Uses of electron‐beam irradiation to prepare pH‐ and temperature‐sensitive hydrogels from reactive poly(vinyl alcohol) grafts

Thermosensitive poly(vinyl alcohol)‐graft‐(maleic anhydride), PVA‐MA, and poly(vinyl alcohol)‐graft‐(N‐isopropylacrylamide maleic anhydride) (PVA‐MA‐NIPAAm) copolymers containing carboxyl groups were prepared using electron beam irradiation at dose 80 kGy. The swelling ratios of the cross‐linked gels were measured at various temperatures. The LCST values were measured using DSC technique. The temperature dependence of the swelling ratios of the cross‐linked copolymers and terpolymers were measured at different temperatures. The swelling ratios of copolymers increased with increasing temperature up to 25–38°C, then decreased. The swelling behavior of both copolymers and terpolymers was referred to formation of hydrogen bonds between amide group of NIPAAm moieties and carboxyl group in MA moieties and to hydrophobic interaction due to methyl groups of NIPAAm. The swelling behaviors of these gels were analyzed in buffer solution at various pH. Swelling ratios of all gels were relatively high and they showed reasonable sensitive to pH. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fast responsive poly(acrylic acid‐co‐N‐isopropyl acrylamide) hydrogels based on new crosslinker

Novel dual temperature‐ and pH‐sensitive poly(acrylic acid‐co‐N‐isopropylacrylamide), AA/NIPAAm, hydrogels were successfully prepared by chemical crosslinking with crosslinkers. Copolymers of AA/NIPAAm were crosslinked in the presence of different mol % of N,N‐methylene bisacrylamide (MBA) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked AA/NIPAAm series are evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MBA concentrations. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. The prepared MAAm type AA/NIPAAm hydrogels exhibited a more rapid deswelling rate than MBA type AA/NIPAAm hydrogels in ultra pure water in response to abrupt changes from 20°C to 50°C. The results of this study provide valuable information regarding the development of dual stimuli‐sensitive hydrogels with fast responsiveness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on preparation and properties of porous biodegradable poly(NIPAAm) hydrogels

A series of biodegradable porous hydrogels, based on thermosensitive N‐isopropylacrylamide (NIPAAm) and biodegradable crosslinker‐polycaprolactone diacrylate (PCLdA) that was synthesized from polycaprolactone diol with acryloyl chloride were prepared by photopolymerization at low temperature. The effect of the crosslinker content and gelation method on the swelling behaviors and physical properties for the poly(NIPAAm) hydrogels was investigated. Results showed that the swelling ratio of the gel in deionized water decreased with an increase of the content of polycaprolactone (PCL) segment in the poly(NIPAAm) hydrogels. The properties of the gels crosslinked with PCLdA were compared with those crosslinked with N, N′‐methylenebisacrylamide (NMBA). The results showed that the critical gel transition temperatures (CGTT) of the gels crosslinked with PCLdA were lower than those of the gels crosslinked with NMBA due to the hydrophobicity of the PCL segment. The results also showed that the gels crosslinked with PCLdA had higher mechanical strength and crosslinking density than those gels crosslinked with NMBA. Comparing the porous gels with nonporous gels, the results showed that the swelling ratio and CGTT of the porous gels were higher than those of the nonporous gels, and the transition temperature curve was smoother for the porous gels. The porous gels also exhibited more rapid thermal response and faster degradation rates. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of pH- and thermoresponsive Poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide-co-itaconic acid) hydrogels crosslinked with <Emphasis Type="Italic">N</Emphasis>-maleyl chitosan

Biodegradable cross-linker N-maleyl chitosan (N-MACH) was synthesized with chitosan (CS) and maleic anhydride (MA) by acylation. With N-MACH cross-linker, a series of cross-linked poly(N-isopropylacrylamide-co-itaconic acid) [P(NIPAAm-co-IA)] hydrogels were prepared, and their pH-and temperature-responsive behaviors, water contents, swelling/deswelling kinetics were investigated. By alternating the NIPAAm/IA weight ratios, hydrogels had the volume phase transition temperature (VPTT) changed from 33 to 38 °C, whereas cross-linking density did not affect the VPTT apparently. The water content of hydrogels was controlled by the monomer weight ratios of NIPAAm/IA, swelling media, and the cross-linking density. The results of the influence of pH value on the swelling behaviors showed that the minimum swelling ratios of the hydrogels appeared in neutral buffer solution, which was attributed to chemical composition of the hydrogels and the swelling media. In the swelling/deswelling kinetics, all the dried hydrogels exhibited fast swelling within 480 min and fast deswelling within 20 min, which was independent of the content of IA and cross-linker.     

