Volume phase transition behavior of N‐isopropyl acrylamide–N‐cyanomethyl acrylamide copolymer gel particles: The effect of crosslinking density

We prepared submicron‐sized N‐isopropyl acrylamide (NIPA)–N‐cyanomethyl acrylamide (NCMA) copolymer gel particles by precipitation polymerization. Volume phase transition behaviors of gel particles with various compositions and crosslinking density were observed by using photon correlation spectroscopy (PCS). The experimental data showed that both the volume transition temperature and the swelling ratio of copolymer gel particles were varied with the mole ratio of NCMA and NIPA. We compared the swelling behaviors of given systems with the thermodynamic model based on the extended Flory–Huggins theory. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1091–1099, 1999     

Swelling behavior of submicron gel particles

We prepared submicron Poly(N-isopropylacrylamide) gel particles. Their swelling behavior was investigated by a photon correlation spectroscopy (PCS) technique. The swelling behavior of submicron gel particles showed a continuous volume phase transition for various temperatures. We combined the extended Flory-Huggins model for mixing solvent and network with a modified Flory-Rehner theory for the elastic contribution. The proposed model agreed very well with swelling behaviors of both submicron gel particles and bulk gels. A continuous volume phase transition behavior of submicron gel particles was predicted successfully by the proposed model. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 109–114, 1998     

Volume-phase transition of submicron-sized N-isopropylacrylamide/N-tert-butylacrylamide particles by photon correlation spectroscopy

N-Isopropylacrylamide (NIPA)/N-tert-butylacrylamide (NTBA) submicron-sized copolymer gel particles of various compositions were prepared by precipitation polymerization and the swelling behaviors of the gels were studied with different compositions and temperature using photon correlation spectroscopy (PCS). The experimental data showed that the volume transition temperature (T_v) of the gels variedwith the amount of monomers having different hydrophobicity added. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2087–2092, 1998     

Thermoreversible hydrogels. IV. Effect of some factors on the swelling behavior of N-tetrahydrofurfurylacrylamide

A thermoreversible hydrogel, poly(N-tetrahydrofurfurylacrylamide) [poly-(NTHFAAm) gel], was prepared from N-tetrahydrofurfurylacrylamide, which was synthesized from N-tetrahydrofurfurylamine and acryloyl chloride (through acylation), with N,N′-methylenebisacrylamide, a crosslinker, in various aqueous solutions. The influences of temperature, gel thickness, and polymerization media on the swelling behaviors in water were investigated. The effect of the gel thickness on the swelling ratio for NTHFAAm gel indicated that the equilibrium swelling time and diffusion coefficient for the thinner gel were faster than those for the thicker gels. The effects of different polymerization media on the gel swelling ratio showed that the larger the solvent molecular size and the poorer the miscibility of the monomer and solvent, the higher the swelling ratio and diffusion coefficient. The drug release profiles in the various gels were also investigated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1597–1603, 1998     

The effects of interaction energy on the volume phase transition of N-isopropylacrylamide-co-N-isopropylmethacrylamide nano-sized gel particles: Applicability of molecular simulation technique

We investigated the volume phase transition temperatures of N-isopropylmethacrylamide (NIPMA)-co-N-isopropylacrylamide (NIPA) gels with various mole ratios. Nanometer-sized NIPA-co-NIPMA gel particles were prepared by precipitation polymerization and their swelling behaviors were measured using photon correlation spectroscopy (PCS). After applying the interaction energies found using the molecular simulation technique, we predicted the swelling equilibria for the hydrogels in a water system. For studying cross-linked hydrogel particles in water, we have combined the modified double-lattice theory with Flory and Erman's theory of elasticity. To correct for the deviation of the volume transition temperature, we considered the additional energy parameter (?_h) between the cross-linker and solvent molecules. We used the corrected model to describe the swelling behavior of the hydrogel and the volume transition temperature. The corrected model was agreed well with their experimental data with no fitting parameters.     

Swelling Behaviors of a New Zwitterionic N-carboxymethyl-N, N-dimethyl-N-allylammonium/acrylic Acid Hydrogel

A series of new zwitterionic N-carboxymethyl-N,N-dimethyl-N-allylammonium (CDMA)/acrylic acid (AA) copolymer hydrogels with different contents of anionic and cationic groups were prepared by aqueous polymerization to investigate their swelling behaviors. Various factors, including the solution pH, the various salt solution, temperature, were studied. The dynamics parameters were also calculated. The swelling capacity, as well as salt-tolerant ability increases with increasing N content in the dilute solution of salts. The hydrogel with 2.43% N and 49.54% COOH reaches 773 g/g swelling capacity. CDMA/AA copolymer gel can improve the pullulating rate of wheat remarkably, which makes them good candidates for considering as potential soil-improvement agent.     

