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1.
Natural pH and ion sensitive polyampholyte gels were successfully prepared by blending carboxymethyl chitosan (CM‐chitosan) and gelatin using glutaraldehyde as crosslinking agent. Their swelling behaviour under the influence of pH and ionic strength of the solution has been studied, and molecular interaction and, morphology of the gels were investigated by infrared spectroscopy and scanning electron microscopy. At the isoelectric point (IEP) the blend gels shrunk most, and when pH deviated from the IEP they behaved as polycations or polyanions. A decrease in swelling degree (Ds) with rising NaCl concentration up to 0.15 M was observed for all gels, while addition of Ca2+ made them shrink due to formation of Ca2+ crosslinked bridges. The blended gels showed increasing sensitivity to pH and ionic strength as the weight fraction of CM‐chitosan increased. Two essential components seem to regulate the swelling behaviour of blended gel: the first is related to osmotic pressure difference caused by the redistribution of mobile ions; the second is related to the possible formation of interactions corresponding to hydrogen bonding and hydrophobic interactions. © 2003 Society of Chemical Industry  相似文献   

2.
This article describes the synthesis of full and semi-interpenetrating polymer networks (IPNs) based on poly(acrylic acid) and gelatin as polymers 1 and 2, which were crosslinked sequentially using N,N′-methylene bisacrylamide (BAm) and glutaraldehyde, respectively. Various samples were prepared by taking varying amounts of acrylic acid and gelatin in the initial feed. Sequential IPNs were prepared by first polymerizing and crosslinking acrylic acid in the presence of gelatin using redox initiators (ammonium persulphate and sodium metabisulphite) and BAm as a crosslinking agent. Gelatin present in the firm gels was then crosslinked using 4% glutaraldehyde. Characterization of these gels was done by measuring their swelling behavior as a function of pH, temperature, and time. Percent swelling increased with increasing amounts of acrylic acid. The swelling ratio was also determined in the pH range of 1 to 12. Acid/alkali or buffers were used for maintaining pH. A significant increase in the percent swelling was observed when pH of distilled water was above 10. On the other hand, in the case of buffer, the swelling ratio increased with increasing the pH, and a maxima was observed at pH 8.4. A further increase in pH resulted in a decrease in the swelling ratio. Thermal and morphological characterization was done using thermogravimetric analyzer and scanning electron microscopy, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 217–227, 2001  相似文献   

3.
In this study, a novel temperature‐sensitive polymer, poly(N‐2‐methoxyisopropylacrylamide), PNMIPA, in the crosslinked hydrogel form was obtained. The monomer, N‐2‐methoxyisopropylacrylamide (NMIPA) was synthesized by the nucleophilic substitution reactions of acryloyl chloride with 2‐methoxyisopropylamine. Hydrogel matrix of PNMIPA was obtained by the bulk polymerization method. The bulk polymerization experiments were performed at +4°C, by using N,N‐methylenebisacrylamide (MBA) as crosslinker, polyethyleneglycol (PEG) 4000 as diluent, and potassium persulfate (KPS) and tetramethylethylenediamine (TEMED) as the initiator and accelerator, respectively. The same polymerization procedures were applied by changing monomer, initiator, crosslinker and diluent concentrations in order to obtain crosslinked gel structures having different temperature–sensitivity properties. The equilibrium swelling ratio of PNIMPA gel matrices at constant temperature increased with increasing initiator concentration and decreasing monomer concentration. The use of PEG 4000 as diluent in the gel synthesis resulted in about two times increase in equilibrium swelling ratios in the low temperature region. A decrease in the equilibrium swelling ratios of gel matrices started at 30°C and the decrease became insignificant at 55°C. Temperature‐sensitivities were determined in two different media. Distilled water medium was used in order to observe the temperature‐sensitivity of the gel clearly and the phosphate buffer medium was used in order to represent the temperature‐sensitive swelling behavior of the gel when it is used in biological media. Step effect was applied on ambient temperature in two opposite directions in order to examine the dynamic swelling and shrinking behaviors of the gels. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

