Swelling properties and molecular simulation of PNIPA porous hydrogels

A series of porous intelligent hydrogels, which exhibited appropriate lower critical solution temperature (LCST) and fast response behavior, were synthesized by radiation method. The structure and surface morphology of hydrogels were examined by the infrared radiation and the scanning electron microscopy, respectively. The influences of the content of crosslinking agent and relative molecular mass of polyethylene glycol (PEG) on the swelling properties of hydrogels were discussed. The molecular mechanics simulations were performed to investigate the phase transformation mechanism of poly(N-isopropyl acrylamide) (PNIPA) hydrogel. The results show that macropores are observed in hydrogels, whereas hydrogels prepared without using PEG have a dense surface. LCST of hydrogels increases with the increase of relative molecular mass of PEG. The swelling mechanism of PNIPA porous hydrogels follows non-Fickian diffusion model. The theoretical maximum water absorption S∞ is approximately consistent with experimental value according to the second-order kinetics model established by Schott. The molecule chains of PNIPA hydrogel begin folding and curling, resulting in volume shrinkage at 305 K. There are much intramolecular nonbonding interactions in molecule chains of hydrogels. The porous hydrogels are expected to be applied in the field of artificial intelligence material.

Research on the Long Time Swelling Properties of Poly (vinyl alcohol)/Hydroxylapatite Composite Hydrogel

Poly(vinyl alcohol)/hydroxylapatite(PVA/HA)composite hydrogel was prepared by repeated freezing and thawing.The water loss properties of the resultant hydrogel were investigated by using optical microscope.Long time immersion tests of PVA/HA composite hydrogel were carried out in the diluted calf serum solution to study the change laws of swelling properties with the freezing-thawing cycles and HA content.The micro-morphologies of PVA/HA composite hydrogel after long time immersion were observed by means of the high-accuracy 3D profiler.The results show that the swelling process of PVA/HA composite hydrogel is the converse process of its water loss.Long time swelling ratio curves of PVA/HA composite hydrogel in the calf serum solution are manifested as four stages of quick increase,decrease,slow decrease and stable balance,and its equilibrium swelling ratio decreases with the increase of freezing-thawing cycles and HA content.It is revealed that the network structure of the composite hydrogel immersed for a long period is significantly improved with the increase of HA content. Perfect network structures of PVA/HA composite hydrogel as well as full and equilibrium tissues after swelling equilibrium are obtained when the HA content is 3% and the number of freezing-thawing cycles is 7.

Synthesis and Swelling Properties of Thermosensitive Hydrogels based on Terpolymerization

Novel thermosensitive hydrogels based on polymerization of N-isopropyl acrylamide, Sodium acrylate, and diacetone acrylamide were synthesized. The swelling ratio and dynamic swelling were investigated. The results indicated that the hydrogels exhibited high water uptake and themosensitivity. The swelling properties and volume phase transition temperature could be adjusted by contents of the comonomers in the gels.

Nano-CaO_(2)Promotes the Release of Carbon Sources from Municipal Sludge and the Preparation of Double-Network Hydrogels with High Swelling Ratios

In this study,hydrogels were prepared from municipal sludge to recycle and realize the value-added utilization of the carbon components in this abundant waste material.The carbon sources were extracted from the municipal sludge using synthesised nano CaO_(2)as an oxidant,and the carbon sources were graft copolymerised with acrylic acid monomer using N,N′-methylenebisacrylamide as a crosslinking agent and ammonium persulfate as an initiator.The factors influencing the hydrogel preparation were investigated by single-factor experiments.Based on the results of the single-factor experiments,a hydrogel with a swelling ratio of up to 19768.4%at 12 h was prepared with an oxidant dosage of 0.20 g,a monomer dosage of 5.8 g,a neutralisation degree of the monomer of 70%,an initiator dosage of 0.15 g,and a crosslinking agent dosage of 0.15 g.The hydrogel preparation conditions were optimized using the response surface method,and the interactions between the different reaction conditions were analysed to obtain the best preparation conditions.X-ray diffraction results showed that hydrogels were amorphous in structure.Scanning electron microscopy images showed that the SiO_(2)particles from the sludge acted as crosslinking points between different layers of hydrogel chains.The crosslinking polymerisation and crosslinking agent worked together to form hydrogels with an inorganic-organic double network structure,and this structure was highly stretchable,resulting in hydrogels with good swelling properties.