Thermoreversible hydrogels VI: Swelling behavior of the (N-isopropylacrylamide-co-diethyl methyl methacryloyloxyethyl ammonium iodide) copolymeric hydrogels in aqueous salt solutions

A series of N-isopropylacrylamide/diethyl methyl methacryloyloxyethyl ammonium iodide (NIPAAm/DEMMAI) copolymeric gels were prepared from blending NIPAAm, cationic monomer DEMMAI, and N,N′-methylene bisacrylamide (NMBA) in various molar ratios in this article. The effects of the amount of the cationic monomer in the copolymeric gels on the swelling behaviors in water and various saline solutions at various temperatures were investigated. Results showed that the swelling ratios of copolymeric gels were significantly larger than those of pure NIPAAm gel, and that the more the DEMMAI content, the higher the gel transition temperature. In the saline solution, results showed that the swelling ratio for pure NIPAAm gel had not changed significantly with an increase of the salt concentration until the salt concentration was larger than 0.1 M. The swelling ratios for the copolymeric gels NIPAAm/DEMMAI were decreased with increasing salt concentration. In various saline solutions, results showed that the anionic effects were greater than cationic effects in the presence of common anion with different cations and common cation with different anions for these hydrogels. Finally, we also tested the reversibility of the NIPAAm/DEMMAI copolymeric gels. The deswelling and reswelling kinetics were dependent on the temperature which was below or above the gel transition temperature. The gel with a small DEMMAI content has a good reversibility.     

Swelling and Diffusion Properties of Poly(acrylamide-co-maleic acid) Hydrogels: A Study with Different Crosslinking Agents

Crosslinked hydrogels comprising acrylamide (AAm) and maleic acid (MA) were synthesized by free radical polymerization in presence of a crosslinker using ammonium persulfate (APS) and N,N,N¹,N¹-tetramethylethylenediamine (TMEDA) as initiator and activator, respectively. The crosslinked hydrogel formation was confirmed by IR analysis. The swelling/de-swelling characteristics were studied in detail for crosslinked poly(acrylamide-co-maleic acid) [poly(AAM-co-MA)] hydrogels containing different amounts of maleic acid. Four different crosslinkers such as 1,2-ethyleneglycol dimethacrylate (EGDMA), 1,4-butanediol diacrylate (BDDA), 1,6-hexanediol diacrylate (HDDA), and diallyl phthalate (DP) were utilized to study their influence on the swelling behavior of the hydrogels. The effect of reaction parameters such as the concentration of crosslinker and initiator on swelling capacity of the crosslinked poly(AAm-co-MA) hydrogels was also investigated. Further, the influence of various salts, simulated biological fluids, and pH solutions on the swelling pattern of hydrogels was studied extensively. Phase separation morphology of crosslinked hydrogels was also studied by differential scanning calorimetry. The morphology of crosslinked hydrogels were revealed using scanning electron microscopy (SEM).     

Thermo‐ and pH‐responsive behaviors of graft copolymer and blend based on chitosan and N‐isopropylacrylamide