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.     

Sorption and permeation of acetic acid–water mixtures by pervaporation using copolymer membrane

Poly (acrylonitrile‐co‐methyl acrylate) copolymer designated as PANMA was used for making pervaporation membrane. This membrane was used for separation of acetic acid–water mixtures over the concentration range of 80–99.5 wt% acetic acid in water. Interaction parameters based on Flory–Huggins lattice model and engaged species induced clustering (ENSIC) model was used to explain swelling of the membranes. Coupling in sorption was explained in terms of activity coefficient of water and acid in feed and membrane using Flory–Huggins model and also by interpolating ENSIC parameters. Flow coupling in pervaporation was also determined from phenomenological deviation coefficients. Intrinsic membrane properties like partial permeability and membrane selectivity of the solvents were also determined. Diffusion coefficient and plasticization coefficient of the solvents were obtained using a modified solution–diffusion model. The copolymer membrane showed high flux and water selectivity for highly concentrated acid. Thus, at 30°C temperature 1–20 wt% water in feed was concentrated to 82–84 wt% water in permeate and for 0.95 wt% water in feed, the membrane showed thickness normalized flux and water selectivity of 1.71 kg m^?2 h^?1 mμ and 409, respectively. OLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Reentrant swelling behavior of thermosensitive N-isopropylacrylamide nano-sized gel particles

The closed-loop phase diagram of poly N-isopropylacrylamide (PNIPA) in a water-N,N-dimethylformamide (DMF) system was measured by thermooptical analysis (TOA). The reentrant swelling behavior of N-isopropylacrylamide (NIPA) nano-sized gel particles in the water-DMF system was measured by using photon correlation spectroscopy (PCS) technique. Theoretically, a modified double lattice model (MDL) can be used to describe the closed-loop phase behavior of linear PNIPA in water-DMF systems. For crosslinked NIPA nano-sized gel particles in a water-DMF system, we combined MDL theory for the mixing contribution and Flory-Erman theory for the elastic contribution. Molecular interaction parameters obtained from the PNIPA solution were used to directly predict the swelling-ratio curves for the NIPA gel. Using our model, the calculated results were in good agreement with the experimental data using only one adjustable parameter.     

in situ thermal gelation of water-soluble poly(N-isopropylacrylamide-co-vinylphosphonic acid)

A copolymer based on N-isopropylacrylamide (NIPAAm) and vinylphosphonic acid (VP) was synthesized to investigate its thermal gelation behaviors in the presence of calcium ion. The copolymer showed a variety of temperature-sensitive phase transition properties as a function of temperature. In an aqueous solution, it exhibited 3 distinctive phase transitions with gradually increasing the temperature: a transparent solution state, a cloudy and white solution state (sol), and a white and semisolid (gel) state. Particularly, in situ reversible sol-gel transition behaviors could be observed over a wide range of temperatures in the presence of varying concentrations of calcium ion. This physical gel that initially was formed homogeneously without changing its dimension in the solution container tended to slowly phase-separate out into a polymer-rich phase and a water-rich phase over the following several days, indicating that a synerisis occurred. The in situ thermal gelation behavior was utilized in the controlled release formulation of a model compound. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1947–1953, 1998     

Rapid pH‐dependent phase transition and elasticity of stimuli‐responsive cationic poly(N,N‐dimethylaminoethyl methacrylate) hydrogels prepared with a dimethacrylate crosslinker

Stimuli‐responsive hydrogels prepared from poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) and its copolymers have attracted much interest to serve in biomedical and pharmaceutical applications. To investigate pH‐dependent swelling and elasticity, a series of cationic hydrogels based on N,N‐dimethylaminoethyl methacrylate were prepared by free radical crosslinking copolymerization at 60 °C in the presence of tetraethylene glycol dimethacrylate as the crosslinker. The equilibrium swelling and the mechanical properties of the PDMAEMA hydrogels were investigated as a function of the gel preparation concentration. To explain the effect of pH on the equilibrium swelling of the hydrogels, pH‐dependent swelling studies were carried out in solutions of pH ranging from 2.1 to 10.7. It was found that the PDMAEMA hydrogels exhibit a rapid pH‐dependent phase transition in aqueous solutions; that is, the gels first remain in the swollen state at acidic pH then collapse in a very narrow range of pH. The results showed that the volume of PDMAEMA hydrogels in acidic conditions is about 10‐ to 40‐fold larger than that in the basic pH region. By using the Flory–Rehner theory, the characteristic network parameters of the PDMAEMA hydrogels were calculated and good agreement obtained between the swelling equilibria of hydrogels and their mechanical properties over the whole range of gel preparation concentration. © 2012 Society of Chemical Industry     

