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1.
pH‐sensitive poly(acrylamide‐co‐itaconic acid) [P(AAm/IA)] hydrogels were prepared by radiation induced copolymerization of acrylamide (AAm) and itaconic acid (IA) at various ratios. Swelling and shrinking behaviors of these hydrogels were found greatly dependent on the composition of the hydrogel and pH of the buffer solution. The basic structural parameters of the P(AAm/IA) networks such as the molecular weight between crosslinks (M c) and polymer–solvent interaction parameter (χ) were also determined using the modified Flory‐Rehner equations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2586–2594, 2004  相似文献   

2.
In this work, we report a series of poly(itaconic acid‐co‐acrylic acid‐co‐acrylamide) (poly(IA‐co‐AAc‐co‐AAm)) hydrogels via frontal polymerization (FP). FP starts on the top of the reaction mixture with aid of heating provided from soldering iron gun. Once polymerization initiated, no further energy is required to complete the process. The influences of IA/AAc weight ratios on frontal velocities, temperatures, and conversions on the reaction time are thoroughly investigated and discussed where the amount of AAm monomer remains constant. Fourier transform‐infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscope (SEM), dynamic mechanical analysis, and the swelling measurement are applied to characterize the as‐synthesized poly(IA‐co‐AAc‐co‐AAm) hydrogels. Interestingly, the swelling ratios of the hydrogels are changed with different IA/AAc contents, and the maximum swelling ratios are ~4439% in water. SEM images describe highly porous morphologies and explain good swelling capabilities. Moreover, the poly(IA‐co‐AAc‐co‐AAm) hydrogels exhibit superior pH‐responsive ability. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2214–2221  相似文献   

3.
In this work, poly((PMMA‐b‐VI)‐co‐AA) (MMA = methyl methacrylate; VI = 1‐vinylimidazole; AA = acrylic acid) hydrogels and poly((PMMA‐b‐VI)‐co‐AA)/TPU (TPU = thermoplastic polyurethane) IPN (interpenetrating polymer networks) hydrogels have been fabricated via versatile infrared laser ignited frontal polymerization by using poly(PMMA‐b‐VI) macromonomer as the mononer. The frontal velocity and Tmax (the highest temperature that the laser beam detected at a fixed point) can be adjusted by varying monomer weight ratios, the concentration of BPO (BPO = benzoyl peroxide) and the amount of TPU. Moreover, the addition of TPU enhances the reactant viscosity to suppress the “fingering” of frontal polymerization (FP) and decrease Tmax of the reaction, providing a new inert carrier (TPU) to assist FP. Through the characterization of Fourier transform‐infrared spectroscopy (FT‐IR), scanning electron microscope (SEM), and differential scanning calorimetry (DSC), the desired structure can be proved to exist in the IPN hydrogels. Furthermore, poly((PMMA‐b‐VI)‐co‐AA)/TPU IPN hydrogels possesses more excellent mechanical behaviors than hydrogels without IPN structure. Besides, the poly((PMMA‐b‐VI)‐co‐AA) hydrogels present splendid sensitive properties toward substances of different flavor including sourness (CA, citric acid or GA, gluconic acid), umami (SG, sodium glutamate), saltiness (SC, sodium chloride), sweetness (GLU, glucose), enabling their potential as artificial tongue‐like sensing materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1210–1221  相似文献   

4.
A series of an ionic hydrogels composed of N,N‐diethylaminoethyl methacrylamide (DEAEMA), N‐vinyl‐2‐pyrrolidone (VP), and itaconic acid were synthesized by free‐radical cross‐linking copolymerization in water–ethanol mixture by using N,N‐methylenebis(acrylamide) as the cross‐linker, ammonium persulfate as the initiator, and N,N,N′,N′‐tetramethylenediamine as the activator. The swelling behaviors of these hydrogels were analyzed in buffer solutions at various pH. It was observed that the swelling behavior of cross‐linked ionic poly(N,N‐diethylaminoethyl methacrylamide‐coN‐vinyl‐2‐pyrrolidone) [P(DEAEMA/VP)] hydrogels at different pH agreed with the modified Flory–Rehner equation based on the affine network model and the ideal Donnan theory. The swelling process in buffer solutions at various pH was found to be Fickian‐type diffusion. The pH‐reversibility and on–off switching properties of the P(DEAEMA/VP) hydrogels may be considered as good candidate to design novel drug‐delivery system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2819–2828, 2005  相似文献   

