Synthesis and properties of P(NIPAAm‐co‐AM)/SiO2 hybrid temperature‐sensitive hydrogels

Using N, N′‐methylene bisacrylamide as crosslinking agent and potassium peroxydisulfate as initiator, the temperature‐sensitive hydrogels were prepared with organic monomer N‐isopropylacrylamide (NIPAAm) and acrylic amide and inorganic material ethyl orthosilicate (TEOS). The structure of hybrid hydrogels was represented by scanning electron microscopy and Fourier transform infrared spectroscopy. The volume phase transition temperature (VPTT) of hybrid hydrogels was determined by differential scanning calorimetry thermograms of the swollen hydrogel. The results showed that the VPTT of the hydrogels increased with the increasing of TEOS dosage. When the temperature was lower than VPTT, the hydrogels exhibited excellent temperature sensitivity and kept at a swelling state, but when the temperature was higher than VPTT, the hydrogels deswelled significantly. In addition, the compressive strength of hydrogels was studied, the results showed that hybrid hydrogels had more ideal mechanical properties than organic hydrogels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and performance of nanocomposite hydrogels based on different clay

To look for economic substitute of Laponite, two kinds of clay minerals purchased in China were chosen to prepare nanocomposite hydrogels. Structure, morphology, temperature-sensitivity and swelling behavior were investigated by XRD, SEM, DSC and gravimetric method. In comparison with hydrogel cross-linked by Laponite XLG, the hydrogel with hectorite (Lvjie trademark) or montmorillonite (G-105) as cross-linker exhibited higher swelling ratios as well as faster response rate. In the case of temperature-sensitivity, the volume phase transition temperature (VPTT) of the hydrogels cross-linked by hectorite (Lvjie trademark) and montmorillonite (G-105) was 31–33 °C, slightly different from hydrogels with Laponite XLG. The hydrogel with montmorillonite (G-105) was brown and fragile. The hectorite (Lvjie trademark) appeared as optimal substitute of Laponite in hydrogels because the prepared hydrogel exhibited high swelling ratio, rapid response rate, excellent thermal responsibility, good dispersion in hydrogel matrix and high storage modulus.     

通过RAFT聚合方法合成具有高强度和高溶胀率的纳米水凝胶

为了得到具有高强度和高溶胀率的纳米水凝胶(NCgels),N-异丙基丙烯酰胺通过可逆加成断裂链转移(RAFT)聚合的方法,插层在含有质量分数为0.25%～15%的可扩展的有机化的蒙脱土(Clay-S)层间并交联。结果表明,与传统水凝胶相比,该水凝胶的强度和溶胀性能得到了很大提高,并且对温度的变化具有较快的响应速率。以质量分数为5%的蒙脱土,链转移剂的质量分数为0.5%制备的纳米水凝胶为例,该水凝胶在20℃的溶胀率为450,而传统水凝胶在相同温度时的溶胀率仅为20;该水凝胶在1min内失去75%的水,在4min内失去约90%的水,而传统水凝胶在15min内仅失去66%左右的水。     

Thermoreversible hydrogels X: Synthesis and swelling behavior of the (N‐isopropylacrylamide‐co‐sodium 2‐acrylamido‐2‐methylpropyl sulfonate) copolymeric hydrogels

A series of thermosensitive hydrogels were prepared from various molar ratios of N‐isopropylacrylamide (NIPAAm) and sodium‐2‐acrylamido‐2‐methylpropyl sulfonate (NaAMPS). Factors such as temperature and initial total monomer concentration and different pH solutions were investigated. Results indicated that the more the NaAMPS content in hydrogel system, the higher the swelling ratio and the gel transition temperature; the higher the initial monomer concentration, the lower the swelling ratio. The result also indicated that the NIPAAm/NaAMPS copolymeric hydrogels had different swelling ratios in various pH environments. The present gels showed a pH‐reversible property between pH 3 and pH 10 and thermoreversibility. The swelling ratios of copolymeric gels were lower in a strong alkaline environment because the gels were screened by counterions. Finally, the drug release behavior of these gels was also investigated in this article. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1760–1768, 2000     

Thermoreversible hydrogels. IX. Swelling behaviors of thermosensitive hydrogels copolymerized by N‐isopropylacrylamide with 1‐vinyl‐3‐(3‐sulfopropyl) imidazolium betaine

