h. However, the hydrogel based on pure AMPS monomer showed higher swelling than the copolymer hydrogels based on AMPS/DEMA. It was found that the copolymer hydrogels based on different compositions showed affinity to absorb Cu²⁺ metal ions as well as basic and acid dyes; however, this affinity was found to decrease with increasing the ratio of DEMA in the initial feeding solutions. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation and properties of modified PHEMA hydrogel with sulfonated PEG graft

A novel poly(ethylene glycol) (PEG) macromer with a methacryloyl and sulfonic acid group at each end of the chain was prepared. Modified hydroxyethyl methacrylate (HEMA) based hydrogels were synthesized by crosslinking polymerization of HEMA in the presence of the above‐mentioned PEG macromer. The effect of the sulfonated PEG graft was examined by comparing the swelling properties with those of a pure poly(hydroxyethyl methacrylate) (PHEMA) hydrogel. The modified PHEMA hydrogel exhibited increasing water absorbency with increasing sulfonated PEG content up to 15 wt %. These hydrogels with the sulfonated PEG graft exhibited a more hydrophilic character than the pure PHEMA gel. Also the swelling degree varied slightly with pH, showing increased swelling at higher pH probably due to the presence of the anionic sulfonate group on the PEG end chain. In addition, the protein adsorption test showed a lower level of fibrinogen adsorption from the sulfonated poly(ethylene glycol) (SPEG) modified gel than on the homo PHEMA hydrogel. Interestingly, scanning electron microscopy showed that the porous and rather uniform morphology of the gels changed with increasing sulfonated PEG content in PHEMA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2484–2489, 2007     

Effect of hydrotalcite on the physical properties and drug‐release behavior of nanocomposite hydrogels based on poly[acrylic acid‐co‐poly(ethylene glycol) methyl ether acrylate] gels

A series of nanocomposite hydrogels used for bioadhesive were prepared from acrylic acid, poly(ethylene glycol) methyl ether acrylate, and intercalated hydrotalcite (HT) by photopolymerization. The microstructures of the intercalated HT and sample gels were identified by X‐ray diffraction (XRD). The results showed that the swelling ratio for these nanocomposite hydrogels increased with an increase in HT, but the gel strength and adhesive force for these gels decreased with an increase in HT. The XRD results indicated that the exfoliation of intercalated HT was achieved in the xerogels and swollen gels. Finally, the drug‐release behaviors for these gels were also examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 692–699, 2004     

Gelation and crosslinking characteristics of photopolymerized poly(ethylene glycol) hydrogels

The gelation and crosslinking features of poly(ethylene glycol) (PEG) hydrogels were scrutinized through the UV polymerization processes of poly(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) mixtures. The real‐time evolutions of the elastic moduli of the prepolymerized mixtures with different crosslinking ratios of PEGMA and PEGDMA and the photoinitiator concentrations were measured during photopolymerization. The rheological properties were compared with other properties of the PEG hydrogels, including the relative changes in the C?C amounts in the mixtures before and after UV irradiation, water swelling ratio, gel fraction, mesh size, and mechanical hardness. As the portion of PEGDMA as a crosslinker increased, the final elastic modulus and gel fraction increased, whereas the swelling ratio and scratch penetration depth at the hydrogel film surface decreased because of the formation of compact networks inside the hydrogels. These results indicate that there was a good correlation between the rheological analysis for predicting the crosslinking transition during photopolymerization and the macroscopic properties of the crosslinked hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41939.     

Effect of bentonite on the physical properties and drug‐release behavior of poly(AA‐co‐PEGMEA)/bentonite nanocomposite hydrogels for mucoadhesive

A series of nanocomposite hydrogels for mucoadhesive were prepared from acrylic acid, poly(ethylene glycol) methyl ether acrylate, and intercalated bentonite clay by photopolymerization. The microstructures were identified by X‐ray diffraction (XRD). Results showed that the swelling ratio for the present nanocomposite hydrogels decreased with an increase of bentonite, whereas the gel strength and Young's modulus of the present gels increased with an increase of bentonite. However, the adhesive force of the present gels did not decrease with an increase of bentonite. XRD results indicated that the exfoliation of bentonite was achieved in the xerogels and swollen gels. Finally, the drug‐release behaviors for these gels were also assessed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2934–2941, 2004     