5.
N‐Isopropylacrylamide/itaconic acid copolymeric hydrogels were prepared by irradiation of the ternary mixtures of N‐isopropylacrylamide/itaconic acid/water by γ‐rays at ambient temperature. The dependence of swelling properties and phase transitions on the comonomer concentration and temperature were investigated. The hydrogels showed both temperature and pH responses. The effect of comonomer concentration on the uptake and release behavior of the hydrogels was studied. Methylene blue (MB) was used as a model drug for the investigation of drug uptake and release behavior of the hydrogels. The release studies showed that the basic parameters affecting the drug release behavior of the hydrogels were pH and temperature of the solution. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

6.
In this article, novel smart hydrogels based on biodegradable pH sensitive poly(L ‐glutamic acid‐g‐2‐hydroxylethyl methacrylate) (PGH) chains and temperature‐sensitive hydroxypropylcellulose‐g‐acrylic acid (HPC‐g‐AA) segments were designed and synthesized. The influence of pH and temperature on the equilibrium swelling ratios of the hydrogels was discussed. The optical transmittance of the hydrogels was also changed as a function of temperature, which reflecting that the HPC‐g‐AA part of the hydrogels became hydrophobic at the temperature above the lower critical solution temperature (LCST). At the same time, the LCST of the hydrogels had a visible pH‐dependent behavior. Scanning electron microscopic analysis revealed the morphology of the hydrogels before and after enzymatic degradation. The biodegradation rate of the hydrogels was directly related to the PGH content and the pH value. The in vitro release of bovine serum albumin from the hydrogels were investigated. The release profiles indicated that both the HPC‐g‐AA and PGH contents played important roles in the drug release behaviors. These results show that the smart hydrogels seem to be of great promise in pH–temperature oral drug delivery systems. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

7.
Novel polyacrylamide‐based hydrogels containing 3‐(trimethoxysilyl)propyl methacrylate and/or tetraethoxy silane were synthesized by means of frontal polymerization, using ammonium persulfate as initiator, N,N′‐methylene bisacrylamide as crosslinking agent and dimethyl sulfoxide as solvent. The obtained samples were treated at pH of 2 or 5 to induce the sol–gel reaction and evaluate their swelling behavior in the conditions. The occurrence of this reaction was assessed by solid‐state NMR. Moreover, the thermal properties of the dry materials were studied by differential scanning calorimetry and thermal gravimetric analysis, and their water‐contact angles were measured. It was found that the amount of Si affects the extent of swelling and the hydrophilicity of the resulting materials. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4618–4625  相似文献   

8.
Reducibly degradable hydrogels of poly(N‐isopropylacrylamide) (PNIPAM) and poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) were synthesized by the combination of reversible addition‐fragmentation chain transfer (RAFT) polymerization and click chemistry. The alkyne‐pending copolymer of PNIPAM or PDMAEMA was obtained through RAFT copolymerization of propargyl acrylate with NIPAM or DMAEMA. Bis‐2‐azidyl‐isobutyrylamide of cystamine (AIBCy) was used as the crosslinking reagent to prepare reducibly degradable hydrogels by click chemistry. The hydrogels exhibited temperature or pH stimulus‐responsive behavior in water, with rapid response, high swelling ratio, and reproducible swelling/shrinkage cycles. The loading and release of ceftriaxone sodium proved the feasibility of the hydrogels as the stimulus‐responsive drug delivery system. Furthermore, the presence of disulfide linkage in AIBCy favored the degradation of hydrogels in the reductive environment. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3604–3612, 2010  相似文献   

9.
Physically crosslinked hydrogels based on N‐vinylcaprolactam/acrylic acid and N‐vinylcaprolactam/methacrylic acid were prepared via free radical polymerization. These temperature responsive hydrogels were characterized in terms of glass transition, phase separation temperature, potentiometric titration and swelling properties. Results showed that phase transition temperature was dependent on the pH value of the solution; increasing pH led to higher lower critical solution temperature (LCST) values which was related to the dissociative behaviors of the carboxylic group of MAc in the buffered solutions. Additionally, with the incorporation of N,N‐dimethylacrylamide into the system, cloud point measurements and MDSC showed an increased in the LCST. This increase was based on hydrophilicity, the hydrophilic–hydrophobic balance was disturbed, and consequently, the LCST behavior was shifted. The pKa of the copolymers ranged between 5.6 and 6.5, while for the terpolymers pKa ranged between 5.3 and 6. At high pH (>10), the ? COOH group is deprotonated and negatively charged (? COO?), while at low pH (1–3) the carboxylic group remains protonated which results in hydrogen bonding between the hydroxyl groups (from NaOH) and the excess of HCl. These results correlate with swelling studies where above the pKa value the hydrogels dissolved rapidly compared to below pKa they did not dissolve at all. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1555–1564  相似文献   