A series of thermosensitive hydrogels were prepared from the various molar ratios of N‐isopropylacrylamide, 1‐vinyl‐3‐(3‐sulfopropyl) imidazolium betaine (VSIB), and N,N′‐methylene‐bis‐acrylamide. The influence of the amount of VSIB in the copolymeric gels on the swelling behaviors in water, in various saline solutions, and at various temperatures was investigated. The results indicated that the higher the VSIB content in the hydrogel system, the higher the swelling ratio and the gel transition temperature. In the saline solution the results showed that when the concentration of salt is higher than the minimum salt concentration (MSC) of poly(VSIB), the deswelling behavior of the copolymeric gel was more effectively suppressed as more VSIB was added to the copolymeric gels. In addition, only the sample containing 12 mol % VSIB (V4) exhibited an antipolyelectrolyte's swelling behavior when the concentration of salt was higher than the MSC of poly(VSIB). This means that the swelling ratio of the hydrogel can be improved with a higher concentration salt solution. In addition, the anion effects were larger than the cation effects in the presence of a common anion (Cl⁻) with different cations and a common cation (K⁺) with different anions for the hydrogel. Finally, the more VSIB in the hydrogel, the higher the diffusion coefficient in dynamic swelling. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 14–23, 2000     

Application of syndiotacticity‐rich PVA hydrogels prepared at a low temperature to thermo‐ and pH‐responsive release devices

Three kinds of physically cross‐linked syndiotacticity‐rich poly(vinyl alcohol) (s‐PVA) hydrogels were prepared at 0°C with use of the buffer solutions (BS) of pHs 4.0, 7.4, and 9.0. Three gels swelled at first and then began to shrink after 12 h when they were dipped in the same BS for preparation at higher temperature than 0°C. The release of Brilliant Blue (3 mg/1 mL) from the cylindrical gels prepared using BS of pH 7.4 was studied at 27, 37, and 47°C. Brilliant Blue has been released spending 4–12 h almost completely. The rate of release from the gel at temperatures of 27, 37, and 47°C became large with increasing temperature. The main factor on release of Brilliant Blue is not the contraction of gel, but swelling, because the degree of swelling (DS) became large with increasing temperatures for 27, 37, and 47°C. The rate of release from the gel (pH 4.0) was larger than that (pH 7.4) due to the increased DS of the hydrogel in early step at pH of 4.0. The apparent diffusion exponents of these releases at pH 7.4 evaluated from first 60% of the fractional release were lower than 0.45 due to the swelling during release. The exponent at pH 4.0 was 0.45 due to immediate swelling. The on‐off of shrinking behavior of atactic PVA (a‐PVA) hydrogel was observed under several temperature changes. The rate of release of Brilliant Blue at 5°C was lower than that at 27°C and no change was observed at 5°C after one on‐off cycle. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 41–46, 2000     

Studies of reinforcement behavior of unique elastomer‐based nanocomposite gels

Unique nanocomposite (NC) gels were prepared by blending water swollen unmodified montmorillonite clay suspension with natural rubber (NR) and styrene‐butadiene rubber (SBR) latices followed by prevulcanization. These were extensively characterized by dynamic light scattering, solvent swelling, tensile, and dynamic mechanical measurements. Reinforcement behavior of NC gels was investigated by adding NC gels into virgin NR and SBR matrices at various loadings. The distribution and morphology of NC gels in the elastomer matrices was studied by X‐ray dot mapping and high‐resolution transmission electron microscopy. Experimental results indicated tremendous improvement of tensile strength (TS) and modulus of the NC gel‐filled matrices along with noticeable changes in dynamic mechanical and rheological properties. Compared with virgin NR, the TS of 16 phr NC gel‐filled NR system increased by 117%. Similar level of enhancement of TS was also registered for the NC gel‐filled SBR systems. NC gel‐filled systems showed higher shear viscosities and lower die‐swell values compared with their virgin counterparts. Contemporary particulate composite and nanofiller reinforcement models were used to understand the reinforcing behavior of these NC gels. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Thermoreversible hydrogels. VIII. Effect of a zwitterionic monomer on swelling behaviors of thermosensitive hydrogels copolymerized by N‐isopropylacrylamide with N,N′‐dimethyl (acrylamidopropyl) ammonium propane sulfonate