4.
Poly(N-vinylimidazole) (PVIm) gels were prepared by irradiating a binary mixture of N-vinylimidazole (VIm)–water in a 60Co-γ source having 4.5 kGy/h dose rate. In the glucose oxidase (GOx) adsorption studies, affinity gels with a swelling ratio of 1100% for PVIm and 40 and 55% for Cu(II)- and Co(II)-chelated PVIm gels, respectively, at pH 6.5 in phosphate buffer were used. FTIR spectra were taken for PVIm and Cu(II)- and Co(II)-chelated PVIm, and glucose oxidase adsorption on these gels, to characterize the nature of the interactions in each species. The results show that PVIm–glucose oxidase interaction is mainly electrostatic and metal ion–chelated PVIm gel–glucose oxidase interaction is of coordinate covalent nature. Cu(II) and Co(II) ions were chelated within the gels via amine groups on the imidazole ring of the gel. Different amounts of Cu(II) and Co(II) ions [maximum 3.64 mmol/g dry gel for Cu(II) and 1.72 mmol/g dry gel for Co(II)] were loaded on the gels by changing the initial concentration of Cu(II) and Co(II) ions at pH 7.0. GOx adsorption on these gels from aqueous solutions containing different amounts of GOx at different pH was investigated in batch reactors. GOx adsorption capacity was further increased when Cu(II) and Co(II) ions were attached [up to 0.53 g GOx/g dry Co(II)-chelated PVIm gels]. More than 90% of the adsorbed GOx was desorbed in 5 h in desorption medium containing 1.0M KSCN at pH 7.0 for plain gel and 0.05M EDTA at pH 4.9 for metal-chelated gel. Nonspecific glucose oxidase adsorption on/in the metal ion–chelated PVIm gel was investigated using 0.02M of phosphate buffer solution. The nonspecific GOx adsorption was determined to be about 18% for PVIm and 8% for the metal ion–chelated PVIm gels. The ionic strength effect was investigated both on PVIm and on the metal ion–chelated PVIm gels for the glucose oxidase adsorption. It was found that ionic strength was more effective on the PVIm gel because of the electrostatic interaction between protonated gel and the deprotonated glucose oxidase side chain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 446–453, 2001  相似文献   

5.
Organic hybrid gels based on poly(N‐isopropylacrylamide) and a natural polymer, gelatin, were prepared through two‐step crosslinking with genipin or glutaraldehyde. The effects of the gelatin content on the swelling behaviors and physical properties of these hybrid gels were investigated. The results indicated that the swelling ratio decreased with an increase in the content of gelatin in these hybrid gels. The swelling ratio for the gel crosslinked by genipin was significantly smaller than that for the gel crosslinked by glutaraldehyde. The results also showed that the gel crosslinked with genipin had a higher crosslinking density and a higher gel strength. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1092–1099, 2005  相似文献   

6.
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  相似文献   

7.
Poly(α‐hydroxy acrylic acid) (PHA) and poly(acrylicacid) (PAA) gels were prepared by irradiating the respective 15 wt% aqueous solutions with γ‐rays. Swelling ratios for PHA gel were measured as a function of pH and divalent cation (Mg2+, Ca2+, Mn2+, Co2+, Ni2+, Cu2+) concentration C2 in the external solution to provide a comparison with the results for PAA gels. It was found that the swelling ratio of PHA gel steeply increases between pH 2 and 4, followed by a gradual swelling in the higher pH region. The corresponding steep swelling of PAA gel was observed at pH 3–6. Cation specificity in the equilibrium swelling ratio at a lower C2 value (1.0 × 10−3 M) was approximately consistent with the binding selectivity in the solution system. Typically, the swelling ratio of PHA gel in the presence of Ca2+ was significantly lower than in the Mg2+ system, while the difference was slight for PAA gel. The response of the swelling ratio to changes in pH and C2 was analysed as a first order relaxation to estimate the time constants. The (de)swelling kinetics measured by both the pH and C2 jump were qualitatively interpreted in terms of main‐chain stiffness and intermolecular hydrogen bonding in the respective polymers. © 2000 Society of Chemical Industry  相似文献   