10.
Novel water‐soluble amphiphilic block copolymers with pendant carboxylic acid groups are synthesized and used for the preparation of ionically crosslinked hydrogels. d ,l ‐Lactide (DLLA) and l ?3‐(2‐benzyloxycarbonyl)ethyl‐1,4‐dioxane‐2,5‐dione (BED) are copolymerized at different ratios via organo‐catalyzed ring‐opening polymerization using a hydroxyl‐terminated poly(ethylene glycol) (PEG–OH) macroinitiator. Dynamic light‐scattering experiments show that, at low concentrations, aqueous solutions of these PEG‐P(BED‐DLLA) copolymers form micelles and aggregates. At higher concentrations, thermo‐sensitive gels are obtained, exhibiting a reversible gel‐to‐sol transition upon a temperature increase. Ionic interactions between the COOH groups and metal ions (Cu2+ or Ca2+) are shown to significantly shift the gel–sol transition to higher temperatures. Thus, the introduction of COOH groups significantly enhances the water solubility of the amphiphilic PEG–polyester copolymer and allows additional crosslinking interactions to form functionalized hydrogels with improved physical properties, making this new class of hydrogels interesting for various applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1222–1227  相似文献   

11.
We report a new facile strategy for quickly synthesizing pH sensitive poly(VI‐co‐HEA) hydrogels (VI = N‐vinylimidazole; HEA = 2‐hydroxyethyl acrylate) by frontal polymerization. The appropriate amounts of VI, HEA, and ammonium persulfate (APS)/N,N,N′,N′‐tetramethylethylenediamine (TMEDA) couple redox initiator were mixed together at ambient temperature in the presence of glycerol as the solvent medium. Frontal polymerization (FP) was initiated by heating the upper side of the mixture with a soldering iron. Once initiated, no further energy was required for the polymerization to occur. The dependence of the front velocity and front temperature on the VI/HEA weight ratios were investigated. The pH sensitive behavior, morphology, and heavy metal removal study of poly(VI‐co‐HEA) hydrogels prepared via FP were comparatively investigated on the basis of swelling measurements, scanning electron microscopy, and inductively coupling plasma spectrometer. Results show that the poly(VI‐co‐HEA) hydrogels prepared via FP exhibit good pH sensitivity and adsorption capacity. The FP can be exploited as an alternative means for synthesis of pH sensitive hydrogels in a fast and efficient way. The as‐prepared hydrogels can be applied to remove heavy metals. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4005–4012, 2010  相似文献   

12.
In this work, a hemicellulose-containing hydrogel was synthesized. As the first step, a temperature- and pH-sensitive copolymer was synthesized from itaconic acid and N-isopropylacrylamide (NIPAAm). Then the hydrogel was prepared by reacting the copolymer with acylated hemicellulose and polyvinyl alcohol. The morphology, compressive strength, thermal stability, swelling/deswelling behavior, drug-release behavior performances of the hydrogels were investigated. The lower critical solution temperature of the hydrogels varied in 34–44°C when the NIPAAm and itaconic acid mass ratios ranged in 100/0–90/10. Both temperature and pH had a significant influence on equilibrium swelling ratio of hydrogels. The equilibrium swelling ratio increased with pH, but decreased with temperature. Cytocompatibility assay demonstrated that this hemicellulose-containing hydrogel was biocompatible. The release process of salicylic acid suggested that this hydrogel had a potential use in controlled drug release.  相似文献   

