Here we report the preparation and characterization of nanostructured thermo-responsive poly(acrylamide) (PAM)-based hydrogels. The addition of slightly crosslinked poly(N-isopropylacrylamide) (PNIPA) nanogels to AM reactive aqueous solution produces nanostructured hydrogels that exhibit a volume phase transition temperature (TVPT). Their swelling kinetics, TVPT's and mechanical properties at the equilibrium-swollen state (Heq) are investigated as a function of the concentration of PNIPA nanogels in the nanostructured hydrogels. Nanostructured hydrogels with PNIPA nanogels/AM mass ratios of 20/80 and above exhibit higher Heq and longer time to reach the equilibrium swelling than those of the conventional PAM hydrogels. However, the PNIPA nanogels possess thermo-responsive character missing in conventional PAM hydrogels. The TVPT of nanostructured hydrogels depends on PNIPA nanogel content but their elastic and Young moduli are larger than those of conventional hydrogels at similar swelling ratios. Swelling kinetics, TVPT, and mechanical properties are explained in terms of the controlled in-homogeneities introduced by the PNIPA nanogels during the polymerization. 相似文献
The thermoresponsive behavior and mechanical properties of nanostructured hydrogels, which consist of poly(acrylamide) nanoparticles embedded in a cross-linked poly(N-isopropylacrylamide) hydrogel matrix, are reported here. Nanostructured hydrogels exhibit a tuned volume phase transition temperature (TVPT), which varies with nanoparticle content in the range from 32 up to 39–40 °C. Moreover, larger equilibrium water uptake, faster swelling and de-swelling rates, and larger equilibrium swelling at 25 °C were obtained with nanostructured hydrogels compared with those of conventional ones. Elastic and Young’s moduli were larger than those of conventional hydrogels at similar swelling ratios. The tuned TVPT and the de-swelling rate were predicted with a modified Flory–Rehner equation coupled with a mixing rule that considers the contribution of both polymers. These behaviors are explained by a combination of hydrophilic/hydrophobic interactions and by the controlled inhomogeneities (nanoparticles) introduced by the method of synthesis. 相似文献
Thermo-sensitive poly (N-isopropylacrylamide) (PNIPA) hydrogel with fast response rate was prepared by polymerizing N-isopropylacrylamide (NIPA) in an aqueous hydroxyl-propyl-methyl cellulose solution. The volume phase transition temperature
of PNIPA hydrogels was characterized by differential scanning calorimetry (DSC), and the surface morphology was observed by
scanning electron microscopy (SEM). The swelling ratios of the hydrogels at different temperatures were measured. Furthermore,
the deswelling kinetics of the hydrogels was also studied by measuring their water retention capacity. In comparison with
a conventional PNIPA hydrogel prepared in water, the hydrogel synthesized in aqueous hydroxyl-propyl-methyl cellulose solution
has higher swelling ratios at temperatures below the lower critical solution temperature and exhibits a much faster response
rate to temperature changes. For example, the hydrogel made in aqueous hydroxyl-propyl-methyl cellulose solution lost 89%
water within 1 min and about 93% water in 4 min, whereas the conventional hydrogel lost only about 66% water in 15 min from
the deswelling measurement in similar conditions.
Translated from Chinese Journal of Applied Chemistry, 2006, 23(6): 581–585 (in Chinese) 相似文献
The synthesis by a two-stage polymerization process of microstructured polyacrylamide hydrogels with large swelling capacity and improved mechanical properties is reported. First, crosslinked polyacrylamide particles of nanosize scale are made by inverse microemulsion polymerization. These particles are then dried and redispersed in an aqueous solution of acrylamide and polymerized in the presence of a crosslinking agent. The microstructured hydrogels, in contrast to transparent conventional polyacrylamide hydrogels, are translucid due to the presence of the dispersed particles. The swelling capacity of these hydrogels increases as the particle content increases and their Young and elastic moduli (at equilibrium swelling) diminish only slightly. Mechanical tests disclose that the microstructured hydrogels have larger Young moduli than conventional hydrogels with an identical degree of swelling. Copyright 2001 Academic Press. 相似文献
New thermoresponsive crosslinked hydrogels with controlled multiblock copolymer structure were prepared from equimolar amounts of α,ω-diamino poly(propylene glycol)s with molecular weights (MW) 230, 400, and 2,000 g mol?1 and diepoxy-terminated poly(ethylene glycol)s of approximate MW 1,000; 2,000; and 4,000 g mol?1. Their thermoresponsive character was investigated on the 10–70 °C interval, while the swelling behavior was tested at 21, 37, and 50 °C. All hydrogels displayed temperature sensitivity, but a volume phase transition was noticed only in the case of poly(propylene glycol) (PPG)2000-containing hydrogels. The volume phase transition temperature (TVPT) depended on the MW of the hydrophilic poly(ethylene glycol) (PEG) chains attached to the PPG2000 block, as well as on the added salts. Longer PEG blocks determined a shift of TVPT towards higher values, while the influence of the salt added was in agreement with the Hofmeister series, except for NaH2PO4 which determined the destruction of the hydrogel network. The equilibrium swelling degree depended on the MW of both PEG and PPG blocks, as well as on temperature. The analysis of the swelling process indicated a modification of the gel characteristics with temperature and second-order kinetics for the water penetration into the hydrogel. 相似文献