Synthesis and Properties of Rosin-Based Composite Acrylamide Hydrogels

Hydrogels have been widely applied in agricultural drought-resistance,pollution regulation,drug delivery and so on.Acrylamide(AM)is usually used as raw material to synthesize acrylamide hydrogels.However,inherently low mechanical strength greatly limits their applications in some special areas.Therefore,it is necessary to choose suitable functional monomers to optimize acrylamide hydrogels and improve their mechanical performances.In this paper,a novel acrylamide monomer modified by rosin was synthesized,and then polyacrylamide/rosinbased acrylamide(RAM)composite hydrogels were prepared via free radical polymerization using potassium persulfate as initiator,N,N′-methylene-bisacrylamide(MBA)as a crosslinker.The influence of RAM monomer was investigated in detail.The chemical structure,pore structure,swelling properties,thermal performances and mechanical properties of composite hydrogels were characterized by Fourier Transform Infrared spectrometer(FT-IR),thermogravimetric analysis(TG),scanning electron microscope(SEM),and universal testing,respectively.The results showed that the thermal stability and mechanical property of RAM hydrogels were improved significantly.The compressive strength of RAM hydrogels was increased to 3.5 times than that of AM hydrogels,and the tensile strength was 5.1 times compared with AM hydrogels as well.Moreover,RAM hydrogels exhibited a faster initial swelling rate due to the new pore structure formed after introducing the RAM monomer.

Synthesis and properties of physically crosslinked poly (vinyl alcohol) hydrogels

The present study is an investigation of the properties of poly(vinyl alcohol),which would be a better contact lens mate- rial than conventional HEMA in some ways.A transparent PVA hydrogel was prepared from a PVA solution in a mixed solvent consisting of water and a water-miscible organic solvent,DMSO,by the freezing-thawing method.The water content,visible light transmittance,mechanical and swelling properties of the hydrogels were evaluated as a function of PVA concentration and number of freeze-thaw cycles.The results show that the properties of PVA hydrogels depend on the polymer concentration,the number of freeze-thaw cycles and the addition of the organic solvent.

Preparation of Peanut Shell Cellulose Double-Network Hydrogel and Its Adsorption Capacity for Methylene Blue

To achieve optimal recovery and value-added utilisation of cellulose in peanut shells,the cellulose in peanut shells was first extracted using the sodium hydroxide-sodium chlorite method.Then,cellulose hydrogel was prepared by graft copolymerisation using N,N’-methylenebisacrylamide as the cross-linking agent,sodium persulfate as the initiator,and acrylic acid as the monomer.Orthogonal optimisation experiments were designed to obtain optimal process parameters for hydrogel preparation with the cellulose dosage of 0.40 g,initiator dosage of 0.20 g,polymerisation temperature of 70°C,cross-linking agent of 0.25 g,and monomer dosage of 3.0 mL.The effect of initiator dosage on hydrogel synthesis was the most significant,followed by monomer dosage and reaction temperature.Characterisation using X-ray diffraction analysis and scanning electron microscopy revealed that the hydrogel was amorphous and exhibited a distinct three-dimensional double network structure.Hydrogel swelling kinetic analysis showed that the hydrogel swelling process was divided into three stages,and fitted the Schott secondary swelling kinetic model.The prepared hydrogel had a good adsorption effect on methylene blue;the adsorption of methylene blue by the hydrogel was 1.259 mg/g at 25°C when the initial concentration of methylene blue was 5 mg/L.The adsorption kinetics of the hydrogel fit the pseudo-first-order kinetic model,pseudo-secondorder kinetic model,Eovich model and particle diffusion model.The best fitting effect was obtained with the pseudo-second-order kinetic model.The adsorption isotherm analysis of methylene blue on hydrogel showed that the adsorption process was consistent with Langmuir and Freundlich models.The correlation coefficient of the Freundlich isotherm model was higher,indicating that the adsorption of methylene blue on hydrogel was mainly chemisorption.