13.
A new series of linear and crosslinked copolymers, obtained from 3‐octyl‐1‐vinylimidazolium bromide (VImBr) and N‐isopropylacrylamide (NIPAAm), were prepared by radical polymerization. Namely, VImBr was synthesized from 1‐bromooctane and an ionic liquid such as 1‐vinylimidazole. NIPAAm was used because it gives raise to well known thermoresponsive (co‐)polymers. The copolymers were thoroughly characterized by means of 1H NMR and 13C NMR spectroscopies. Besides, differential scanning calorimetry, Fourier transform infrared spectroscopy, and scanning electron microscopy were also used. Moreover, the swelling behavior and the thermoresponsive properties of the corresponding hydrogels were studied. It was found that the VImBr incorporation into the copolymers does have a dramatic influence on both the thermal properties of the dried materials and the lower critical solution temperature of the corresponding hydrogels. In detail, the glass transition temperature was dependent on the monomer ratios, and ranged from 5 to 155 °C. Analogously, the lower critical solution temperature of the resulting hydrogels ranged from less than 10 up to 38 °C, thus including the physiological temperature. NMR spectroscopies, which were performed on the linear polymers, indicated that the monomers exhibit an alternating tendency resulting in a microstructure in which blocks are not present, at least when the two monomers are in equimolar amounts. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3521–3532  相似文献   

14.
Super water absorbent polymer hydrogels were synthesized by frontal polymerization. These materials were obtained by copolymerizing N‐isopropyl acrylamide (NIPAAm) and 3‐sulfopropyl acrylate potassium salt (SPAK) in the presence of N,N′‐methylene‐bis‐acrylamide as a crosslinker. It was found that their swelling behavior in water can be easily tuned by using either the appropriate monomer ratio or the amount of the crosslinker used. Namely, the swelling ratio was found to range from about 1000% for the NIPAAm homopolymer in the presence of 5.0 mol % of crosslinker, up to 35,000% for the sample containing 87.5 mol % of SPAK and 1.0 mol % of crosslinker. The affinity toward water was also confirmed by contact angle analysis. Moreover, the obtained hydrogels exhibit a thermoresponsive behavior, with a lower critical solution temperature of about 28–30 °C. This value is close to that of poly(NIPAAm) but with a swelling capability that dramatically increases as the amount of SPAK increases. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

15.
We report the facile synthesis of poly(VI‐co‐MAA) superabsorbent polyampholytic hydrogels (VI = N‐vinylimidazole, MAA = methacrylic acid) via plasma‐ignited frontal polymerization (PIFP). On igniting the top surface of the reactants with air plasma, frontal polymerization occurred and poly(VI‐co‐MAA) hydrogels were obtained within minutes. The preparation parameters were investigated, along with swelling capacity, morphology, and chemical structures of poly(VI‐co‐MAA) hydrogels. Interestingly, the hydrogels are superabsorbent in water and show ampholytic characteristic toward pH. Moreover, the hydrogels are able to capture cationic dyes through electrostatic interaction, offering the potential for further development as dye adsorbents for water purification. In addition, nanocomposite hydrogels were obtained by embedding quantum dots (carbon dots or CdS nanocrystals) into the polymer matrix, which endows the nanocomposite hydrogels with favorable fluorescence and potential applications in bioimaging and biosensing. The results indicate that FP can be applied as an alternative means for facile synthesis of multifunctional hydrogels with additional efficiency and energy‐saving. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 912–920  相似文献   

16.
Dual temperature‐ and pH‐sensitive hydrogels composed of N‐isopropylacrylamide (NIPAM) and 2‐acrylamido‐2‐methyl‐propanosulfonic acid (AMPS) were prepared by free‐radical crosslinking copolymerization in aqueous solution at 22 °C. The mole percent of AMPS in the comonomer feed was varied between 0.0 and 7.5, while the crosslinker ratio was fixed at 5.0/100. The effect of AMPS content on thermo‐ and pH‐ induced phase transitions as well as equilibrium swelling/deswelling, interior morphology and network structure was investigated. The volume phase transition temperature (VPT‐T) was determined by both swelling/deswelling measurements and differential scanning calorimetry (DSC) technique. In addition, the volume phase transition pH (VPT‐pH) was detected from the derivative of the curves of the swelling ratio (dQv/dpH) versus pH. The polymer‐solvent interaction parameter (χ) and the average molecular mass between crosslinks ( ) of hydrogels were calculated from swelling ratios in buffer solutions at various pHs. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter of hydrogels were also determined by using the modified Flory–Rehner equation. The negative values for ΔH and ΔS indicated that the hydrogels had a negative temperature‐sensitive property in water, that is, swelling at a lower temperature and shrinking at a higher temperature. It was observed that the experimental swelling data of hydrogels at different temperature agreed with the modified Flory‐Rehner approach based on the affine network model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1713–1724, 2008  相似文献   