Poly(methyl methacrylate) nanosize particles, made by microemulsion polymerization, were dispersed in an acrylamide aqueous solution, which was polymerized in the presence of a cross-linking agent to yield microstructured hydrogels. The kinetics of swelling and the mechanical properties of these hydrogels were investigated as a function of concentration of particles. The microstructured hydrogels exhibit higher equilibrium swelling and larger Young modulus than conventional (that is, without particles) polyacrylamide hydrogel. The morphology of the microstructured hydrogels was examined by transmission electron microscopy. 相似文献
A series of macroporous poly(N-isopropylacrylamide-co-acrylic acid) (PNIPAm-AA) hydrogels with different composition were synthesized by free-radical copolymerization in the presence
of silica particles as a pore generating agent. The equilibrium swelling ratio, half swelling time and dynamic swelling kinetics
of the copolymers previously soaked in different acidic buffer solutions were investigated at pH 7 at 25°C. Experimental results
revealed that the swelling rate of the macroporous hydrogels was greatly increased compared to conventional hydrogels due
to existence of the macroporous structures. It was found that the swelling history of previously putting in acidic solutions
copolymers had strong influence on their dynamic swelling kinetics especially for the samples ranging in composition between
30 and 70 mol % of NIPAAm, whereas the swelling history had little influence on the equilibrium swelling ratio of copolymers.
The swelling pattern exhibits sigmoid swelling curves. This is explained by an autocatalytic mechanism. The hydrogen bonding
dissociation plays an important role in the dynamic swelling behavior. 相似文献
Thermally sensitive hydrogels of poly[N-isopropylacrylamide (NIPA)-co-acrylic acid (AA)] hydrogels with N,N-methylene bisacrylamide (BIS) as crosslinker have been synthesized via a two-step procedure in which, the initial polymerisation is conducted for various times at 18 °C, this step being followed by polymerisation for one fixed time at −22 °C. The gravimetrically determined rates of swelling/deswelling for these materials termed “cryogels” prepared by this two-step polymerisation are much higher than those for the same type of hydrogel prepared via conventional methods (30 °C for 24 h). For example the time for the former xerogel to take up 70% of its final water content at 25 °C is just 18 min, compared with a time 300 min for the latter to attain the same uptake of water. During deswelling (shrinking) at 50 °C, which is above the lower critical temperature, the hydrogel loses 60 and 90 wt% water in 1 and 10 min respectively, compared to a timescale for the corresponding crosslinked copolymers prepared by conventional methods of about 100 min for 50 wt% water loss. A third type of hydrogel was made by a cold treatment (CT), for which the hydrogel prepared by conventional polymerization was stored in the frozen state. The swelling rate of these CT xerogels was the same as that for xerogels prepared by conventional polymerization, but the deswelling rate of the former was higher than that of the latter; for example, during deswelling, a loss of 90% water is attained within a few minutes.Scanning electron microscopy, digital photographs and flotation experiments together with swelling ratio studies reveal that the polymeric network of cryogel produced by the two-step polymerization method is characterized by an open structure with more pores and higher swelling ratio but lower mechanical strength compared to the conventional hydrogels. Such rapid response hydrogels have potential applications in separation and drug release technologies for example. 相似文献
Composite hydrogels—macroscopic hydrogels with embedded microgel particles—are expected to respond to external stimuli quickly because microgels swell much faster than bulky gels. In this work, the kinetics of the pH‐induced swelling of a composite hydrogel are studied using turbidity measurements. The embedded microgel is a pH‐ and thermosensitive poly(N‐isopropylacrylamide‐co‐acrylic acid) microgel and the hydrogel matrix is polyacrylamide. A rapid pH‐induced swelling of the embedded microgel particles is observed, confirming that composite hydrogels respond faster than ordinary hydrogels. However, compared with the free microgels, the swelling of the embedded microgel is much slower. Diffusion of OH? into the composite hydrogel film is identified as the main reason for the slow swelling of the embedded microgel particles, as the time of the pH‐induced swelling of this film is comparable to that of OH? diffusion into the film. The composition of the hydrogel matrix does not significantly change the characteristic swelling time of the composite hydrogel film. However, the swelling pattern of the film changes with composition of the hydrogel matrix. 相似文献
Ionically cross-linked polyampholytic hydrogels were synthesized by redox copolymerization of acrylamide and an ionic complex
of (N,N-diethylamino)ethyl methacrylate and acrylic acid (designated as PADA hydrogel). The swelling behavior of the hydrogels in
water indicated that a minimal equilibrium swelling ratio is found when the molar ratio of anionic/cationic monomers was 1.55.
