Swelling behavior and structural characteristics of polyvinyl alcohol/montmorillonite nanocomposite hydrogels

A series of nanocomposite hydrogels based on polyvinyl alcohol containing 0–10 wt % of the organically modified montmorillonite clay were prepared by freezing‐thawing cyclic method. The morphology of the nanocomposite hydrogels was observed by the scanning electron microscopy technique. The structural properties were determined by measuring the network mesh size, crosslinking density, and average molecular weight of polymer chains between crosslinks. The swelling behavior and the effect of swelling medium temperature on the swelling kinetics and characteristics of the nanocomposite hydrogels were also investigated. The results showed that two structural characteristics i.e., network mesh size and average molecular weight of polymer chains between crosslinks have inverse dependence on the clay loading level in the nanocomposite hydrogel, while crosslinking density shows completely direct dependence. Swelling measurements demonstrated a linear relation between the degree of swelling and the square root of immersion time at all swelling medium temperatures. The results indicated that the swelling characteristics of the nanocomposite hydrogels including the equilibrium degree of weight and volume swelling and the equilibrium water content were decreased by increasing the quantity of the clay incorporated into the hydrogel as well as by decreasing the temperature of swelling medium. While, the time required to reach to the equilibrium condition, as another swelling characteristic of the hydrogels, exhibited a completely opposite behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Poly(N-isopropylacrylamide) Hydrogels Crosslinked by Small-Molecular Crosslinkers Through Click Chemistry

A well-defined azido-poly(N-isopropylacrylamide) (PNIPA) was prepared by reversible addition-fragmentation chain transfer polymerization of NIPA and glycidyl methacrylate followed by the azidization of pendant epoxyl groups. Then the polymer was crosslinked via Click chemistry by bis- or tetra-alkynyl terminated compounds, which were synthesized through esterification of 1,3-propanediol and pentaerythritol with propiolic acid and 6-heptynoic acid, to fabricate PNIPA hydrogels. And the swelling properties of obtained hydrogels were studied as functions of crosslinker dosage and species. The results showed that the decrease of crosslinker dosage or increase of chain length thereof could enhance swelling capacities of hydrogels due to bigger free volumes within networks; the functionality of crosslinkers almost had no influence on swelling properties of hydrogels. In addition, no obvious distinction was found for lower critical solution temperature and swelling response to a temperature jump during reswelling and deswelling course, no matter what and how much crosslinker was used.     

Control of swelling properties of polyvinyl alcohol/hyaluronic acid hydrogels for the encapsulation of chondrocyte cells

Hydrogel scaffolds for tissue engineering are important biomaterials. The target in this study was to prepare polyvinyl alcohol/hyaluronic acid hydrogels for the encapsulation of chondrocyte cells by a simple cross‐linking reaction. Control of the swelling properties and morphology of the hydrogels for cultivation of chondrocytes was studied. The hydrogels were prepared from polyvinyl alcohol and hyaluronic acid derivatives bearing primary amine and aldehyde functionalities, respectively. The formation of the hydrogel upon mixing the aqueous solutions of the polymer derivatives took place at room temperature in a few seconds. The swelling properties of the hydrogels were found to depend on the polymer concentration and degree of substitution of the modified polymers. Scanning electron microscopy studies showed that the hydrogels had a suitable porous morphology for cell encapsulation. Furthermore, in vitro cell viability tests with the hydrogels showed no cytotoxicity for chondrocytes and that the cells grew well in the hydrogel scaffolds. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42272.     

Radiation synthesis and characterization of 2‐hydroxyethyl‐methacrylate‐based hydrogels containing di‐ and tri‐protic acid and its application on wastewater treatment