A series of thermosensitive hydrogels were prepared from the various molar ratios of N‐isopropylacrylamide, zwitterionic monomer, N,N′‐dimethyl (acrylamidopropyl) ammonium propane sulfonate (DMAAPS), and N,N′‐methylene‐bis‐acrylamide. The influence of the amount of DMAAPS in the copolymeric gels on the swelling behaviors in water, various saline solutions, and various temperatures was investigated. Results indicated that the higher the DMAAPS content in the hydrogel system, the higher the swelling ratio and the gel transition temperature. In the saline solution results showed that, when the salt concentration was greater than the minimum salt concentration (MSC) of poly(DMAAPS), the deswelling behavior of the N‐isopropylacrylamide gel was suppressed more effectively when more DMAAPS was added into the copolymeric gels; but the swelling ratios of the present copolymeric gels did not significantly change while the salt concentration was lower than the MSC of poly(DMAAPS). In addition, only the sample containing 12 mol % DMAAPS (D4) exhibited an antipolyelectrolyte's swelling behavior when the salt concentration was greater than the MSC of poly(DMAAPS). In other words, only when the amount of DMAAPS added into the gel is over some proportion, can the hydrogel show an antipolyelectrolyte's swelling behavior in concentrated salt solution. In saline solutions, the anion effects were greater than the cation effects in the presence of common anion (Cl⁻) with different cations and common cation (K⁺) with different cations for these gels. Finally, the more DMAAPS content in the hydrogel, the higher the diffusion coefficient in dynamic swelling. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2170–2180, 1999     

Hydrogel characteristics of a novel temperature‐sensitive polymer,poly(N‐2‐methoxyisopropylacrylamide)

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     

Preparation and characterization of sodium alginate/poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide)/clay semi-IPN magnetic hydrogels

pH- and temperature-responsive semi-interpenetrating magnetic nanocomposite hydrogels (NC hydrogels) were prepared by using linear sodium alginate (SA), poly(N-isopropylacrylamide) (PNIPAM) and Fe₃O₄ nanoparticles with inorganic clay as an effective multifunctional cross-linker. The effects of cross-linker and SA contents on various physical properties were investigated. The NC hydrogels exhibited a volume phase transition temperature (VPTT) around 32 °C with no significant deviation from the conventional chemically cross-linked PNIPAM hydrogels (OR hydrogels). The swelling ratios of NC hydrogels were much larger than those of OR hydrogels. Moreover, the swelling ratios of NC hydrogels gradually decreased with increasing the contents of clay and increased with increasing the contents of SA. The pH sensitivity of NC hydrogels was evident below their VPTT. The NC hydrogels had a much better mechanical property than the OR hydrogels. The results showed that the incorporation of clay did not affect the saturation magnetization of the hydrogels.     

pH‐thermoreversible hydrogels. I. Synthesis and swelling behaviors of the (N‐isopropylacrylamide‐co‐acrylamide‐co‐2‐hydroxyethyl methacrylate) copolymeric hydrogels

A series of pH‐thermoreversible hydrogels that exhibited volume phase transition was synthesized by various molar ratios of N‐isopropylacrylamide (NIPAAm), acrylamide (AAm), and 2‐hydroxyethyl methacrylate (HEMA). The influence of environmental conditions such as temperature and pH value on the swelling behavior of these copolymeric gels was investigated. Results showed that the hydrogels exhibited different equilibrium swelling ratios in different pH solutions. Amide groups could be hydrolyzed to form negatively charged carboxylate ion groups in their hydrophilic polymeric network in response to an external pH variation. The pH sensitivities of these gels also depended on the AAm content in the copolymeric gels; thus the greater the AAm content, the higher the pH sensitivity. These hydrogels, based on a temperature‐sensitive hydrogel, demonstrated a significant change of equilibrium swelling in aqueous media between a highly solvated, swollen gel state and a dehydrated network response to small variations of temperature. pH‐thermoreversible hydrogels were used for a study of the release of a model drug, caffeine, with changes in temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 221–231, 1999     

Synthesis and swelling properties of 2‐hydroxyethyl methacrylate‐co‐1‐vinyl‐3‐(3‐sulfopropyl)imidazolium betaine hydrogels

A series of 2‐hydroxyethyl methacrylate/1‐vinyl‐3‐(3‐sulfopropyl)imidazolium betaine (HEMA/VSIB) copolymeric gels were prepared from various molar ratios of HEMA and the zwitterionic monomer VSIB. The influence of the amount of VSIB in copolymeric gels on their swelling behavior in water and various saline solutions at different temperatures and the drug‐release behavior, compression strength, and crosslinking density were investigated. Experimental results indicated that the PHEMA hydrogel and the lower VSIB content (3%) in the HEMA/VSIB gel exhibited an overshooting phenomenon in their dynamic swelling behavior, and the overshooting ratio decreased with increase of the temperature. In the equilibrium water content, the value increased with increase of the VSIB content in HEMA/VSIB hydrogels. In the saline solution, the water content for these gels was not affected by the ion concentration when the salt concentration was lower than the minimum salt concentration (MSC) of poly(VSIB). When the salt concentration was higher than the MSC of poly(VSIB), the deswelling behavior of the copolymeric gel was more effectively suppressed as more VSIB was added to the copolymeric gels. However, the swelling behavior of gels in KI, KBr, NaClO₄, and NaNO₃ solutions at a higher concentration would cause an antipolyelectrolyte phenomenon. Besides, the anion effects were larger than were the cation effects in the presence of a common anion (Cl^?) with different cations and a common cation (K⁺) with different anions for the hydrogel. In drug‐release behavior, the addition of VSIB increased the drug‐release ratio and the release rate. Finally, the addition of VSIB in the hydrogel improved the gel strength and crosslinking density of the gel. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2888–2900, 2001     