In NaCl solution, the hydrogels exhibited the typical swelling behavior of conventional polyampholytic gels. Their equilibrium
swelling ratios increased with an increase in the NaCl concentration. In solutions of multivalent ions (CaCl2 and trisodium citrate solutions), the equilibrium swelling ratios of the hydrogels increased first and were then followed
by a decrease with an increase in salt concentration. Interestingly, an unexpected abrupt swelling phenomenon was observed
when the fully swollen hydrogels in salt solution were transmitted to pure water. The unique swelling behavior of PADA hydrogels
depends not only on the molar ratio of the anionic/cationic monomers but also on the valency of the ions. 相似文献
Thermosensitive hydrogels were prepared by free-radical polymerization in aqueous solution from N-isopropylacrylamide (NIPA) and acrylamide (AAm) monomers. N,N-Methylenebis(acrylamide) (MBAAm) was used as a crosslinker. A kinetic study of the absorption determined the transport mechanism. The diffusion coefficients of these hydrogels were calculated for the Fickian mechanism. It was shown that the swelling behavior of the P(NIPA-co-AAm) hydrogels can be controlled by changing the amount of MBAAm. The swelling equilibrium of the P(NIPA-co-AAm) hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In SDS and DTAB solutions, the equilibrium swelling ratio of the hydrogels increased, this is ascribed to the conversion of non-ionic P(NIPA-co-AAm) hydrogel into polyelectrolyte hydrogels due to binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method, it was found that the electric conductivity of the P(NIPA-co-AAm)—surfactant systems depended strongly on both the type and concentration of surfactant solutions. 相似文献
A series of novel hydrogels based on poly(N-isopropylacrylamide) (PNIPAAm) with pendant poly(N-(2-(dimethylamino) ethyl)-methacrylamide) (PDMAEMA) grafts were designed and synthesized. The influence of the pendant PDMAEMA grafts on the properties of the resulted hydrogels was examined in terms of morphology observed by scanning electron microscopy (SEM), thermal property characterized by differential scanning calorimetry (DSC) and shrinking/swelling kinetics upon external temperature changes. In comparison with the conventional PNIPAAm hydrogels, resulting hydrogels presented favorable pH sensitivity as well as improved thermosensitive properties, including enlarged water containing capability at room temperature and faster shrinking/swelling rate upon heating. In addition, fish DNA, used as a model drug, was loaded into the hydrogels, and the controlled release behavior of the drug-loaded hydrogels at different temperatures (22 and 37 °C) was further studied. 相似文献
Deuterium isotope effects on swelling kinetics and volume phase transition in typical polymer hydrogels (poly(N-isopropylacrylamide) and polyacrylamide gels) are discussed. Deuterium substitutions affect on the swelling kinetics and volume phase transition of the polymer hydrogels. The slower swelling kinetics of hydrogels in D2O than in H2O arises mainly from the high viscosity of the medium. The deuterium isotope effect on the swelling-shrinking curve of hydrogels would come from the different polymer-solvent interaction. The microenvironments of hydrogels studied by solvatochromic fluorescence probe are compared with the bulk state. The zipper-type hydrogen-bonding inter-polymer complexes (poly(acrylic acid)-polyacrylamide and poly(acrylic acid)-poly(N-acryloylglycineamide)) are also investigated and show the huge isotope effect on the phase separation temperature. 相似文献
Novel linear poly(NIPA‐co‐CL) copolymers have been synthesized by radical copolymerization of N‐isopropylacrylamide (NIPA) and 2‐methylene‐1,3‐dioxepane (MDO). The structure of copolymers was confirmed by 1H NMR and IR spectroscopy. Cross‐linked poly(NIPA‐co‐CL) hydrogels have also been prepared in toluene using N,N′‐methylenebisacrylamide as cross‐linking agent. The hydrogels thus obtained exhibit good temperature response and are biodegradable in the presence of proteinase K.
Temperature influence on the enzymatic degradation by proteinase K of poly(NIPA‐co‐CL) hydrogel (G‐60). 相似文献
Stimuli-sensitive porous hydrogels prepared with an emulsion templating method developed by the authors are potentially applicable
in the medical and pharmaceutical fields; thermosensitive N-isopropylacrylamide (NIPA) hydrogels having randomly distributed sphere-like cavities have been prepared by the polymerization
in an aqueous phase in an oil-in-water (O/W) emulsion, followed by the washing of oil (oleyl alcohol) microdroplets. The surfactant
plays a dominant role in the preparation of porous hydrogels and the pore size. This study concerns with the surfactant effects
on the stability of pre-gel O/W emulsions. The porous NIPA hydrogels were successfully prepared using the surfactants forming
the stable emulsion and their internal structures and swelling properties were characterized. The O/W emulsions and the porous
hydrogels prepared using various amounts of oil and surfactant were characterized. The information obtained serves for preparation
of porous hydrogels having suitable porous structure for their applications. 相似文献