Relaxational behavior and swelling‐pH master curves of poly[(diethylaminoethyl methacrylate)‐graft‐(ethylene glycol)] hydrogels

Poly[(diethylaminoethyl methacrylate)‐graft‐(ethylene glycol)] hydrogels were prepared with a molar ratio of 10:1 of diethylaminoethyl methacrylate to poly(ethylene glycol) of number‐average molecular weights (M_n) 200, 400 and 1000 g mol^?1 using tetra(ethylene glycol) dimethacrylate to give a crosslinking ratio between 0.5 and 4.0 %. Glucose oxidase and catalase were immobilized in the matrix during polymerization. The maximum enzyme loading used was 6.6 × 10^?4 g of glucose oxidase per g of polymer. The equilibrium and dynamic swelling properties of these hydrogels were investigated. The pH‐dependent equilibrium swelling characteristics showed a sharp transition between the swollen and the collapsed state at pH 7.0. The dynamic response of the hydrogel discs to pH was analyzed in pulsatile pH conditions. The effects of particle size, crosslinking and molecular weight of poly(ethylene glycol) (PEG) on the dynamic swelling response were investigated. The pulsatile nature of the response was analyzed using Boltzmann superposition. Swelling–pH master curves were obtained. Copyright © 2004 Society of Chemical Industry     

Hydrogels for oral drug delivery of peptides: Synthesis and characterization

In this study hydrogels were synthesized by the copolymerization of acrylamide and itaconic acid in the presence of poly(N‐vinyl‐2‐pyrrolidone) in an aqueous medium. The incorporation of a small amount of itaconic acid resulted in the transition of the swelling behavior from Fickian to non‐Fickian. The hydrogels showed good response to the valency of the counterions and pH of the swelling media. The equilibrium water uptake increased with the pH of the external solution, thus attaining a maximum value at pH 7–8. The gels exhibited a number of deswelling–swelling cycles while maintaining mechanical strength and shape stability. The amount of itaconic acid present in the system affected the swelling behavior of the hydrogels in a rather unusual way. At pH 2.0 the equilibrium water uptake increased with the amount of acid monomer up to 15 mM, remained almost constant for a very small range of concentrations (i.e., up to 22 mM), and then finally decreased with the further increase of the acid content. However, a continuous increase was observed at the pH 7.0 of the swelling media. The hydrogels showed very poor temperature dependency and the activation energies for the samples with and without itaconic acid were 29.09 and 19.92 kJ mol^?1, respectively. Finally, the swelling and deswelling processes were explained on the basis of two different mechanisms that were followed by the gels. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1717–1729, 2002     

Enzymatically degradable and pH‐sensitive hydrogels for colon‐targeted oral drug delivery. I. Synthesis and characterization

Cylindrical hydrogels, composed of starch and poly(acrylic acid), were synthesized, and their swelling behavior was studied as a function of the pH of the medium. The gels underwent a sharp transition from Fickian swelling behavior (swelling exponent n = 0.30) to non‐Fickian swelling behavior (n = 0.96) as the pH of the swelling medium changed from 2.0 to 7.4. The hydrogels also underwent partial enzymatic degradation in an amylase‐containing medium of pH 7.4 at 37°C. The effects of the enzyme concentration in the swelling media, the amount of starch present in the gel, the initial water content, the degree of crosslinking, and the diameter of cylindrical hydrogels on the degradation behavior were studied. The degradation of the gels followed Michaelis–Menten kinetics, and the value of the Menten constant was 41.62 × 10^?2. The gels exhibited minimum swelling in an acidic pH medium through the formation of a complex hydrogen‐bonded structure and underwent enzymatic degradation in a medium of pH 7.4 (i.e., simulating intestinal fluid) along with chain‐relaxation‐controlled swelling. Therefore, the gels have potential for colon‐targeted drug delivery. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3630–3643, 2004     