17.
Novel stimuli‐responsive hydrophilic microspheres were prepared by free radical polymerization of hydroxyethyl methacrylate (HEMA) and methacrylic acid (MA), as hydrophilic monomers, and N‐isopropylacrylamide (NIPAAm) and N,N′‐ethylenebisacrylamide (EBA), as thermo‐sensitive monomer and crosslinker, respectively. Hydrophilic comonomers were introduced in the macromolecular network to synthesize materials with tunable thermal behavior. In addition, by introducing in the polymerization feed both a hydrophilic and a pH‐sensitive monomer, such as MA, dual stimuli‐responsive (pH and temperature) hydrogels were synthesized. The incorporation of monomers in the network was confirmed by infrared spectroscopy, while the network density and the shape of hydrogels was found to strictly depend on the concentration of monomers in the polymerization feed. Thermal analyses showed negative thermo‐responsive behavior with pronounced water affinity of microspheres at a temperature lower than lower critical solution temperature (LCST). In our experiment, the LCST values of the hydrogels were in the range 34.6–37.5°C, close to the body temperature, and the amount of hydrophilic moieties in the polymeric network allows to collect shrinking/swelling transition temperatures higher than the LCST of NIPAAm homopolymers. In order to test the preformed materials as drug carriers, diclofenac diethylammonium salt (DDA) was chosen and drug entrapment percent was determined. Drug release profiles, in media at different temperature and pH, depend on hydrogels crosslinking degree and drug–bead interactions. By using semi‐empirical equations, the release mechanism was extensively studied and the diffusional contribute was evaluated. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

18.
Simple‐structured copolymer, poly(NIPMAM‐co‐CPMA), consisting of N‐isopropylmethacrylamide (NIPMAM) and (Z)‐4‐(1‐cyano‐2‐(4‐(dimethylamino) phenyl)vinyl)phenylmethylacrylate (CPMA) units as thermo‐ and pH‐responsive fluorescent signaling parts, respectively, has been synthesized by reversible addition–fragmentation chain transfer polymerization. The copolymer PCN250 (m/n = 250) shows absorbance enhancement or decrease at different pH value. However, the fluorescence intensity of this copolymer shows enhancement with a rise in temperature regardless of pH value in the range of pH = 4–10. In addition, fluorescence suppression of copolymer (PCN250) was observed with high proton concentration. Moreover, the lower critical solution temperature of the copolymers, poly‐(NIPMAM‐co‐CPMA), with different component was also investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

19.
The synthesis via copper(I)‐catalyzed azide alkyne cycloaddition (CuAAC) of three new monomer derivatives of N‐vinyl‐2‐pyrrolidone (VP) carrying cyclic pyrrolidine, piperidine, and piperazine groups and the corresponding copolymers with unmodified VP is shown. The systems bearing pyrrolidine and piperidine displayed both thermo‐ and pH‐response, which has not been reported previously for a polymer with polyvinylpyrrolidone (PVP) backbone. A broad modulation of the LCST with the copolymer composition and pH was observed in a temperature range 0–100 °C. The polymers carrying piperazine exhibited broad buffering regions and no thermosensitivity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1098–1108  相似文献   

20.
Polymers that possess lower critical solution temperature behavior such as poly(2‐alkyl‐2‐oxazoline)s (PAOx) are interesting for their application as stimulus‐responsive materials, for example in the biomedical field. In this work, we discuss the scalable and controlled synthesis of a library of pH‐ and temperature‐sensitive 2‐n‐propyl‐2‐oxazoline P(nPropOx) based copolymers containing amine and carboxylic acid functionalized side chains by cationic ring opening polymerization and postpolymerization functionalization strategies. Using turbidimetry, we found that the cloud point temperature (CP) is strongly dependent on both the polymer concentration and the polymer charge (as a function of pH). Furthermore, we observed that the CP decreased with increasing salt concentration, whereas the CP increased linearly with increasing amount of carboxylic acid groups. Finally, turbidimetry studies in PBS‐buffer indicate that CPs of these polymers are close to body temperature at biologically relevant polymer concentrations, which demonstrates the potential of P(nPropOx) as stimulus‐responsive polymeric systems in, for example, drug delivery applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1573–1582  相似文献   

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