Swelling behavior of anionic acrylamide-based hydrogels in aqueous salt solutions: Comparison of experiment with theory

A series of hydrogels were prepared from acrylamide and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) monomers with 0–80 mol % AMPS and using N,N′-methylenebis(acrylamide) as the crosslinker. The swelling capacities of hydrogels were measured in water and in aqueous NaCl solutions. The volume swelling ratio q_v of hydrogels in water increases sharply when the mole fraction f_c of AMPS increases from 0 to 0.06. At higher values of f_c from 0.06 up to 0.18, no change in the swelling capacities of hydrogels was observed; in this range of f_c, q_v becomes nearly constant at 750. However, as f_c further increases, q_v starts to increase again monotonically over the entire range of f_c. At a fixed value of f_c, the swelling ratio of hydrogels decreases with increasing salt concentration in the external solution. The results of the swelling measurements in aqueous salt solutions were compared with the predictions of the Flory–Rehner theory of swelling equilibrium. It was shown that the theory correctly predicts the swelling behavior of hydrogels up to 80 mol % charge densities. The method of estimation of the network parameters was found to be unimportant in the prediction of the experimental swelling data. The network parameters used in the simulation only correct the deficiency of the swelling theory. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 567–575, 1998     

Swelling behavior of thermoreversible poly(N‐isopropylacrylamide‐co‐N‐vinylimidazole) hydrogels

Thermoresponsive hydrogels based on N‐isopropylacrylamide and N‐vinylimidazole were synthesized, and their swelling–deswelling behavior was studied as a function of the total monomer concentration. For copolymeric structures with better thermoresponsive properties with respect to poly(N‐isopropylacrylamide‐co‐N‐vinylimidazole) hydrogels, these hydrogels were protonated with HCl and HNO₃, and the copolymer behaviors were compared with those of the unprotonated hydrogels. The temperature was changed from 4 to 70°C at fixed pHs and total ionic strengths. The equilibrium swelling ratio, dynamic swelling ratio, and dynamic deswelling ratio were evaluated for all the hydrogels. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1619–1624, 2004     

Synthesis and characterization of dextran hydrogels prepared with chlor‐ and nitrogen‐containing crosslinkers

In this study, we have synthesized dextran hydrogels by the crosslinking reactions of dextran with some selective Cl‐, and N‐containing functional monomers, such as epichlorohydrin (ECH), N,N′‐methylenebisacrylamide (MBAm), and glutaraldehyde (GA). Crosslinking reactions were carried out in the basic aqueous solutions (2.8NNaOH) at 25–50°C. The optimum conditions for effective crosslinking, i.e., temperature, crosslinking time, and amount of crosslinker, were determined for each system. The hydrogel discs of 3 mm diameter and 1.5 mm thickness were subjected to a number of Tris‐buffer solutions of desired pH (2.0–9.0) at 37°C. Swelling kinetics of the hydrogels were evaluated with second–order swelling model. The pH‐dependent swelling of hydrogels was strongly influenced by the functional group of crosslinker and crosslinker content. While the hydrogels prepared with ECH and MBAm shows higher swelling ability at basic medium than that of acidic medium, GA‐containing hydrogels exhibited just the opposite behavior. Mesh sizes (ξ) and average molecular weights between crosslinks (M_c) were estimated from swelling data using the Flory‐Rehner theory. Characterization studies were completed by Fourier transform infrared spectroscopy and thermal gravimetric analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4213–4221, 2006     

Swelling of and solute exclusion by poly(N-alkylacrylamide) gels

Temperature-sensitive hydrogels of poly(N-isopropylacrylamide) poly(N,N-diethylacrylamide), poly(N-N-propylacrylamide), copolymer of N-isopropylacrylamide and methylacrylamide, and copolymer of N,N-diethylacrylamide and N-tert-butylacrylamide were prepared. The swelling characteristics of the gels were studied and gel extraction of macromolecules, based on the solute exclusion by the gel network, were investigated. © 1995 John Wiley & Sons, Inc.     