Radiation‐crosslinked 2‐hydroxyethylmethacrylate/citric acid (HEMA/CAc), 2‐hydroxyethylmethacrylate/tartaric acid (HEMA/TA), and 2‐hydroxyethylmethacrylate/succinic acid (HEMA/Sc) copolymers were prepared by using ⁶⁰Co γ‐rays. The gel fraction yield and the swelling behavior of the prepared hydrogels were studied. It was shown that increasing irradiation doses was accompanied by an increase in yield of gel fraction and a decrease in swelling degree. The parameters of equilibrium swelling, maximum swelling, initial swelling rate, swelling exponent, and diffusion coefficient of the hydrogels were determined by studying the swelling behavior of the hydrogels prepared. It was seen that the equilibrium swelling degree increases as the content of acid increases, as a result of introducing more hydrophilic groups. When the hydrophilic polymer (acids) varies in the content range of 40–80 mg, swelling exponents (n) decreases, thereby indicating a shift in the water‐transport mechanism from the anomalous (non‐Fickian)‐type to the Fickian‐type. Characterization and some selected properties of the prepared hydrogels were studied, and accordingly the possibility of its practical use in the treatment of industrial wastes such as dyes and heavy metals (Fe, Ni, Co, and Cu) were also studied. The effect of treatment time, pH of feed solution, initial feed concentration, and temperature on the dye and heavy metals uptake was determined. The uptake order for a given metal was HEMA/TA hydrogel > HEMA/CAc > HEMA/Sc hydrogel. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of hydrogels based on gamma irradiation of acrylic acid and methacrylic acid

In this work, hydrogels based on different ratios of acrylic acid (AAc) and methacrylic acid (MAc) monomers were prepared by gamma radiation copolymerization. The hydrogels were characterized by IR spectroscopy and thermogravimetric analysis (TGA). The effect of temperature and pH on the degree of swelling of AAc/MAc hydrogels was also studied. The results showed that the gel fraction of AAc is relatively higher than MAc, while the gel fraction of AAc/MAc hydrogels decreased slightly with increasing the ratio of MAc monomer in the initial solution. The IR spectroscopic analysis indicates the formation of copolymer networks and the presence of hydrogen bonding. The thermal study showed that PAAc hydrogel displayed higher thermal stability than PMAc and AAc/MAc hydrogels, over the studied compositions. The results showed that PAAc hydrogel reached equilibrium swelling state in water after 4 h, whereas PMAc and AAc/MAc hydrogels reached the equilibrium after 7 h. In this regard, AAc/MAc hydrogels showed degree of swelling in water lower than PAAc and higher than PMAc hydrogels. It was found that the swelling of the hydrogels based on AAc and MAc monomers or their copolymers increases with increasing temperature up to 50°C. Moreover, it was observed that the degree of swelling of hydrogels were not affected by increasing the pH values up to 4 and increased greatly within the pH values from 5 to 9. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Synthesis of crosslinked superabsorbent carboxymethyl cellulose/acrylamide hydrogels through electron‐beam irradiation

A study on the possibility of the preparation of superabsorbent hydrogels based on crosslinked carboxymethyl cellulose polymer and acrylamide monomer through electron‐beam irradiation was carried out. The effects of the irradiation dose and polymer–monomer compositions on the crosslinking density were studied. The hydrophilic properties of the superabsorbent hydrogels were identified by the swelling percentage. The prepared hydrogels had higher swelling in distilled water than in salt solutions. Moreover, the hydrogels exhibited the highest swelling at pH 7. Also, increasing the temperature up to 50°C caused an increase in the swelling. The thermal properties of the hydrogels were characterized with thermogravimetric analysis. The use of the prepared superabsorbent hydrogels for the growth of rice was also investigated through the water‐retention property. The water retention in the soil was enhanced with the hydrogels. Superabsorbent hydrogels based on carboxymethyl cellulose polymer and acrylamide monomer could be considered as water‐managing materials for agriculture and horticulture in desert and drought‐prone areas. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2003–2008, 2007     

Swelling behaviour and paracetamol release from poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide-itaconic acid) hydrogels

Copolymer hydrogels of N-isopropylacrylamide and itaconic acid (IA), crosslinked with N,N′-methylenebisacrylamide, were prepared by radical copolymerization. These hydrogels were investigated with regard to their composition to find materials with satisfactory swelling and drug release properties. A paracetamol is used as a model drug to investigate drug release profile of the hydrogels. It was found that the investigated hydrogels exhibited pH- and temperature-dependent swelling behaviour with restricted swelling and lower equilibrium degree of swelling at lower pH values and temperatures above the LCST value of PNIPAM (around 34 °C). The diffusion exponent for paracetamol release indicate that the mechanism of paracetamol release are governed by Fickian diffusion, while in all release media initial diffusion coefficient was lower than late time diffusion coefficient. Furthermore, the paracetamol release rate depends on the hydrogel degree of swelling and it increased in the first stage of diffusion process, whereas was no significant difference thereafter. The presence of the IA moieties incorporated into the network weakened the shear resistance of the hydrogels. In order to calculate the pore size the characteristic ratio for PNIPAM, C _n  = 11.7, was calculated. Based on the pore size, the investigated hydrogels can be regarded as microporous. According to the obtained results swelling behaviour, mechanical properties, drug-loading capacity and the drug release rate could be controlled by hydrogel composition and crosslinking density, which is important for application of the investigated hydrogels as drug delivery systems.     