Thermo‐ and pH‐sensitive polymers were prepared by graft polymerization or blending of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm). The graft copolymer and blend were characterized by Fourier transform‐infrared, thermogravimetric analysis, X‐ray diffraction measurements, and solubility test. The maximum grafting (%) of chitosan‐g‐(N‐isopropylacrylamide) (NIPAAm) was obtained at the 0.5 M NIPAAm monomer concentration, 2 × 10⁻³ M of ceric ammonium nitrate initiator and 2 h of reaction time at 25°C. The percentage of grafting (%) and the efficiency of grafting (%) gradually increased with the concentration of NIPAAm up to 0.5 M, and then decreased at above 0.5 M NIPAAm concentration due to the increase in the homopolymerization of NIPAAm. Both crosslinked chitosan‐g‐NIPAAm and chitosan/PNIPAAm blend reached an equilibrium state within 30 min. The equilibrium water content of all IPN samples dropped sharply at pH > 6 and temperature > 30°C. In the buffer solutions of various pH and temperature, the chitosan/PNIPAAm blend IPN has a somewhat higher swelling than that of the chitosan‐g‐NIPAAm IPN. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1381–1391, 2000     

Effect of LCST on the swelling of PAAm-NIPA copolymers: a fluorescence study

Temperature sensitive copolymers were prepared by free radical crosslinking copolymerization in aqueous solution with different molar percentage of N-isopropylacrylamide (NIPA) and acrylamide (AAm) monomers. N,N′-methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) were used as a crosslinker and an initiator, respectively. The steady-state fluorescence (SSF) technique was used to determine the low critical phase transition temperature (LCST) for PAAm-NIPA copolymers. Swelling experiments were performed in water at various temperatures by real time monitoring of pyranine (Py) fluorescence intensity, I which decreased as swelling proceeded. The Stern–Volmer equation is modified for low quenching efficiencies to interpret the behavior of pyranine intensity during the swelling of PAAm-NIPA copolymers. The Li–Tanaka equation was used to determine the swelling time constants, τ ₁ and the cooperative diffusion coefficients, D ₀ from fluorescence intensity, weight and volume variations of the copolymers at various temperatures. It was observed that τ ₁ first increased up to LCST, and then decreased; naturally D ₀ decreased up to LCST and then increased upon increasing temperature. It was understood that (LCST) increases as PAAm contents increase in the PAAm-NIPA copolymers.     

Effect of crosslinkers on size and temperature sensitivity of poly(N-isopropylacrylamide) microgels

In this work, we study the effect of crosslinkers on the size and swelling properties of temperature sensitive N-isopropylacrylamide (NIPAAm) microgels produced by dispersion polymerization. The crosslinkers studied were N,N′-methylenebisacrylamide (MBA), ethylene glycol dimethacrylate (EGDMA) an 3,9-divinyl-2,4,8,10-tetra-oxaspiro[5.5] undecane (DVA). The type of crosslinker had a major impact on the size and swelling behavior, although the proportion of crosslinker used in each case was low (maximum 5 mol%). The effect can be related to the hydrophilic/hydrophobic characteristics of the crosslinkers. DVA produces smaller hydrogels with reduced swelling ratio, MBA produces bigger microgels with higher swelling ratio, while EGDMA results in an intermediate behavior. With increasing amount of crosslinker used in the synthesis, the extent of the swelling ratio decreases for DVA and EGDMA crosslinked microgels, while increases for MBA crosslinked microgels. There is also a slight effect on the critical transition temperature (T _c) of the microgels from 30 °C (DVA) to 34 °C (MBA) as observed in copolymers of NIPAAm with hydrophilic or hydrophobic comonomers.     

Thermoreversible hydrogels XIII: Synthesis and swelling behaviors of [N-isopropylacrylamide-co-sodium 2-acrylamido-2-methylpropyl sulfonate-co-N,N-dimethyl(acrylamido propyl) ammonium propane sulfonate] copolymeric hydrogels

A series of copolymeric hydrogels were prepared from various molar ratios of N-isopropylacrylamide (NIPAAm), sodium-2-acrylamido-2-methylpropyl sulfonate (NaAMPS) and N,N′-dimethyl(acrylamido propyl) ammonium propane sulfonate (DMAAPS). The swelling behaviors of these copolymeric hydrogels were investigated in various saline solutions. The result showed that the phase transition temperatures of these gels changed insignificantly, and the thermosensitivity, in contrast, diminished. In addition, the copolymer gels exhibited polyelectrolytic behavior under lower salt concentration (10⁻⁵∼10⁻¹ M), exhibited a nonionic gel (like NIPAAm) behavior at the salt concentration from 0.1 to 0.4 M, and showed an antipolyelectrolytic behavior (polyzwitterionic effect) at a salt concentration over 0.4 M. Finally, the presented coplymeric gels are investigated for use in drug release application.     