Poly(methacrylamide‐co‐acrylic acid) hydrogels for gastrointestinal delivery of theophylline. I. Swelling characterization

pH sensitive copolymeric hydrogels have been synthesized by free‐radical polymerization of methacrylamide and acrylic acid in aqueous medium. The gels were characterized by FTIR spectroscopy, thermogravimetric analysis, and swelling measurements. To determine the suitability of theses hydrogels for gastrointestinal oral delivery of model drug theophylline, their swelling behavior was investigated as a function of pH and various structural parameters such as the average molecular weight between crosslinks, crosslink density, and mesh size were calculated. Likewise initial, average and late time diffusion coefficients were also evaluated in simulating intestinal fluid of pH 6.8 at 37°C. The gel underwent sharp volume phase transition in the vicinity of pH 5.8. The mesh sizes of the hydrogel were between 8.4 and 9.2 Å in the collapsed state (pH range 1–2; SGF) and between 514 and 524 Å in the swollen state (pH range 7–8; SIF). The experimental data was found to fit well to Beren‐Hopfenberg equation thus suggesting that later part of swelling was chain relaxation controlled. The activation energy, as determined from Arrhenius equation was found to be 13.71 kJ mol^?1. Likewise, enthalpy of mixing was also evaluated using Gibbs‐Helmholtz equation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2995–3008, 2006     

Dynamic swelling behavior of pH‐sensitive anionic hydrogels used for protein delivery

There have been many attempts to use anionic hydrogels as oral protein delivery carriers because of their pH‐responsive swelling behavior. The dynamic swelling behavior of poly(methacrylic acid‐co‐methacryloxyethyl glucoside) and poly(methacrylic acid‐g‐ethylene glycol) hydrogels was investigated to determine the mechanism of water transport through these anionic hydrogels. The exponential relation M_t/M_∞ = ktⁿ (where M_t is the mass of water absorbed at time t and M_∞ is the mass of water absorbed at equilibrium) was used to calculate the exponent (n) describing the Fickian or non‐Fickian behavior of swelling polymer networks. The mechanism of water transport through these gels was significantly affected by the pH of the swelling medium. The mechanism of water transport became more relaxation‐controlled in a swelling medium of pH 7.0, which was higher than pK_a of the gels. The experimental results of the time‐dependent swelling behaviors of the gels were analyzed with several mathematical models. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1606–1613, 2003     

Radiation polymerization and concentration separation of P(NIPA‐co‐AMPS) hydrogels

Extraction or concentration with temperature‐sensitive hydrogels is a novel separation technology. In this study, N‐isopropylacrylamide (NIPA) was synthesized by acrylonitrile and isopropanol. Poly(N‐isopropylacrylamide) (PNIPA) and copolymer of NIPA and 2‐acrylamide‐2‐methylpropane sulfonate [P(NIPA‐co‐AMPS)] hydrogels were prepared by radiation polymerization. Dependence of their swelling behavior on temperature was studied. Effects of radiation dose on polymerization, feed composition on thermoresponse, electrolyte on relative swelling ratio, and swelling and deswelling kinetics were investigated. The experimental results showed that P(NIPA‐co‐AMPS) hydrogels with low content of AMPS/NIPA (1–5 %), prepared at a radiation dose‐rate of 1 kGy/h and total dose of 30–40 kGy, could enhance the swelling ratio of PNIPA hydrogels significantly and raise the phase‐transition temperatures. P(NIPA‐co‐AMPS) hydrogels produced under optimum conditions were used to concentrate aqueous bovine serum albumin (BSA, M = 69 000 g mol^?1) solution. When aqueous BSA concentration was below 5 %, the separation efficiency was more than 80 % with low cost and low energy consumption. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels

Novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels were prepared by free radical copolymerization of acrylamide and itaconic acid (IA) in chitosan solution. The hydrogels were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and the swelling ratios of the hydrogels in water (pH 6.8) and pH 1.2. The influence of composition on the thermal properties of the hydrogels was assessed. The glass transition temperatures of the samples increased with IA content, ranging from 110 to 136 °C. Swelling of the hydrogels was found to obey second‐order kinetics with respect to the remnant swelling, indicating that diffusion is controlled by the relaxation of chains. The equilibrium swelling degree was strongly dependent on pH and composition. At both pH values the highest water uptake was obtained for the IA‐free sample M1. From the equilibrium swelling results the average molar mass between crosslinks, M_c, and the crosslink density of the chitosan‐poly(acrylamide‐co‐itaconic acid) samples were calculated. The results evidenced the reinforcing effect of IA on the hydrogel structure. It is concluded that these highly swellable pH‐sensitive hydrogels can be useful for applications in biomedicine and pharmacy. © 2013 Society of Chemical Industry     

Water‐sorption and metal‐uptake behavior of pH‐responsive poly (N‐acryloyl‐N′‐methylpiperazine) gels

Hydrogels based on N‐acryloyl‐N′‐methylpiperazine (AcrNMP) swelled extensively in solutions of low pH due to the protonation of the tertiary amine. The water transport in the gels under an acidic condition was non‐Fickian and nearly Fickian in neutral pH with the collective diffusion coefficients determined as 2.08 × 10⁻⁷ and 5.00 × 10⁻⁷ cm⁻² s⁻¹, respectively. These gels demonstrated good metal‐uptake behavior with various divalent metal ions, in particular, copper and nickel, with the uptake capacity increased with increasing pH. The swelling ratio of the gel in the presence of metal ions decreased with increasing metal ion uptake. The results suggest that high metal ion uptake can lead to physical crosslinking arising from the interchain metal complex formation. The metal‐loaded gels could be stripped easily with 1M H₂SO₄ without any loss in their uptake capacity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 268–273, 2001     

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     

Photopolymerized pH‐sensitive semi‐IPN: Synthesis,water uptake analysis,and preliminary drug release study

A series of pH‐sensitive semi‐IPN hydrogels, composed of varying amounts of monomer acrylic acid(AAc), crosslinker N,N′ methylene bisacrylamide, polymer cellulose acetate (CA) were synthesized via photoinitiated polymerization in dimethyl formamide (DMF) medium. The CA/P (AAc) hydrogels were characterized by FTIR, and TG analysis. The equilibrium water uptake data was used to determine various network parameters. For all the samples synthesized, the swelling exponent “n,” initial diffusion coefficient D and average diffusion coefficient D_ave were found to be in the range of 0.51–0.72, 3.16 to 7.14 × 10^?6 cm² min^?1 and 94.16–120.56 cm² min^?1, respectively. The hydrogel demonstrated fair pH‐dependent swelling behavior, with nearly 20% swelling in the medium of pH 1.0 and 615% in the medium of pH 7.4 at 37°C, respectively. The gel showed excellent swelling–deswelling cycles which were interpreted quantitatively by first order kinetic swelling and deswelling models. Finally, the preliminary insulin release study, carried out in the media of varying pH, observed almost 16% release of entrapped drug in the simulating gastric fluid (SGF) of pH 1.0 in first 2 h and nearly 51% in next 6 h in simulating intestinal fluid(SIF) of pH 7.4 at 37°C. POLYM. ENG. SCI., 53:2129–2140, 2013. © 2013 Society of Plastics Engineers     

Cytarabine trapping in poly(2-hydroxyethyl methacrylate-co-acrylamide) hydrogels: drug delivery studies