8.
Two kinds of water-insoluble PVA-MA hydrogel films were prepared from PVA-MA, an esterification product of poly(vinyl alcohol) and maleic anhydride, by heat treatment and a crosslinking reaction, respectively. Both films changed their dimensions upon environmental pH changes. The crosslinked gel expanded to approximately 230% of its original length, with most changes occurring in the pH range of 2–7. The heat-treated PVA-MA film swelled stepwisely, with about 45% of the total expansion occurring at pH 2–7 and the remaining 55% at pH 9–12. Results from IR spectra analysis and acid-base titration suggest that the ionization of carboxylic acid accounts for the pH-induced gel swelling irrespective of the differences in the swelling behavior of these two gels. The pKa values of the heat-treated PVA-MA gel increased from 4 to 10 while the degree of dissociation varied from 0 to 80%, whereas that of the crosslinked PVA-MA film is limited in a range of 3.3–4.2. The permeability of glucose across the crosslinked PVA-MA film increased when pH was raised from 2 to 7. No significant change of permeability was noticed between pH 7 and 12. For the heat-treated PVA-MA film, glucose permeability increased when pH was changed from 2 to 7 and from 7 to 12. © 1996 John Wiley & Sons, Inc.  相似文献   

9.
Dilute aqueous solutions can be effectively concentrated with crosslinked partially hydrolysed polyacrylamide gels. Because the gels are near their critical point, they can be regenerated with small changes in pH. The selectivity of concentrating nonelectrolyte solutes can be adjusted by changes in gel crosslinking; the selectivity of separating electrolytes seems largely the result of Donnan equilibria. The regeneration of the gels is effected largely by altering the ionization of carboxylic acid groups within the gel, and less influenced by ion pairing. The regeneration is compromised at high salt concentrations which reduce the gel's swelling.  相似文献   

10.
《分离科学与技术》2012,47(13):2041-2048
The preparation of super absorbent hydrogels based on Kappa-carrageenan and polyacrylamide was carried out by electron beam irradiation technique. The gels were characterized for their temperature and pH responsive behavior by equilibrium swelling experiments and for their structure by FTIR, DSC, and SEM techniques. The effect of polymer composition, dose applied, pH, and temperature on swelling was evaluated. The suitability of these systems as matrix materials for the uptake of Cu2+ and Ni2+ ions from aqueous solutions was studied. The influence of gel structure and pH conditions on metal ion uptake capacity of gels were investigated. The metal ion uptake capacity has been correlated with the swelling ability of the gels.  相似文献   

11.
In the present work crosslinked methyl methacrylate-co-itaconic acid (MMA-co-IA) hydrogels were prepared by free radical copolymerization of methyl methacrylate (MMA) with itaconic acid (IA) using ethylene glycol dimethacrylate (EGDMA) and N, N methylene bisacrylamide (MBAAm) as crosslinkers and benzoyl peroxide as initiator. Prepared hydrogels were investigated for dynamic and equilibrium swelling studies. For swelling behaviour, effect of pH, monomeric compositions, degree of crosslinking and type of crosslinking agent were investigated. Swelling studies were performed in the USP phosphate buffer solutions of varying pH 1.2, 4.5, 5.5, 6.5 and 7.0. Results showed that swelling increased by increasing IA content in hydrogels structure. This may be due to the presence of more carboxylic groups available for ionization. Swelling was decreased with increase in crosslinking ratio owing to tighter hydrogel structure. Hydrogels were characterized by Fourier transform infrared (FTIR), and scanning electron microscope (SEM). Polymer-solvent interaction parameters (χ) of hydrogels were determined by using Flory–Rehner theory of equilibrium swelling values. The analysis of diffusion mechanism from gels using Peppas model showed that all monomeric compositions and degrees of crosslinking followed Fickian diffusion.  相似文献   

12.
Novel polyaspartamide copolymers containing histamine pendants (PHEA‐HIS) were prepared from polysuccinimide, which is the thermal polycondensation product of aspartic acid, via a successive ring‐opening reaction using histamine (HIS) and ethanolamine (EA). The prepared water‐soluble copolymer was then crosslinked by reacting it with hexamethylene diisocyanate in order to provide a hydrogel with both good gel strength and reversible CO2 absorption characteristics. PHEA‐HIS gel is also pH‐sensitive and eligible to coordinate to metal ions such as Pb2+, Cu2+, and Ni2+ due to the imidazole units in its structure. The CO2‐responsive swelling behavior, metal‐ion adsorption, and morphology of the crosslinked gels were investigated. The approach described here results is a promising hydrogel with potential for a variety of industrial and biomedical applications including CO2 capture, CO2‐responsive and switchable sensors, and smart drug delivery systems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43305.  相似文献   