Preparation and properties of thermosensitive organic‐inorganic hybrid gels containing modified nanosilica

A series of thermosensitive organic–inorganic hybrid gels containing nanosilica or modified nanosilica were prepared from N‐isopropylacrylamide (NIPAAm), and N,N′‐methylene‐bis‐acrylamide (NMBA) and nanosilica (AE200) or modified AE200 (mAE200); and NIPAAm, NMBA, 3‐(trimethoxysilyl) propyl methacrylate (TMSPMA) as coupling agent and AE200 or mAE200 in this study. The effect of inorganic nanosilica on the swelling behaviors and mechanical properties were investigated by adding different amount of nanosilica and modified nanosilica. Results showed that the swelling ratios of the hybrid gels decrease with increasing nanosilica content. Existence of silane coupling agent would also reduce the swelling ratios of the hybrid gels. Adding coupling agent or nanosilica would improve the gel strength. Modification of nanosilica by grafting amino‐silane via sol–gel process was carried out and the effect of addition of modified silica on gel properties was also investigated. Results showed that the hybrid gels containing modified silica would have higher swelling ratios and moduli than those containing unmodified silica. Gels containing both silane coupling agent and silica would have higher crosslinking density because the silica would be better crosslinked with coupling agent. POLYM. COMPOS., 31:1712–1721, 2010. © 2010 Society of Plastics Engineers.     

Characterization of strong polyelectrolyte hydrogels based on poly(vinyl alcohol)

Maleic anhydride (MA) was grafted onto both partially and fully hydrolyzed poly(vinyl alcohol) (PVA) in the presence of an initiator. Strong polyelectrolyte polymers were prepared by sulfonation of PVA–MA grafts. The sulfonation was completed by reaction of hydroxyl groups of PVA–MA grafts with two different sulfonating reagents (chlorosulfonic acid and pyridine sulfonic acid). The sulfonation degree was evaluated by acid–base titration and ¹H NMR analysis. The solution behaviour of the prepared grafts was evaluated from viscosity measurements. Four kinds of water‐insoluble PVA–MA and PVA–MA‐SO₃H hydrogels were prepared by heat treatment, physical gelation and chemical crosslinking with different weight ratios of N,N‐methylene bisacrylamide (MBA) crosslinker. The swelling parameters were measured for all prepared gels in deionized water and aqueous solutions at different pH values from 2 to 12 having constant ionic strength (I = 0.1). All gels exhibit a different swelling behaviour upon environmental pH changes. Copyright © 2004 Society of Chemical Industry     

Thermoreversible hydrogels. VII. Synthesis and swelling behavior of poly(N‐isopropylacrylamide‐co‐3‐methyl‐1‐vinylimidazolium iodide) hydrogels

A series of N‐isopropylacrylamide/3‐methyl‐1‐vinylimidazolium iodide (NIPAAm/MVI) copolymer gels were prepared from the various molar ratios of NIPAAm, cationic monomer MVI, and N,N′‐methylene bisacrylamide (NMBA) in this study. The influence of the amount of MVI in the copolymer gels on the swelling behaviors was investigated in various aqueous saline solutions. Results showed that the swelling ratios (SRs) of copolymer gels were significantly greater than those of NIPAAm homopolymer gels, and the higher the MVI content, the higher the volume phase transition temperature. The SRs for the NIPAAm/MVI copolymer gels decreased with an increase of the salt concentration. In various saline solutions, results showed that the effect of divalent ions on the SR was greater than that of monovalent ions for these hydrogels. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3242–3253, 1999     

Synthesis,properties and self‐assembly of intelligent core‐shell nanoparticles based on chitosan with different molecular weight and N‐isopropylacrylamide