交联三维网络结构PINPAm的制备及其性能研究

聚N-异丙基丙烯酰胺(PINPAm)水凝胶是一种亲水但不溶于水,具有交联三维网络结构的高分子聚合物,具有一定条件下的溶胀/退溶胀行为,同时具有输送和渗透性、能量转换、吸附分离、生物相容性等功能。本文研究了用不同量的引发剂过硫酸铵(APS)对水凝胶形成的影响;反应温度分别为低温(低于5℃、20℃、30℃、40℃对水凝胶形成的影响。所制备的PNIPAm水凝胶分别测定了相转变温度(LCST)和凝胶溶胀率(SR)。结果表明引发剂量用量增多时水凝胶形成反应时间变短;反应温度升高水凝胶外观出现由无色透明凝胶→乳白半透明凝胶→乳白色凝胶→乳白色且无固定形态凝胶的变化。低温生成的水凝胶相转变温度(LCST)在33~34℃之间,水凝胶体积发生不连续收缩现象;交联剂N,N-亚甲基双丙烯酞胺(BIS)使用量越多溶胀率越小。     

Macroporous dehydroalanine polymer hydrogel with fast temperature response and high repetition durability

Thermoresponsive hydrogels based on poly(methyl 2‐isobutyramidoacrylate) (PMIBA) were prepared by free‐radical crosslinking polymerization of the corresponding monomer using N,N′‐methylenebisacrylamide as a crosslinker. The PMIBA hydrogels showed a reversible temperature‐induced volume change with a volume phase transition temperature (VPTT) at 19°C, while they contained more than 60 wt % water even in the equilibrium deswollen state. When the external temperature was raised rapidly above the VPTT, the PMIBA gels shrank smoothly with time at a faster rate than conventional poly(N‐isopropylacrylamide) hydrogels of the same size. The fast and smooth deswelling response of the PMIBA gel is ascribed to its sponge‐like structure with 0.1–1 µm pore sizes formed in the deswollen state. The smooth deswelling response due to the macroporous structure resulted in high durability against repeated changes in the external temperature. The PMIBA gel showed little degradation in the swelling ability when subjected to 50 times of thermal cycling across the VPTT. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Preparation and Characterization of Porous Poly (N-isopropylacrylamide) /Clay Nanocomposite Hydrogels

Summary  A novel porous PNIPA/Clay nanocomposite hydrogel (NC hydrogel) was prepared by in situ free-radical polymerization using inorganic clay as a crosslinker and calcium carbonate (CaCO₃) particle as a pore-forming agent and subsequent extraction of CaCO₃ with acid. The structure and morphology of the hydrogels were characterized by means of FTIR, TEM and SEM. The temperature responsive behaviors, the deswelling behaviors and the mechanical properties of the NC hydrogels were investigated in detail. The results showed that the swelling ratios below VPTT and the deswelling rates of the NC hydrogels were significantly improved as compared with the hydrogels without introduction of CaCO₃. Moreover, the NC hydrogels thus prepared also exhibited good mechanical properties.     

Swelling behavior of poly(acrylamide)/clay nanocomposite hydrogels in acrylamide aqueous solution

The swelling behaviors of poly(acrylamide) (PAAm)/clay nanocomposite hydrogels (hereinafter abbreviated as NC gels) in acrylamide (AAm) aqueous solution have been investigated. As‐prepared PAAm/clay hydrogels (S‐M gels) were posttreated by immersing them in AAm aqueous solution. It was found that the swelling ratio of the NC gels increased greatly when the concentration of the solution is below a critical concentration (c*), whereas the gels were disintegrated in the solution when the concentration of the solution is above the c*. Some disc‐like particles were found in the AAm solution accompanying with the unusual swelling behaviors. This unusual swelling behavior is resulted from the change of network structure of the NC gels in AAm aqueous solution, which was further convinced by transmission electron microscopy and element analyses. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Adsorption of ammonium and nitrate ions by poly(N‐isopropylacrylamide) gel and poly(N‐isopropylacrylamide‐co‐chlorophyllin) gel in different states

