Swelling kinetics of a hydrogel of poly(ethylene glycol) and poly(acrylamide‐co‐styrene)

A hydrogel incorporating the hydrophilic polymer poly(ethylene glycol) and a copolymer of acrylamide and styrene was synthesized, and the dynamics of the water‐sorption process were studied. The effects of the composition of the hydrogel and the temperature of the swelling medium were investigated with respect to the water‐sorption characteristics of the hydrogel, and the kinetic parameters, including the swelling exponent and diffusion constant, were evaluated. The hydrogel was also judged for the antithrombogenic property of its surface. The experimental findings were explained on the basis of the core–shell polymeric structure of the hydrogel. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1419–1428, 2002     

Synthesis of ethyl propionate catalyzed by poly(N‐AEAAm‐co‐AAc)‐cl‐MBAm hydrogel‐immobilized lipase of Bacillus coagulans MTCC‐6375

A purified alkaline thermotolerant bacterial lipase of Bacillus coagulans MTCC‐6375 was efficiently immobilized onto poly(N‐AEAAm‐co‐AAc‐cl‐MBAm)‐hydrogel at pH 8.5 and at temperature 55°C in 16 h. The hydrogel‐bound matrix possessed 1.04 U/g (matrix) lipase activity with a specific activity of 1.8 U/mg of protein. The immobilized lipase resulted in formation of 52.5 mM of ethyl propionate (52% conversion) at 55°C in 9 h in n‐nonane. Ethanol and propionic acid when used in a ratio of 300 : 100 mM, respectively, in n‐nonane along with 10 mg of hydrogel‐bound lipase resulted in optimal synthesis of ethyl propionate (82.5 mM). Addition of molecular sieves (3 Å, 0.7 g/reaction volume) further enhanced the conversion rate to 82.4% resulting in 83.5 mM of ethyl propionate. Incubation temperature below or above 55°C had a marked effect on the synthesis of ethyl propionate. However, esterification performed in n‐heptane at 65°C resulted in 87.5 mM of ethyl propionate with a conversation rate of 89.3%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of poly(vinyl chloride‐co‐vinyl acetate)‐graft‐poly[(meth)acrylates] by atom transfer radical polymerization

The graft polymerization of methyl methacrylate and butyl acrylate onto poly(vinyl chloride‐co‐vinyl acetate) with atom transfer radical polymerization (ATRP) was successfully carried out with copper(I) thiocyanate/N,N,N′,N′,N″‐pentamethyldiethylenetriamine and copper(I) chloride/2,2′‐bipyridine as catalysts in the solvent N,N‐dimethylformamide. For methyl methacrylate, a kinetic plot of ln([M]₀/[M]) (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) versus time for the graft polymerization was almost linear, and the molecular weight of the graft copolymer increased with increasing conversion, this being typical for ATRP. The formation of the graft polymer was confirmed with gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The glass‐transition temperature of the copolymer increased with the concentration of methyl methacrylate. The graft copolymer was hydrolyzed, and its swelling capacity was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 183–189, 2005     

Competitive removal of Pb2+, Cd2+, and Zn2+ by poly(acrylamide‐co‐maleic acid) hydrogels/differential pulse polarographic determination

Poly(acrylamide‐co‐maleic acid) [P(AAm/MA)] hydrogels, with various compositions, were prepared from ternary mixtures of acrylamide (AAm)/maleic acid (MA)/water by using ⁶⁰Co γ‐rays. The effect of composition of these hydrogels, on the competitive removal of Pb²⁺, Cd²⁺, and Zn²⁺ ions from aqueous solution, was investigated. The hydrogel compositions and their adsorption behaviors were determined by use of differential pulse polarography, a very sensitive electroanalytical technique. It was observed that the external stimuli of pH, temperature, and ionic strength have an important role on the adsorption. The increments of MA content in P(AAm/MA) hydrogels caused a significant increase in the adsorption these ions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2401–2406, 2004     

Porous poly(2-hydroxyethyl acrylate) hydrogels prepared by radical polymerisation with methanol as diluent

Dynamic-mechanical and water sorption properties of porous and non-porous hydrogels have been studied as a function of their porosity and crosslinking density. Porous hydrogels with different crosslinking densities were prepared by co-polymerisation of 2-hydroxyethyl acrylate and ethyleneglycol dimethacrylate in solution in methanol. Pores were formed due to the segregation of the solvent from the polymer network during the polymerisation process. The porosity of the samples was observed by scanning electron microscopy. The pores collapse during the drying process after polymerisation but they reopen when the xerogel is immersed in liquid water. Bulk polymer networks with varying crosslinking densities were also synthesised and used as a reference in the analysis of the porous hydrogels. Water sorption from the gas phase and from the liquid phase was studied by means of equilibrium sorption isotherms and immersion experiments, respectively. Dynamic-mechanical spectroscopy conducted on the xerogels shows that the elastic modulus in the rubber-like state highly depends on the amount of solvent used in the polymerisation what is attributed to the presence of discontinuity surfaces in the xerogel although the pores are closed.     