In this study, a series of chitosan‐graft‐poly(N‐isopropylacrylamide) (CTS‐g‐PNIPAAm) copolymers based on different molecular weight (Mw) of CTS and NIPAAm were synthesized through the polymerization of NIPAAm in an acid aqueous solution. The structures were verified by Fourier transform infrared and nuclear magnetic resonance. The influence of the CTS Mw on the properties of the resulting copolymers and self‐assembled nanoparticles was fully examined. The grafting ratio and grafting efficiency of the copolymers increased with the CTS Mw. All the copolymers have a similar low critical solution temperature of 33.5°C, which was independent of the CTS Mw. Furthermore, the copolymers were less temperature sensitive, when CTS Mw increased to 200 kDa. Besides, once the CTS Mw increased to 700 kDa, the copolymers were less pH sensitive near the tumor site (from pH 7.4 to 6.8). The copolymers could form uniform nanoparticles once the temperature increased to 34°C, which was reversible. After crosslinking by N,N‐methylenebisacrylamide (MBA), structurally stable nanoparticles could be obtained. The results from Transmission electron microscope (TEM) and Atomic force microscopy (AFM) showed that the MBA crosslinked nanoparticles were uniformly spherical with a loose structure. Surface tension method indicated that the critical aggregate concentrations were 0.045, 0.042, 0.037, and 0.036 mg mL^?1 prepared from CTS 50, 100, 200, and 700 kDa, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermosensitive and ampholytic hydrogels for salt solution

A series of N‐isopropylacrylamide/[[3‐(methacryloylamino)propyl]dimethy(3‐sulfopropyl)ammonium hydroxide] (NIPAAm/MPSA) copolymer hydrogels were prepared with various compositions. Swelling of the hydrogels in water, aqueous NaCl, KCl, CaCl₂, and MgCl₂ solutions was studied. NIPAAm/MPSA hydrogels have a higher degree of swelling in water and salt solutions than that of poly(N‐isopropylacrylamide) (PNIPAAm). Also, NIPAAm/MPSA hydrogels are more salt resistant when deswelling in salt solutions. For <7 mol % MPSA, the formed hydrogels retain both temperature reversibility and high swelling. A higher content of MPSA (>11 mol %) leads to better salt resistance but a decrease in thermosensitivity. The swelling of NIPAAm/MPSA hydrogel in 0.05M NaCl is non‐Fickian. In NaCl and KCl aqueous solutions, the zwitterionic hydrogels do not show obvious antipolyelectrolyte swelling behavior, whereas in divalent salt CaCl₂ and MgCl₂ solutions, the swelling ability of NIPAAm/MPSA hydrogels is enhanced at low salt concentration, then decreases with further increase in salt concentration. The lower critical solution temperatures of NIPAAm/MPSA hydrogels are also affected by concentrated salt solution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2032–2037, 2003     

Synthesis and characterization of polyelectrolyte hydrogels with controlled swelling behaviour

Copolymerization of sulfopropyl methacrylate potassium salt (K‐SPMA) and 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) has been studied in the range 10–90% K‐SPMA in the feedstock. The reactivity ratios have been determined for K‐SPMA/AMPS copolymers. The copolymer compositions, utilized for determining the reactivity ratio, have been determined from nitrogen content. Crosslinked poly(AMPS) and K‐SPMA/AMPS copolymers were prepared in water in the presence of potassium persulfate as initiator and N,N‐methylene bisacrylamide (MBA) as tetrafunctional crosslinker. Irradiation of K‐SPMA and AMPS with an electron‐beam was carried out at 50 wt% aqueous solution with low pH and irradiation dose 40–120 kGy. The swelling behaviour of highly crosslinked K‐SPMA/AMPS copolymer polyelectrolyte gels in aqueous medium was studied in the presence of different types of salts. The crosslink density, the average molecular weight between the crosslinks and the dissociation constant (pK_a) of the crosslinked polymer were determined from stress–strain measurements. © 2001 Society of Chemical Industry     