Copolymeric hydrogels of poly(2-hydroxyethyl methacrylate-co-acrylamide) [p(HEMA-co-A)] crosslinked with ethylene glycol dimethacrylate, with a high equilibrium degree of swelling (37–65 wt%) in saline solution (NaCl 0.9 wt%) were synthesized as devices for controlled release of cytarabine (ara-C). Two compositions of the copolymer, each with a different degree of crosslinking have been studied, HEMA80/A20 and HEMA60/A40. The antineoplasic drug was included in the feed mixture of polymerization, and discs 3.7 ± 0.4 mm thick and 11.8 ± 0.2 mm in diameter with 5–40 mg (1.0–8.3 wt%) of ara-C were obtained. The diffusion studies followed Fick's second law. The diffusion coefficients for swelling of the gels were between 3.60 × 10⁻¹¹ and 15.8 × 10⁻¹¹ m² s⁻¹; those for release of ara-C were between 0.31 × 10⁻¹¹ and 7.18 × 10⁻¹¹ m² s⁻¹. The activation energies for swelling were in the range 23.4–31.9 kJ mol⁻¹ and those for ara-C release were 42.2–61.6 kJ mol⁻¹; their values indicate that the drug release process depends on drug–matrix and drug–water interactions that are influenced by the aqueous solution content and the network size of the gels. Total release of the drug takes place between 17 h from H60/A40/E2 at 310 K and 6 days from H80/A20/E10 at 288 K. Ara-C degradation was not observed either during loading of the gels or during drug release. © 1999 Society of Chemical Industry     

Swelling behavior of poly(acrylamide‐co‐N‐vinylimidazole) hydrogels under different environment conditions

A series of random copolymers of acrylamide and N‐vinylimidazole, poly(AAm‐co‐NVI), with various compositions were prepared using redox copolymerization. The influence of environmental conditions such as pH, temperature, and ionic strength on the swelling behavior of the copolymeric hydrogels was investigated. The hydrogels exhibited the highest equilibrium swelling in basic medium at high temperature. Equilibrium swelling decreased with rising ionic strength at pH 5.0. As pH increased, equilibrium swelling of the hydrogels increased at pH 11.0 and I = 0.20 M. Swelling kinetics of the hydrogels was found to be non‐Fickian at 25°C. The process tended to be Fickian at higher pH and temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1783–1788, 2005     

Effect of hydrophobic monomer on the synthesis and swelling behaviour of a collagen‐graft‐poly[(acrylic acid)‐co‐(sodium acrylate)] hydrogel

BACKGROUND: Graft polymerization of vinylic monomers onto natural backbones is an efficient approach for the synthesis of natural‐based superabsorbents. The nature of the monomers will affect the swelling behaviour of the superabsorbents. Here, a novel superabsorbent was synthesized through grafting of acrylic acid onto collagen in the presence of hydrophobic styrene as co‐monomer. Subsequently, the effect of styrene on the swelling behaviour of the superabsorbent was studied. RESULTS: The highly swelling superabsorbent was prepared by introducing styrene into a collagen‐graft‐poly(acrylic acid) hydrogel. By inclusion of styrene monomer, the swelling capacity of the hydrogel was increased; this is discussed according to the network composition. The effect of swelling media (salt solutions and various pH values) was investigated. The results of absorbency under load showed that hydrogels containing phenyl groups exhibit better behaviour; however, by introducing styrene, the rate of water uptake and resistance to water holding under heating was reduced. Scanning electron micrographs of hydrogels revealed a decrease in porosity on using styrene. CONCLUSION: Inclusion of styrene monomer in the ionic superabsorbent caused high swelling capacity with better absorbency under load. This can be used to prepare highly swelling superabsorbents with good mechanical properties. The pH reversibility of the synthesized superabsorbent makes it a candidate for use in the controlled release of drugs and in agrochemicals. Copyright © 2008 Society of Chemical Industry     

Synthesis and properties of radiation‐induced acrylamide–acrylic acid hydrogels

Acrylamide (AAm)/acrylic acid (AAc) hydrogels in the cylindirical form were prepared by γ‐irradiating binary systems of AAm/AAc with 2.6–20.0 kGy γ‐rays. The effect of the dose and relative amounts of AAc and pH on the swelling properties, diffusion behavior of water, diffusion coefficients, and network properties of hydrogel systems was investigated. The swelling capacities of AAm/AAc hydrogels were in the range of 1000–3000%, while poly(acrylamide) (PAAm) hydrogels swelled in the range of 450–700%. Water diffusion into hydrogels was found to be non‐Fickian‐type diffusion. Diffusion coefficients of AAm/AAc hydrogels were found between 0.79 × 10^?5 and 2.78 × 10^?5 cm² min^?1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3570–3580, 2002     