13.
Hydrogels based on N‐acryloyl‐N′‐methylpiperazine (AcrNMP) swelled extensively in solutions of low pH due to the protonation of the tertiary amine. The water transport in the gels under an acidic condition was non‐Fickian and nearly Fickian in neutral pH with the collective diffusion coefficients determined as 2.08 × 10−7 and 5.00 × 10−7 cm−2 s−1, respectively. These gels demonstrated good metal‐uptake behavior with various divalent metal ions, in particular, copper and nickel, with the uptake capacity increased with increasing pH. The swelling ratio of the gel in the presence of metal ions decreased with increasing metal ion uptake. The results suggest that high metal ion uptake can lead to physical crosslinking arising from the interchain metal complex formation. The metal‐loaded gels could be stripped easily with 1M H2SO4 without any loss in their uptake capacity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 268–273, 2001  相似文献   

14.
The aqueous kinetic swelling properties of a class of cross-linked hydrophobic polyamine copolymer gels based on n-alkyl esters of methacrylic acid (nAMA) and N,N-dimethylaminoethyl methacrylate (DMA) have been studied as a function of solution ionic composition (pH, ionic strength, and buffer content), gel composition, and temperature. Water uptake and swelling in these gels are driven by ionization of the DMA amine groups, which overcomes the hydrophobic tendency of these gels to exclude water in the unionized state. Sorption kinetics in initially glassy gel disks are generally biphasic, characterized by an initial phase of relatively slow water uptake followed by an accelerated phase during which significant volume expansion of the gel occurs. This sorption/swelling behavior strongly suggests a moving penetrant front mechanism. The initial rate of water sorption increases markedly as (1) solution pH decreases, (2) gel nAMA comonomer content decreases, (3) gel nAMA side-chain length decreases, and (4) temperature increases. Furthermore, the initial phase of sorption in initially glassy gels is generally non-Fickian and approaches zero-order behavior as (1) pH increases, (2) nAMA content increases, and (3) temperature decreases. In direct contrast, sorption in initially dry, rubbery gels is monophasic, but non-Fickian, and approaches zero-order behavior as temperature increases. This behavior is contrary to the Fickian sorption behavior normally observed in polymers above their glass transition temperatures. Finally, sorption kinetics critically depend upon the nature of the ions in solution: Kinetics are significantly faster in the presence of weak electrolytes than that of strong electrolytes. We discuss the importance of the rate of ion transport in determining the overall sorption kinetics and how sorption kinetics can be non-Fickian in rubbery gels. Also, we propose a mechanism for the observed enhanced kinetics in the presence of weak electrolytes.  相似文献   

15.
A series of electric field sensitive copolymer P(AA‐co‐AAEM) gels of acrylic acid (AA) with acetoacetoxy ethyl methacrylate (AAEM) were prepared by free‐radical copolymerization, with N,N′‐methylene bisacrylamide (MBAAm) and ammounium persulfate (APS) as crosslinking agent and initiator, respectively. The structures and properties of the gels were tunable by changing the monomer feed weighty ratio (R) (R = WAAEM/(WAAEM + WAA) of AAEM and AA. The influences of the NaCl concentration and pH buffer solutions on the equilibrium swelling ratios of the gels were studied in detail. It is shown that both NaCl concentration and pH value of the buffer solution affect the swelling properties of the P(AA‐co‐AAEM) gels greatly. Moreover, the gel deswelling behavior induced by a direct current electric field was investigated and an excellent electric‐sensitivity was found. Among all the samples, the gel with monomer feed weighty ratio (R) = 0.1479 showed the best electrical contraction properties. On the basis of the experimental results, the mechanism of the electricity‐induced deswelling behavior was presented. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

16.
Poly (vinyl alcohol) with pendent styrylpyridinium groups (SbQ) is insolubilized by photoirradiation. An association takes place in SbQ groups. The association of polymer chains becomes marked with increasing the number of SbQ groups. Mainly intermolecular crosslinks were formed. Transparent and homogeneous macrogels consisting of several intermolecular crosslinks are obtained. The proportion of the free water to the bound water in PVA-SbQ gels was 3.3?2.9 despite of the large change in conversion of photodimerization of SbQ groups, x=0.27?0.58. The water uptake after swelling of the gels in water increased 6–27 times compared to the original weight at pH=7. The higher the degree of photocrosslinking, the lower was the degree of swelling. The water diffusion coefficients, D, were (2.2?5.8) × 10?5 cm2 S?1 for a 88% saponified PVA with 1 . 3 mol% SbQ groups. The volume of the gel increased discontinuously about 10-fold for the 99% saponified PVA with 0 . 096 mol% SbQ and 51% water (49% acetone). The acetone concentration at the transition decreased with increasing the degree of saponification of the PVA.  相似文献   