Palladium and platinum sorption on a thiocarbamoyl‐derivative of chitosan

Novel proton exchange membranes are solvent‐cast from N,N‐dimethylacetamide (DMAc) solutions of the crosslinked poly(arylene ether ketone) copolymer with pendant carboxylic acid group (C‐SPAEK) via poly(ethylene glycol) (PEG) with different amounts. These membranes are formed as a result of physical and chemical crosslinking. In this study, ¹H‐NMR and FTIR have been used to confirm the chemical structures of the copolymers. Mechanical and thermal properties, swelling and proton conductivity are affected by the crosslinker (PEG) content in the copolymers. Compared to the noncrosslinked C‐SPAEK membrane, the crosslinked membranes become more flexible and greatly reduced water uptake and swelling ratio with only slight sacrifice in proton conductivities. And the crosslinked membranes keep higher proton conductivities without a sharply decrease at higher temperature. These results show that the crosslinked membranes have potential applications as proton exchange membranes for fuel cell. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermo-responsive nanofibers prepared from poly(N-isopropylacrylamide-co-N-methylol acrylamide)

Thermo-responsive nanofibers were successfully prepared via electrospinning in this study. Poly(N-isopropylacrylamide-co-N-methylol acrylamide), poly(NIPAAm-co-NMA), was used as the material for preparing the electrospinning nanofibers. Poly(NIPAAm-co-NMA) copolymers showed thermo-responsive property in aqueous solution, and such copolymers of NIPAAm and NMA were synthesized via random redox copolymerization. Here, NMA provided the thermal crosslinking function for the copolymer. Thermal curing process was then applied on the copolymer nanofibers for thermal crosslinking and the crosslinked nanofibers could keep the fiber morphology and the copolymer characters while soaking in water. The thermal curing conditions led to different swelling performance, LCST, and morphology of copolymer nanofibers while dipping in water. This study demonstrated that novel nanofibers exhibited thermo-responsive characteristics. The nanofibers of these copolymers were suggested for application as a new kind of sensors, drug carriers, and engineering tissues.     

Complex-radical copolymerization of <Emphasis Type="Italic">N-</Emphasis>vinyl pyrrolidone with isostructural analogs of maleic anhydride

Radical copolymerizations of N-vinyl-2-pyrrolidone (VP) with isostructural analogs of maleic anhydride (MA), such as citraconic anhydride (CA) and N-substituted maleimides [maleimide (MI), N-ethylmaleimide (EMI) and N-phenylmaleimide (PhMI)] were studied. Compositions of copolymers synthesized in a wide range of monomer feed ratios were determined by alkali titration (for anhydride copolymers), FTIR and ¹H NMR spectroscopy using 1495 and 630 cm^-1 (for VP-MI), 1289 and 1225 cm^-1 (for VP-EMI) and 1050 and 3067 cm^-1 (for VP-PhMI) analytical bands and integral areas of CH₂ (pyrrolidone ring) and CH (MI), CH₃ (EMI) and CH= (benzene ring in PhMI) groups, respectively. Electron-donor VP monomer was found to have substantially different reactivities in the radical copolymerization with MA, CA and N-substituted (H, C₂H₅ and phenyl) malemides as electron-acceptor comonomers. Effects of H-bonding and N→O=C coordination on the monomer reactivity ratios were evaluated. Tendency to alternation of the monomer pairs increases in the order of VP–MA > VP–CA > VP-MI > VP-PhMI > VP-EMI. Structure-thermal property-relationship for the synthesized copolymers was also studied.     

Ion‐exchange resins. II. Acrylamide crosslinked copolymers as precursors for some ion exchangers

Crosslinked copolymers of acrylamide (AA) and ethylacrylate and some ion exchangers derived from them containing either primary amine groups, obtained by the Hofmann degradation of the amide groups, or carboxylic groups, obtained by the alkaline hydrolysis of the ester groups, were studied. Divinylbenzene and N,N′‐methylenebisacrylamide were used as crosslinkers. The starting copolymers and the corresponding ion exchangers were characterized by IR spectroscopy, swelling behavior, and thermogravimetric analysis. The ion‐exchanger properties were correlated with the crosslinker nature and the chemical reactions performed on the AA copolymers. The average molecular weight between two crosslinks, determined from the swelling data in water, was compared with that calculated on the basis of the copolymerization stoichiometry only for the carboxylic cation exchangers. In this way, the preservation of the crosslink density after the hydrolysis was revealed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2701–2707, 2003