Thermoreversible hydrogels X: Synthesis and swelling behavior of the (N‐isopropylacrylamide‐co‐sodium 2‐acrylamido‐2‐methylpropyl sulfonate) copolymeric hydrogels

A series of thermosensitive hydrogels were prepared from various molar ratios of N‐isopropylacrylamide (NIPAAm) and sodium‐2‐acrylamido‐2‐methylpropyl sulfonate (NaAMPS). Factors such as temperature and initial total monomer concentration and different pH solutions were investigated. Results indicated that the more the NaAMPS content in hydrogel system, the higher the swelling ratio and the gel transition temperature; the higher the initial monomer concentration, the lower the swelling ratio. The result also indicated that the NIPAAm/NaAMPS copolymeric hydrogels had different swelling ratios in various pH environments. The present gels showed a pH‐reversible property between pH 3 and pH 10 and thermoreversibility. The swelling ratios of copolymeric gels were lower in a strong alkaline environment because the gels were screened by counterions. Finally, the drug release behavior of these gels was also investigated in this article. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1760–1768, 2000     

Rheological properties of poly(ethylene glycol)/poly(N‐isopropylacrylamide‐co‐2‐acrylamido‐2‐methylpropanesulphonic acid) semi‐interpenetrating networks

For the increasing demands of multifunctional materials in applications such as drug delivery system, a pH‐ and temperature‐responsive polyelectrolyte copolymer gel system was studied using rheometry. Rheological properties, determined by plate–plate rheometry in oscillatory shear, of hydrogels formed by free radical initiated copolymerization of N‐isopropylacrylamide (NIPA) and 2‐acrylamido‐2‐methylpropanesulphonic acid (AMPS) in the presence of methylene bisacrylamide (MBAA) as crosslinker are compared with the properties of semi‐interpenetrating network (SIPN) polyelectrolyte gels made by incorporation of poly(ethylene glycol) with molar mass 6000 g mol^?1 (PEG6000). Based on our systematic studies for this PEG/SIPN system, the effects of initiator and crosslinker concentration, relative proportions of comonomer units in the main chains, PEG6000 content and temperature on viscoelastic properties, unusual high storage moduli at small strain for the SIPN were discussed. The SIPN gel with characteristics of PEG molecules as well as pH and temperature responsiveness from AMPS and NIPA units has potential application in drug delivery system design. Ice‐like rheological behavior of the PEG/AMPS‐NIPA SIPN gels at low temperature was first time reported and water remains homogeneous without phase separation in PEG/AMPS‐NIPA SIPN hydrogels at low temperature may be considered as an ideal candidate for water storage material. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Examining the preparation and characterization of coatings based on linear aromatic terpoly(methoxy‐cyanurate‐thiocyanurate)s

Two series of terpoly(methoxy‐cyanurate‐thiocyanurate)s based on thiodiphenol and dithiodiphenyl sulfide and on dihydroxydiphenyl ether and dithiodiphenyl ether, were prepared in good yield and purity and fully characterized. Most of the resulting polymers, formed at room temperature using phase transfer catalysis, can be cast into films with good resilience and thermal stability (some examples suffer practically no mass loss when held isothermally at 190 °C and only display appreciable losses when held continuously at 225 °C). Char yields of 53%?61% are achieved in nitrogen depending on backbone structure. Some problems were encountered with solubility, particularly with copolymers, which limited molecular weight analysis, but values of M_n = 8000–13 000 g mol^?1 were obtained for the polymers based on thiodiphenol and dithiodiphenyl sulfide, and M_n = 5000–13 000 g mol^?1 for the polymers based on dihydroxydiphenyl ether and dithiodiphenyl ether. DSC reveals polymerization exotherms with maxima at 184–207 °C (ΔH_p = 43–59 kJ mol^?1), which are believed to be due to isomerization of the cyanurate to the isocyanurate (activation energies span 159–195 kJ mol^?1). Molecular simulation shows that diphenylether and diphenylsulfide display very similar conformational energy surfaces and would therefore be expected to adopt similar conformations, but the diphenylsulfide offers less resistance to deformations that increase the proximity of the two phenyl rings and results in more resilient films. © 2013 Society of Chemical Industry     