17.
A series of porous thermoreversible copolymeric hydrogels were prepared from N‐isopropylacrylamide (NIPAAm) and hydrophobic monomers such as 2,2,3,3,4,4,5,5‐octafluoropentyl methacrylate (OFPMA) and n‐butyl methacrylate (BMA) and CaCO3 or poly(ethylene glycol) 8000 (PEG8000) as porosigen by emulsion polymerization. The effect of hydrophobic monomers and porosigens on the fundamental properties, such as equilibrium swelling ratio, swelling kinetics, gel strength, crosslinked densities, etc., and fast swelling–deswelling behavior for the present copolymeric hydrogels were investigated. Results showed that the deswelling rates for the gels porosigened by CaCO3 were more rapid than those gels foamed by PEG8000. Results also showed that the swelling rates for the gel foamed by CaCO3 were higher than those for the gel foamed by PEG8000. At the same time, results also showed that the gels with OFPMA foamed by CaCO3 exhibit a faster swelling–deswelling behavior than those gels with BMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3152–3160, 2006  相似文献   

18.
In this study, we synthesized the new kinds of semiconducting polymeric gels having negative (n-type) and positive (p-type) counter ions as charge carriers. The polyacrylamide gel was doped with pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid, trisodium salt), having \textSO3 - {\text{SO}}_{3}^{ - } ions as side groups and Na+ as counter ions, so-called p-type semiconducting gel. The doping process was performed during the polymerization where the pyranine binds to the polymer strands over OH group chemically via radical addition. In a similar way, N-isopropylacrylamide (NIPA) gel was doped with methacrylamidopropyltrimethyl ammonium chloride (MAPTAC), having Cl as counter ions, so-called n-type semiconducting gel. Here MAPTAC was embedded by copolymerization within the polymer network (NIPA). These semiconducting gels can show different electrical properties by changing the concentration of the doping agents, swelling ratio etc. We have shown that the pn junction, formed by combining p-type and n-type gels together in close contact, rectifies the current similar to the conventional Si and Ge diodes.  相似文献   

19.
Grafting of N-isopropylacrylamide, NIPAAm, onto partially and fully hydrolyzed poly(vinyl alcohol–g-maleic anhydride), PVA–MA, was carried out in presence of ammonium persulfate as initiator. The crosslinked PVA–MA–NIPAAm copolymers were prepared in presence of different weight percentages of methylene bisacrylamide, MBA, as crosslinker and N,N,N,N′-tetramethylethylenediamine, TMEA, as accelerator. Crosslinked PVA–MA–NIPAAm copolymers were prepared at two different temperatures 5 and 55 °C. The structural features of these grafts were confirmed by 1H NMR analysis. Solution behaviors of both PVA–MA and PVA–MA–NIPAAm were evaluated from viscosity measurements. The swelling ratios of the crosslinked polymers were measured at different temperatures and pH values. The phase transition of the crosslinked gels was measured from DSC analysis. Crosslinked PVA–MA–NIPAAm grafts show different pH and temperature sensitivity. The swelling behaviors of PVA–MA–NIPAAm were referred to formation of hydrogen bonding between amide and carboxylic groups and also to hydrophobic aggregation of NIPAAm grafts.  相似文献   

20.
Poly (acrylamide‐co‐methyl methacrylate) hydrogels of different ratios were prepared by using chemical and physical crosslinks to study the effect of nature of crosslinks on swelling behavior of hydrogels. The chemically crosslinked gels were prepared by using NN′‐methylene bis acrylamide, while physically crosslinked hydrogels were prepared by precipitation polymerization method, using dioxane as solvent. Detailed swelling kinetics such as swelling ratio, transport exponent n, diffusion coefficient D and the effect of pH on equilibrium swelling studies. The study revealed that the nature of crosslinks alter the swelling characteristics of the hydrogel. In chemically crosslinked hydrogels the water transport is Fickian in nature, while in the case of the physically crosslinked hydrogels the water transport mechanism is anomalous indicating major change in relaxation mechanism due to nature of crosslinks. The results also indicate that with increasing acrylamide content the swelling ratio of the hydrogels were also increased, but the transport exponent n remains nearly constant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 779–786, 2003  相似文献   

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