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 and network parameters of hydrophobic poly(N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐lauryl acrylate) hydrogels

Hydrophobic poly(N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐lauryl acrylate) [P(DMAPMA‐co‐LA)] hydrogels with different LA content were synthesized by free‐radical crosslinking copolymerization of corresponding monomers in water by using N,N‐methylenebis(acrylamide) as the crosslinker, ammonium persulfate as the initiator, and N,N,N′,N′‐tetramethylethylenediamine as the activator. The swelling equilibrium of the hydrogels was investigated as a function of temperature and hydrophobic comonomer content in pure water. An interesting feature of the swelling behavior of the P(DMAPMA‐co‐LA) hydrogels with low LA content was the reshrinking phase transition where the hydrogels swell once and collapse as temperature was varied in the range of 30–40°C. The average molecular mass between crosslinks (M?_c) and polymer–solvent interaction parameter (χ) of the hydrogels were calculated from equilibrium swelling values. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter for the hydrogels were determined by using the Flory–Rehner theory based on the phantom network model of swelling equilibrium. The positive values for ΔH and ΔS indicated that the hydrogels had a positive temperature‐sensitive property in water, that is, swelling at a higher temperature and shrinking at a lower temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4159–4166, 2006     

Ground particle size influence on the swelling of a copolymer of AA/AMPS in water

The influence of the ground particle size on the swelling behavior of a copolymer of AA/AMPS in water was observed to determine the best size considering water absorbency in view of fastest and highest equilibrium swelling. The copolymer gel, from acrylamide and 2‐acrylamido‐2‐methyl‐propanosulfonic acid and synthesized in the presence of N,N‐methylene‐bis‐acrylamide, was obtained by a radical solution technique, and identified by FTIR spectroscopy. By grinding, various particle diameters were obtained, and then separated by sieves. Studies of dynamic and equilibrium swelling in deionized water at 20°C showed the influence of the particle size on the kinetics of swelling and its equilibrium swelling capacity. A mathematical model for the absorption, including diffusion and relaxation modes, permitted to assess the absorption mechanism, and offered quantitative information about water diffusivity in the copolymer. The fastest swelling was obtained with diameters of 22.5–215 μm. Particle sizes ranging from 67.5 to 355 μm yielded the greatest equilibrium swelling, with mass ratios of about 1100. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Swelling equilibria for heterogeneous polyacrylamide gels

To correlate swelling equilibria for heterogeneous polyacrylamide gels in water to the monomer concentration at preparation, it is necessary to modify the classic Flory–Rehner theory. The necessary modification concerns the relation which links the number of segments between juction points to the monomer concentration at preparation; that relation is here adjusted empirically. Modified theory is compared to experimental swelling equilibria for polyacrylamide gels synthesized in water by free-radical copolymerization of acrylamide (AAm) and N,N′-methylenebis(acrylamide) (BIS) at various monomer concentrations. Synthesis conditions studied are (1) different AAm-to-BIS ratios with fixed total monomer concentrations, (2) different total monomer concentrations with fixed AAm-to-BIS ratios, and (3) different AAm-to-BIS ratios with a fixed number of BIS moleculcs. The modified theory and experiment show good agreement. © 1996 John Wiley & Sons, Inc.     

Determination of average molecular weight between crosslinks and polymer–solvent interaction parameters of poly(acrylamide‐g‐ethylene diamine tetraacetic acid) polyelectrolyte hydrogels

Hydrogels containing tetraprotic acid moieties sensitive to pH changes of the swelling medium were prepared from the ternary systems acrylamide/ethylene diamine tetraacetic acid/water by irradiation with γ‐rays at ambient temperature. Gel compositions of poly(acrylamide‐g‐ethylene diamine tetraacetic acid) [P(AAm‐g‐EDTA)] hydrogels were determined by using a differential pulse polarography technique. Equilibrium swelling behavior of these hydrogels was studied using an equation, based on the Flory–Huggins thermodynamic theory, the phantom network theory of James–Guth, and the approaches of Brannon‐Peppas and Peppas, which was modified by the authors for determination of M _c and χ parameters. The equation modified by the authors for the determination of M _c and χ parameters were observed to describe very well the swelling behavior of the charged polymeric network. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2168–2175, 2004