Temperature‐responsive characteristics of poly(N‐isopropylacrylamide) hydrogels with macroporous structure

Macroporous poly(N‐isopropylacrylamide) (PNIPA) hydrogels were synthesized by free‐radical crosslinking polymerization in aqueous solution from N‐isopropylacrylamide monomer and N,N‐methylenebis (acrylamide) crosslinker using poly(ethylene glycol) (PEG) with three different number‐average molecular weights of 300, 600 and 1000 g mol^?1 as the pore‐forming agent. The influence of the molecular weight and amount of PEG pore‐forming agent on the swelling ratio and network parameters such as polymer–solvent interaction parameter (χ) and crosslinking density (ν_E) of the hydrogels is reported and discussed. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying different molecular weights and compositions of PEG during polymerization. At a temperature below the volume phase transition temperature, the macroporous hydrogels absorbed larger amounts of water compared to that of conventional PNIPA hydrogels, and showed higher equilibrated swelling ratios in aqueous medium. Particularly, the unique macroporous structure provides numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to external temperature changes during the swelling and deswelling process. These macroporous PNIPA hydrogels may be useful for potential applications in controlled release of macromolecular active agents. Copyright © 2006 Society of Chemical Industry     

Swelling mechanism of porous P(VP‐co‐MAA)/PNIPAM semi‐IPN hydrogels with various pore sizes prepared by a freeze treatment

BACKGROUND: The objective of the work reported was to investigate the effect of gel microstructure on the swelling mechanism. A series of porous gels with various pore sizes were prepared by freeze‐treating a conventional hydrogel that contained various amounts of water at ? 20 °C. Scanning electron microscopy and differential scanning calorimetry were used to characterize the microstructure of the porous gels. RESULTS: The experimental results showed that the water content during freezing was the key factor controlling the microstructure. Measurement of swelling kinetics showed that a greater amount of water during the freezing process would lead to a rapid swelling rate. The apparent diffusion coefficients (D_p) at all times during the swelling process were obtained by fitting the experimental data to the diffusion equation. The values of D_p suggested that the swelling mechanism of the gels depends on the pore size. The diffusion exponent (n) obtained by fitting the fractional mass change (M_t/M_∞) to equation of Fick's law further confirmed that the swelling mechanism of the gels is determined by the pore size. CONCLUSION: The swelling mechanism of the gels is determined by the microstructure related to the pore size and the thickness of struts. The microstructure can be controlled by adjusting the water content of the hydrogels by changing the pH of the swelling medium prior to freezing. Copyright © 2008 Society of Chemical Industry     

pH‐thermoreversible hydrogels. I. Synthesis and swelling behaviors of the (N‐isopropylacrylamide‐co‐acrylamide‐co‐2‐hydroxyethyl methacrylate) copolymeric hydrogels

A series of pH‐thermoreversible hydrogels that exhibited volume phase transition was synthesized by various molar ratios of N‐isopropylacrylamide (NIPAAm), acrylamide (AAm), and 2‐hydroxyethyl methacrylate (HEMA). The influence of environmental conditions such as temperature and pH value on the swelling behavior of these copolymeric gels was investigated. Results showed that the hydrogels exhibited different equilibrium swelling ratios in different pH solutions. Amide groups could be hydrolyzed to form negatively charged carboxylate ion groups in their hydrophilic polymeric network in response to an external pH variation. The pH sensitivities of these gels also depended on the AAm content in the copolymeric gels; thus the greater the AAm content, the higher the pH sensitivity. These hydrogels, based on a temperature‐sensitive hydrogel, demonstrated a significant change of equilibrium swelling in aqueous media between a highly solvated, swollen gel state and a dehydrated network response to small variations of temperature. pH‐thermoreversible hydrogels were used for a study of the release of a model drug, caffeine, with changes in temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 221–231, 1999