Preparation and Hydrophilicity of Copolymerization of Chitosan Selectively Grafted by Polyethylene Glycol

Copolymerization of chitosan selectively grafted by polyethylene glycol was prepared. Chitosan was selectively grafted by monomethoxy polyethylene glycol（mPEG-OH）, which contained a hydroxyl group combining with hexamethylene diisocyanate（HDI） to form a novel macromonomer namely monomethoxy polyethylene glycol isocyanate（mPEG-NCO） containing a isocyanate group with higher chemical activity in ethyl glyoxalate solution absolutely without water. The selective grafted copolymerization of Chitosan with mPEG-NCO was conducted under heterogeneous conditions as suspension in dimethylformamide. The hydrophilic copolymers of chitosan were prepared by condensation reaction of isocyanate group on mPEG- NCO with hydroxy groups on chitosan chains because amino groups on chitosan chains were protected by complexion formation with copper ions. The effect of reaction condition on the grafting extents was discussed. Swelling properties of mPEG-g-CS were researched. The graft copolymer mPEG-g-CS was characterized by the infrared spectra. The experimental result showed that the copper ions were very effective to protect amino groups from condensation reaction. The swelling degree in water increases with adding of grafting ratio. The maximum swelling degree was up to above 132% when the grafting ratio was about 270%. The graft copolymer can be soluble partially in pure water.

Synthesis and Characterization of Crosslinked Hydrogel of Konkoli (Maesopsis eminii) Grafted Polymethylacrylamide for a Preliminary Study as an Insulin Delivery System

Polysaccharide has lately received a significant attention in the formulation of drug delivery system based on the abundant availability, non-toxicity and the various ways its nature, structure and functionality can be modified. In this preliminary work on Konkoli (Maesopsis eminii) galactomannan (KG), it was modified by grafting with methacrylamide (MAAm) using ammonium persulphate (ASP) as initiator. The grafted galactomannan was then crosslinked using N, N-methylenebisacrylamide (N, N-MBAAm) to produce the hydrogel called konkoli grafted polymethylacrylamide (KG-g-poly (MAAm)). FTIR analyses confirm crosslinking and other changes in the functionality of KG-g-poly (MAAm) compared to KG. Swelling properties which are fundamental to the potential properties of any hydrogel as a drug delivery system were studied for KG-g-poly (MAAm) with varied amount of monomer (MAAm), crosslinker and pH with respect to time and temperature. There was a rapid rise followed by a dramatic fall in the swelling capacity with increase in both monomer and crosslinker concentration. The swelling capacity of KG-g-poly (MAAm) also improves as the pH of the medium was changed from acidic to alkaline. Generally, the swelling capacity of KG-g-poly (MAAm) increases with time and temperature of immersion. This result therefore encourages further studies as it presents KG-g-poly (MAAm) potentials in such application as insulin delivery system.

Quick pH-responsive Films Prepared from Urethane Acrylate Anionomers Under UV Radiationand Their Responsive Performances

Urethane acrylate anionomers(UAA) were prepared in various compositions by three steps. Under UV radiation, UAA formed pH-sensitive films with drying film thicknesses of 60, 200 and 330 μm. The equilibrium swelling ratios(SR) of the films in various pH buffer solutions increased with the increase of the molecule weight of UAA. The influence of the film thicknesses on the swelling performances of the films was investigated. The film with a thickness of 60 μm could reach the equilibrium state in 2.5—3.5 min.A high SR was obtained for a thick film due to its low average network density. The cured film could swell reversibly and rapidly with the change of pH, which is important for a controlled release system.

Hybrid Hydrogels Toughened by Chemical Covalent Bonding and Physical Electrostatic Interactions

Polystyrene nanoparticles with negative charges（n-PSs） were synthesized using styrene（St） and sodium styrene sulfonate（NaSS） as initial materials by surfactant-free emulsion polymerization. Subsequently, a hybrid hydrogel was prepared using acrylamide（AAm） and methacryloyloxyethyltrimethyl ammonium chloride（DMC） as co-monomers with N,N＇-methylenebisacrylmnide（MBA） as a chemical crosslinker and n-PSs as a physical electrostatic interaction agent. The resulting hybrid hydrogels exhibited excellent tensile strength and elongation at break. The tensile stress of hybrid hydrogels was seven times greater than that ofhydrogels without n-PSs. The elongation at break of hydrogels reached 700%, which was much higher compared to those of the hydrogels without n-PSs. Furthermore, swelling measurements of the hydrogels indicate that there is an overshoot in the swelling process and the extent of overshoot decreases with the increasing n-PSs. Therefore, the work presented here provides a method for improving the mechanical properties of hydrogels via the introduction of polymeric nanoparticles.