Photopolymerised thermo-responsive poly(N,N-diethylacrylamide)-based copolymer hydrogels for potential drug delivery applications

Novel thermo-sensitive N,N-diethylacrylamide (DEAAm) based copolymer hydrogels were prepared via UV-induced free radical bulk polymerisation. UV polymerisation was employed to avoid the use of potentially toxic solvents; solution polymerisation has been the most common means for the preparation of PDEAAm-based hydrogels in the literature to date. The resultant hydrogels were analysed using nuclear magnetic resonance, Fourier transform infrared spectroscopy and modulated differential scanning calorimetry. Parameters such as the crosslinking degree and the nature of the incorporated hydrophilic component, N-vinyl-2-pyrrolidone (NVP) or N,N-dimethylacrylamide (DMAAm) were found to impact hydrogel structure, mechanical properties and swelling kinetics. Pulsatile swelling studies indicated that the hydrogels had thermo-reversible properties which were greatly affected by test temperature, nature of hydrophilic monomer used and crosslinker content. Aminophylline was selected as a model solute for drug loading and release studies by thermal deswelling in HCl buffer (pH 1.4) and phosphate buffer media (pH 6.8). The observed lag time prior to significant drug release from the more crosslinked P(DEAAm-NVP) hydrogels could make them suitable for delayed specific release in the intestine and potential alternatives to layers or membranes in time-specific and site-specific swelling-controlled drug delivery systems.     

Study of the properties of hydrolyzed polyacrylamide hydrogels with various pore structures and rapid pH-sensitivities

Nonionic polyacrylamide (PAAm) hydrogels were synthesized using three methods: room temperature polymerization, cryo-polymerization, and modified cryo-polymerization. Anionic PAAm hydrogels were obtained after hydrolyzing the nonionic hydrogels under alkaline conditions. The composition of anionic hydrogels was characterized by Fourier transform infrared (FT-IR) spectroscopy and element analysis. Morphological studies showed that the hydrogels exhibited various pore structures when they were synthesized using different methods. An additional mechanism for the formation of cryogels was proposed. Investigation of the swelling properties of the hydrogels and analysis of the swelling kinetics showed that the hydrolyzed PAAm hydrogels had rapid pH-sensitive rates.     

Indomethacin release behaviors from pH and thermoresponsive poly(vinyl alcohol) and poly(acrylic acid) IPN hydrogels for site-specific drug delivery

A temperature- and pH-responsive drug delivery system was studied by using interpenetrating polymer network (IPN) hydrogels constructed with poly(acrylic acid) (PAAc) and poly(vinyl alcohol) (PVA). The release of indomethacin incorporated into these hydrogels showed pulsatile patterns in response to both pH and temperature. Indomethacin diffused from the polymer matrices through the swelling and deswelling mechanism. The release amount increased at higher temperature because of the swelling caused by the dissociation of hydrogen bonding. The drastic change of drug release was achieved by alternating pH of the buffer solution and was attributed to the change of states of ionic groups within IPN hydrogels. The free water contents were calculated by using differential scanning calorimetry (DSC), and were proved to be the main factor in the swelling. These results demonstrated that the drug release could be controlled by the swelling/deswelling degree of IPN hydrogels as functions of pH and/or temperature. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65: 685–693     

Preparation and characterization of thermosensitive poly(N‐isopropylacrylamide)/poly(ethylene oxide) semi‐interpenetrating polymer networks

Temperature‐sensitive poly(N‐isopropylacrylamide) hydrogels were successfully synthesized by using poly(ethylene oxide) as the interpenetrating agent. The newly prepared semi‐interpenetrating polymer network (semi‐IPN) hydrogels exhibited much better properties as temperature‐sensitive polymers than they did in the past. Characterizations of the IPN hydrogels were investigated using a swelling experiment, FTIR spectroscopy, and differential scanning calorimetry (DSC). Semi‐IPN hydrogels exhibited a relatively high temperature dependent swelling ratio in the range of 23–28 at room temperature. DSC was used for the determination of the lower critical solution temperature of the semi‐IPN hydrogel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3032–3036, 2003     