Undesirable effects of heating on hydrogels

Heating is the most conventional drying method for removing water from as‐synthesized hydrogels in laboratory and industry. In this article, the effects of the heating temperature (60–200°C) and time (10 min–24 h) on swelling properties of highly absorbent hydrogels based on 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS), acrylic acid (AA), potassium acrylate (KA), and acrylamide (AM) were studied. Crosslinkers methylene bisacrylamide (MBA) and poly(ethyleneglycol) dimethacrylate (PEGDMA) were used in the syntheses. Depending on the hydrogel structural composition and its drying temperature and time, the swelling capacities were extremely changed. Generally, AA‐, KA‐, and AM‐based hydrogels showed more hydrolytic‐thermal stability than the corresponding AMPS‐based hydrogels. MBA‐crosslinked hydrogels generally exhibited higher vulnerability against heating. Swelling of PEGDMA‐crosslinked poly(AM‐KA‐AA) hydrogel was greatly increased after heating, whereas its analogousAM‐free sample exhibited huge loss of swelling. PEGDMA‐crosslinked poly(AMPS) samples also exhibited swelling reduction after drying. Rheological studies showed that the storage modulus was highly reduced (～ 5200 Pa) after heating of MBA‐crosslinked poly(AMPS) hydrogels, which reconfirmed the crosslink cleavage. Mechanistic discussions were proposed for the thermal‐induced swelling changes. It was concluded that the chemical nature of both crosslinker and monomer must be taken into consideration to choose the temperature and time of the hydrogel drying. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development of Sodium Carboxymethyl Cellulose-based Poly(acrylamide-co-2acrylamido-2-methyl-1-propane sulfonic acid) Hydrogels for In Vitro Drug Release Studies of Ranitidine Hydrochloride an Anti-ulcer Drug

The formation of sodium carboxymethyl cellulose (SCMC) based semi-interpenetrating networks (semi-IPN) with poly(acylamide-co-2-acrylamido-2-methy-l-propanesulfonic-acid) hydrogels. The hydrogels were prepared by free-radical polymerization using redox initiator. The characterizations of hydrogels were done by swelling experiments, FTIR spectroscopy and DSC analysis. Morphology of the samples were examined by SEM. Experimental results indicate that the semi-IPN hydrogel containing 0.10 g of SCMC and 5.829 mM of AMPS, shows the highest swelling capacity (64.83 g/g). The swelling behavior of the semi-IPN hydrogel (AS5) was studied in different pH solutions. The ranitidine hydrochloride drug loading and release of the semi-IPN hydrogels were studied by using a UV spectrophotometer.     

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.     

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.     

Polyampholytic hydrogels: Poly(N-isopropylacrylamide)-based stimuli-responsive networks with poly(ethyleneimine)

Polyampholytic hydrogels are crosslinked networks composed of positively and negatively charged repeat units that show entirely different properties from their originate polyelectrolyte polymers. Here we report a series of stimuli-responsive polyampholytic hydrogels designed with poly(N-isopropylacrylamide-co-sodium acrylate)/poly(ethyleneimine) [poly(NIPAM-co-SA)/PEI] through the interpenetrating network method. The polyampholytic IPN hydrogel containing 0.5 g PEI showed a higher swelling capacity than the remaining PEI-formulated hydrogels. These gels demonstrated a relatively higher swellability at pH 5 or 6. The interaction of various surfactants and polymer solutions was evaluated at different concentrations. Both the non-ionic (Tween 80) and anionic (sodium dodecyl sulfate, SDS) surfactants promoted their swelling properties, while the cationic (dodecylpyridinium chloride, DPC) surfactant drastically reduced the swelling nature of the polyampholytic semi-IPN hydrogels. Because of more physical attractions between the polyampholytic IPN gels and DPC, it showed a greater thermal stability. The surfactant interactions were eventually studied using scanning electron microscopy. Further, the effect of different salts on the swelling properties of the polyampholytic IPN hydrogels has been demonstrated in detail.     

Swelling–shrinking hysteresis of poly(N‐isopropylacrylamide) gels in sodium dodecylbenzenesulfonate solutions

The swelling and shrinking behaviors of a series of poly(N‐isopropylacrylamide) (PNIPA) hydrogels are studied in aqueous solutions of sodium dodecylbenzenesulfonate (SDBS). Between 0 and 3 mol % 2‐acrylamido‐2‐methylpropanesulfonic acid sodium salt (AMPS) is used as an ionic comonomer in the hydrogel synthesis. It is shown that the collapsed PNIPA gels in water at 52°C start to swell above a critical SDBS concentration in the external solution. This critical concentration decreases as the ionic group content of PNIPA gel increases. A comparison of the swelling and shrinking experiments in SDBS solutions indicates strong hysteresis behavior of PNIPA gels. A more diluted solution is required to make a swollen gel start to reshrink than to cause gel swelling. The results show strong attractive forces between the isopropyl groups of the PNIPA network and the DB groups of SDBS molecules. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1228–1232, 2002     

Swelling and auramine-<Emphasis Type="Italic">O</Emphasis> adsorption of carboxymethyl cellulose grafted poly(methyl methacrylate)/Cloisite 30B nanocomposite hydrogels