Synthetic hydrogels 3. Solvent effects on poly(2-hydroxyethyl methacrylate) networks

Poly(2-hydroxyethyl methacrylate) networks were synthesized in aqueous solutions of propylene glycol, ethylene glycol, ethylene glycol monomethyl ether, or ethylene glycol dimethyl ether and the influences of solvent on phase separation during the polymerization process studied. Results from conversion-phase diagrams, turbidity measurements, swelling studies, and viscosity measurements show that the phase separation process is dependent upon the solubility parameter of the organic solvent, the instantaneous monomer concentration at each stage of the gel formation process, and the crosslinker content of the reaction mixture.     

Preparations and properties of thermosensitive terpolymers of N‐isopropylacrylamide,sodium 2‐acrylamido‐2‐methyl‐propanesuphonate,and N‐tert‐butylacrylamide

Terpolymers based on N‐isopropylacrylamide, sodium 2‐acrylamido‐2‐methyl‐propanesulfonate, and N‐tert‐butylacrylamide were synthesized by free‐radical copolymerization with 2,2′‐azobisisobutyronitrile as an initiator. The lower critical solution temperatures (LCSTs) of the linear polymer aqueous solutions were determined by the measurement of the transmittance on UV at different temperatures. The influence of the polymer concentration, polymer composition, and ionic strength on the LCSTs of the linear polymers was investigated. The LCST decreased with increases in the hydrophobic monomer N‐tert‐butylacrylamide, polymer concentration, and ionic strength. The phase transition became sharp when the polymer concentration and ionic strength increased. Meanwhile, the crosslinked hydrogels were prepared with the same recipe used for the linear terpolymers, but a crosslinker was added to the reaction system. The swelling ratios of the hydrogels at various temperatures and salt solutions were determined. The hydrogels possessed both high swelling ratios and thermosensitivity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Swelling of pH‐sensitive chitosan–poly(vinyl alcohol) hydrogels

The swelling properties of different chitosan–poly(vinyl alcohol) (PVA) hydrogels were investigated as functions of the medium pH and salt concentration. The maximum swelling ability of the hydrogels was at a buffer pH of approximately 3, regardless of the PVA content in the hydrogels. The maximum mass of the swollen hydrogels was about 13 times that of their contracted counterparts. The cyclical swelling and contraction between pH 3 and pH 7 buffers and pH 3 and pH 3 buffers with salt confirmed the Donnan swelling mechanism of these hydrogels. The swelling mechanism was considered the transfer of water molecules driven by a concentration gradient. This was represented by a simplified mass‐balance model, which neglected the effect of the ionization reaction, for the initial swelling period. The effective mass‐transfer coefficient of water molecules during swelling, estimated with this model, gradually decreased with increasing PVA content in the hydrogels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4665–4671, 2006     

Preparation of pH‐sensitive poly(vinyl alcohol‐g‐methacrylic acid) and poly(vinyl alcohol‐g‐acrylic acid) hydrogels by gamma ray irradiation and their insulin release behavior

A series of pH‐responsive hydrogels were studied as potential drug carriers for the protection of insulin from the acidic environment of the stomach before releasing in the small intestine. Hydrogels based on poly(vinyl alcohol) networks grafted with acrylic acid or methacrylic acid were prepared by a two‐step process. Poly(vinyl alcohol) hydrogels were prepared by gamma ray irradiation (50 kGy) and then followed by grafting either acrylic acid or methacrylic acid onto these poly(vinyl alcohol) hydrogels with subsequent irradiation (5–20 kGy). These graft hydrogels showed pH‐sensitive swelling behavior and were used as carriers for the controlled release of insulin. The in vitro release of insulin was observed for the insulin‐loaded hydrogels in a simulated intestinal fluid (pH 6.8) but not in a simulated gastric fluid (pH 1.2). The release behavior of insulin in vivo in a rat model confirmed the effectiveness of the oral delivery of insulin to control the level of glucose. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 636–643, 2004     

Encapsulation and controlled release in polyacrylamide hydrogels

A novel host–guest system was developed by the encapsulation of simple organic guest molecules in the hydrophilic molecular architecture of crosslinked polyacrylamide hydrogels. The crosslinking agents used for the preparation of the host systems were hexanediol dimethacrylate (HDDMA) and divinyl benzene (DVB). This enabled us to construct hydrogels with different hydrophobic–hydrophilic equilibria. The model guest system used for the studies was benzoic acid. The selections gave simple but excellent host–guest systems with fine polar–apolar balancing. Polyacrylamide hydrogels with encapsulated benzoic acid were prepared with varying crosslink densities (5, 10, 15, and 20 mol %) by the solution polymerization technique. The rate of release of the host from the host–guest assembly was studied in different swelling conditions. The rate of release depended on the interaction forces between the polymer and the solvents. Polar forces, dispersion forces, and hydrogen bonding all played a vital role. The swelling behavior of the host‐polymer system and the host–guest assembly was analyzed and compared by the Flory–Rehner method. The amount of benzoic acid encapsulated in the DVB‐crosslinked polymer was higher than in the HDDMA‐crosslinked polymer, and the rate of release was in the order 5 > 15 > 10 > 20% for the DVB‐crosslinked polymer. The rate of release for the HDDMA‐crosslinked host–guest assembly was in the order 10 > 5 > 15 > 20%. These results were in excellent agreement with those of the Flory–Rehner analysis of the swelling properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1816–1824, 2004