亲水-疏水PVP-semi-IPN-PCL水凝胶的制备与溶胀性能

N-乙烯基吡咯烷酮（NVP）在聚己内酯（PCL）的乙酸乙酯溶液中进行自由基聚合,制备了亲水-疏水性聚乙烯吡咯烷酮（PVP）/聚己内酯（PCL）半互穿网络水凝胶（PVP-semi-IPN-PCL）。凝胶中PCL的熔融温度T_m无明显变化,而T_m吸热峰形状随PVP含量变化。凝胶平衡溶胀率（ESR）随PVP含量的升高而增大,结合水量的增大尤其显著。由于“笼蔽效应”,低浓度引发剂时,偶氮二异丁睛（AIBN）引发制备的凝胶ESR低于过氧化苯甲酰（BPO）引发剂。交联剂浓度较低时,以戊二醛交联形成凝胶的ESR较N,N-亚甲基双丙烯酰胺（NMBA）交联形成的凝胶大。浓度较高时,戊二醛交联凝胶ESR较NMBA低。PVP含量（质量）分别为20%、40%、60%、80%时,凝胶溶胀动力学Fick模型中的n值分别为0.854、0.471、0.466、0.253,说明在合适的PVP含量时,凝胶的溶胀动力学符合Fick模型。     

A novel pH‐sensitive and freeze‐thawed carboxymethyl chitosan/poly(vinyl alcohol) blended hydrogel for protein delivery

BACKGROUND: Blended hydrogels are widely applied in medical fields. They can provide many advantages, such as biocompatibility and biodegradability. Many materials and methods are used to obtain blended hydrogels. In this work, carboxymethyl chitosan (CMCS) and poly(vinyl alcohol) (PVA) blended hydrogels were prepared using the freezing and thawing technique. The properties of the hydrogels prepared, i.e. gel fraction, swelling and pH‐responsive behaviors, were investigated. RESULTS: The gel fraction increased with increasing time of freezing and thawing as determined through gravimetric analysis. It was also found that the equilibrium degree of swelling improved obviously due to the addition of CMCS compared to pure PVA hydrogel. The blended hydrogel with composition CMCS/PVA 80/20 (by weight) possessed the highest swelling ratio. The results of the influence of pH values on the swelling behavior showed that minimum swelling ratios of the hydrogels occurred near the isoelectric point of CMCS. Protein release studies were performed under various pH conditions: the release was much slower under acid than under basic conditions. The release showed a burst in the first 15 h and then steadily increased. CONCLUSION: The addition of CMCS can improve the physical properties of pure PVA hydrogels and provide pH sensitivity. It is concluded that PVA hydrogels containing CMCS could be potentially applied as oral delivery systems for protein drugs. Copyright © 2009 Society of Chemical Industry     

温度和pH双重刺激响应型水凝胶的溶胀性能研究

以丙烯酰胺、丙烯酸和双丙酮丙烯酰胺为原料,以N,N'-亚甲基双丙烯酰胺为交联剂,2-酮戊二酸为引发剂,采用光引发聚合方法制备出系列新型温度和pH响应型水凝胶。考察了交联剂用量、水凝胶组成、温度和pH值对凝胶溶胀性能的影响。结果表明,随交联剂用量的增加,凝胶的溶胀率减小,随凝胶组成中AA含量的增加,凝胶的溶胀率增加。凝胶的溶胀率随温度的升高而减小,随pH值的增大而增加,表现出显著的温敏和pH敏感性。     

温度和pH双重敏感性聚氨酯水凝胶的合成及性能研究

采用逐步聚合凝胶法完成对含有端烯基聚氨酯(UAA)预聚物与N-异丙基丙烯酰胺(NIPA)共聚,得到具有温度和pH双重敏感性的聚氨酯水凝胶。通过对该凝胶最大溶胀形貌观察,在不同温度及pH环境中对溶胀性能的探讨,发现该凝胶空间结构、溶胀性等方面适合作药物缓释。选用模拟药物茶碱,在模拟人体消化系统,即不同pH条件下对其缓释,7 h基本释放完,茶碱浓度相对稳定。因此,该材料在介入诊疗方面有极大的应用潜力,是一种有着巨大应用前景的生物医用材料。     

Preparation and characterization of a novel pH‐, thermo‐, and ionic strength‐responsive hydrogels based on xanthan gum–poly(aspartic acid)