Carboxymethyl cellulose (CMC) grafted poly(methyl methacrylate)/Cloisite 30B nanocomposite hydrogels were prepared for adsorptive removal of auramine-O (as a cationic dye model) from wastewater. For the synthesis of nanocomposite hydrogel by free radical polymerization method, potassium persulfate (KPS), methyl methacrylate (MMA), N,N′-methylene bisacrylamide (MBA) and Cloisite 30B were used as initiator, monomer, cross-linker and nano-filler, respectively. The nanocomposite hydrogels were characterized by FTIR, TGA, SEM and XRD techniques. The FTIR results showed that the monomer was grafted onto carboxymethyl cellulose chains successfully. Swelling behavior of nanocomposite hydrogel as a function of KPS, MBA, MMA concentration and CMC/Cloisite 30B weight ratio was studied by Taguchi method using Minitab 16 software. According to ANOVA results, the most effective factor of equilibrium swelling of nanocomposite hydrogel was CMC/Cloisite 30B weight ratio. Addition of Cloisite 30B to hydrogel up to a certain amount improved swelling, though its high amount decreased swelling. The effects of pH and ionic strength on swelling of optimum hydrogels were investigated. Maximum swelling of nanocomposite hydrogel occurred at pH 7.0. The kinetic data of adsorption fitted well to pseudo-second-order model. The best isotherm for investigation of adsorption mechanism was Langmuir model suggesting the formation of a monolayer on the adsorbent surface. FTIR results, before and after auramine-O adsorption, showed that complexation is the main mechanism of adsorption. High adsorption capacity of nanocomposite hydrogels made them more efficient in wastewater treatment application.     

Removal of anionic dyes from aqueous solution using poly [N-vinyl pyrrolidone/2-(methacryloyloxyethyl) trimethyl ammonium chloride] superswelling hydrogels

Summary A superswelling poly [N-vinyl pyrrolidone/2-(methacryloyloxyethyl)trimethyl ammonium chloride], poly(NVP/METAC) hydrogels were prepared by free radical polymerization using ethylene glycol dimethacrylate as crosslinker. The hydrogels were characterized by FT-IR spectroscopy and their surface morphology was determined using Scanning Electron Microscope (SEM). The influence of feed composition of both the monomers and crosslinker on equilibrium swelling and dye adsorption properties of the hydrogels were examined. The equilibrium swelling ratio and binding ratio of the hydrogel/dye systems greatly depends on the METAC and crosslinker concentration in the gels. The effects of pH of the medium and initial dye concentration on the adsorption were also studied. The binding ratio of the hydrogel/dye system increases in the following order: OR-II>RO-14>RO-13.     

Water Sorption and Dye Uptake Studies of Highly Swollen AAm/AMPS Hydrogels and Semi-IPNs with PEG

A semi-interpenetrating network (semi-IPNs) hydrogel, composed of acrylamide (AAm) with 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) as co-monomer, with poly(ethylene glycol) (PEG) and two multifunctional cross-linkers such as 1,4-butanediol dimethacrylate (BDMA), and trimethylolpropane triacrylate (TMPTA) was prepared. AAm/AMPS hydrogels and AAm/AMPS/PEG semi-IPNs were synthesized by free radical solution polymerization. Swelling experiments were performed in water at 25°C, gravimetrically. For sorption of Toluidin Blue (Basic Blue 17, TB) into AAm/AMPS hydrogels and AAm/AMPS/PEG semi-IPNs was studied by batch sorption technique at 25°C. Dye removal capacity, removal effiency and partition coefficient of the hydrogels was investigated.     

Mechanical properties and drug release rate of poly(vinyl alcohol)/poly(ethylene glycol)/clay nanocomposite hydrogels: Correlation with structure and physical properties

Poly(vinyl alcohol)/poly(ethylene glycol) hydrogels containing curcumin as a drug and the various amounts of a montmorillonite nanoclay are prepared using the freezing–thawing method. Nanoclay quantity influence on the physicomechanical properties and the drug release rate of the hydrogel as well as relationship between them is investigated. X-Ray diffraction and Atomic force microscopy analysis reveal the nanoclays have an intercalation structure in the hydrogel, and the hydrogel crystallization decreases with increasing the nanoclay inclusion. From the SEM micrographs observation, it was revealed that due to the presence of the nanoclay in the hydrogel, its porosity decreased. The naonoclay has an amount-depended dual effect on the hydrogel swelling. The swelling mechanism is a normal Fickian diffusion for all the hydrogel samples. Strong physical interactions between the nanoclays and the polymer chains in the nanocomposite hydrogels are evidenced by the rheological studies. These interactions lead to significant reinforcement of the hydrogel tensile strength, intensified by the nanoclay amount. Interestingly, the nanoclays show the capability of accelerating and, also, decelerating the drug release of the hydrogel. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47843.     

Facile synthesis of biocompatible polyglycerol hydrogel based on epichlorohydrin

A series of hydrophilic polyglycerol (PG) hydrogel was designed and synthesized via one pot with epichlorohydrin (ECH), H₂O, and NaOH as the starting materials. The equilibrium swelling ratios of PG hydrogels could be tuned by simply changing the feed amount of NaOH. The gels were characterized by carbon nuclear magnetic resonance (¹³C NMR) spectroscopy, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The As‐synthesized PG hydrogels showed temperature‐sensitive swelling behaviors. The results of MTT assay suggested that the PG hydrogels prepared by this novel synthesis method showed comparable cytocompatibility with the recognized poly(ethylene glycol) hydrogel. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43451.