A series of interpenetrating polymer networks (IPN) hydrogels with different compositions that based on xanthan gum (XG) and poly(aspartic acid) (PASP) were synthesized. The effects of various external surrounding stimuli, including pH, temperature, and ionic strength on XG–PASP hydrogels swelling properties were investigated. Chemical structural changes of the IPN hydrogels were characterized by Fourier transform infrared spectroscopy (FT‐IR), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and swelling ratio measurement. The swelling process was found to be a Fickian diffusion and reached swelling equilibrium quickly. It was found that the feed composition of PASP was an important factor that affected the properties of IPN hydrogels. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of pH- and/or temperature-sensitive hydrogels

A series of pH-sensitive hydrogels that exhibit volume phase transition phenomena have been synthesized in aqueous solution and characterized with respect to their dynamic swelling behaviors. Positively charged hydrogels were prepared by copolymerizing varying ratios of N-isopropylacrylamide and NN′-dimethylaminopropylmethacrylamide. The hydrogels based on a temperature-sensitive hydrogel demonstrate a large change of equilibrium swelling in response to small variations of pH and/or temperature. These hydrogels exhibit different lower critical solution temperature (LCST) ranges depending on the environmental pH values. Below their LCST, they exhibit small and broad pH sensitivities normally observed in most hydrophilic polyelectrolyte gels, but above their LCST, they exhibit sharp pH dependent phase transition behaviors. The pH-dependent phase transition is strongly affected by temperature, while the temperature-dependent transition is, in turn, largely influenced by the pH. As the temperature is raised, the transitional degree of gel swelling change becomes sharper and larger, and the phase transition pH value shifts to a lower pH. It was also found that swelling is faster than deswelling for these cationic hydrogels, which suggests the existence of a water diffusion barrier during the deswelling. The swelling kinetics of initially dry and glassy gels were strongly dependent on both the pH value and temperature.     

Equilibrium swelling and mechanical properties of hydrogels of acrylamide and itaconic acid or its esters

Summary The equilibrium swelling and the plateau elastic modulus of a family of hydrogels made by the polymerization of acrylamide with itaconic acid or some of its esters were investigated as a function of composition and crosslinking degree to find materials with satisfactory swelling and elastic properties. We show that an appropriate selection of the comonomers and the concentration of the crosslinking agent is very important to produce hydrogels with large swelling capacity and good mechanical attributes. Tailoring of mechanical properties and swelling can also be achieved by this method. Received: 7 September 1999/Revised version: 3 December 1999/Accepted: 6 December 1999     

Hydrogels from glycidyl derivatives of poly(vinyl alcohol)

Poly(vinyl alcohol) (PVA) was modified with phthalic anhydride to obtain half esters with carboxylic acid groups, which made the reaction with epichlorohydrin easier. The oxirane ring underwent a further crosslinking that led to crosslinked polymers with polar groups capable of interacting strongly with water and therefore with properties of hydrogels. The curing kinetics of the crosslinking were studied by differential scanning calorimetry, and the dependence of the activation energy on conversion degree was studied by isoconversional kinetic analysis. Water absorption was determined gravimetrically as a function of time at room temperature. The swelling behavior of these hydrogels was related to the degree of crosslinking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 693–698, 2003     

Humic acid embedded chitosan/poly (vinyl alcohol) pH-sensitive hydrogel: Synthesis,characterization, swelling kinetic and diffusion coefficient

In the present research, humic acid (HA) embedded chitosan (CHT)-poly (vinyl alcohol) (PVA) pH-sensitive hydrogels have been synthesized using glutaraldehyde as a crosslinker. The hydrogels were characterized by Fourier-transform infrared (FT-IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) analysis. The effect of HA content, pH, and temperature on the equilibrium solvent uptake has been investigated. With higher HA contents, the equilibrium swelling capacity increases while lower concentrations of acid cause a decrease in the degree of the swelling. The hydrogels have been found to undergo a number of swelling/deswelling cycles when pH of the swelling medium changes from 1.5 to 11.0. Fick’s law, first-order, and second-order kinetic models were applied to the swelling ratio of hydrogels to explain the mass transfer mechanism and specify swelling kinetic parameters. The swelling parameters such as equilibrium swelling capacity, swelling rate constant, swelling exponent, initial swelling rate, diffusion coefficient, etc., have been evaluated.