The adsorption of ammonium and nitrate by temperature‐stimulus‐responsive poly(N‐isopropylacrylamide) (NIPA) gel and poly(N‐isopropylacrylamide‐co‐chlorophyllin) (NIPA‐CH) gel in different states was investigated. Both the NIPA gel and NIPA‐CH gel could adsorb ammonium and nitrate in a swollen state (swollen gel) and a swelling state (swelling gel), and they adsorbed ammonium more than nitrate. When the gels were shrinking (shrinking gel), they could adsorb a little ammonium from solution, but when the gels were in a shrunken state (shrunken gel), they hardly adsorbed ammonium. The adsorption of both ammonium and nitrate increased for the swelling NIPA gel in comparison with the swollen gel. The NIPA‐CH gel was the opposite in this respect. The difference in the amounts of adsorption of ammonium and nitrate by the swollen and swelling NIPA‐CH gels was more significant than that of the NIPA gels. It was suggested that ions such as ammonium and nitrate could not diffuse into the gels freely. The adsorption of ammonium and nitrate was affected not only by the phase transitions of the gels but also by the electrical charges. The experimental results for the adsorption of ammonium and nitrate during the volume changes of the gels imply that if the gels are applied to the immobilization of microorganisms, they may improve mass transfer between the immobilization matrix and bulk liquid under cyclic temperature changes and promote reactions of the immobilized microorganisms, especially the nitrification of nitrifying bacteria immobilized by the NIPA‐CH gel. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2367–2372, 2005     

Preparation and characterization of nanocomposite hydrogels based on polyacrylamide for enhanced oil recovery applications

In the present work, attempts have been made to prepare nanocomposite type of hydrogels (NC gels) by crosslinking the polyacrylamide/montmorillonite (Na‐MMT) clay aqueous solutions with chromium (III). The X‐ray diffraction patterns of the NC gels exhibited a significant increase in d₀₀₁ spacing between the clay layers, indicating the formation of intercalated as well as exfoliated type of morphology. Exfoliation of the clay layers through out the gel network was found to be predominated, which evidences the high interaction between the polyacrylamide segments and montmorillonite layers. Gelation time as well as variation of viscoelastic parameters such as storage modulus (G′) of the gel network during gelation process at 75°C was studied and followed by rheomechanical spectroscopy (RMS). The NC gels prepared with lower crosslinker concentration showed higher strength and elastic modulus compared with the similar but unfilled polyacrylamide gel. This distinct characteristic of the NC gels yields a gel network structure with high resistance towards syneresis at high temperature in the presence of the oil reservoir formation water. The effects of the composition, such as clay content, crosslinker concentration, and also water salinity upon the gelation rate, gel strength as well as rate of syneresis have been investigated. To optimize the injectivity of the intercalated polyacrylamide solution before the onset of gelation with the gel strength of the final developed gel, sodium lactate was employed as retarder. This was found to be effective to balance these two characteristics of the NC gels, which are aimed to be used for water shut‐off and as profile modifier in enhanced oil recovery (EOR) process during water flooding process. The nanocomposite gels showed much more elasticity and extensibility at low crosslinker concentration compared with the similar but unfilled gel, which makes the NC gels suitable as an in‐depth profile modifier, and also as an oil displacing agent in the heterogeneous oil reservoir in chemical EOR. Effects of the clay content on the thermal stability of the gel network have also been investigated by thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) has been performed upon the NC‐gel samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2096–2103, 2006     

Temperature‐, pH‐, and ion‐stimulus‐responsive swelling behaviors of poly(dimethylaminoethyl methacrylate) gel containing cholic acid

Poly(dimethylaminoethyl methacrylate) hydrogels containing cholic acid (PDMAEMA–CA) were synthesized by radiation crosslinking. The introduction of 10 and 20 mol% cholic acid (CA) into the poly(dimethylaminoethyl methacrylate) (PDMAEMA) hydrogel decreased the maximum swelling ratio (SR) of the gel from 40 to 6 and 5, respectively. The incorporation of CA with dimethylaminoethyl methacrylate led to a decrease in the lower critical swelling temperature of the gel from 44 to 42°C but did not exert big influence on the ion‐stimulus‐responsive properties of the gel. However, the pH sensitivity of the PDMAEMA–CA gel was quite different from that of PDMAEMA gel. The SR of PDMAEMA gel decreased at pH 2.5, whereas the SRs of the PDMAEMA–CA gels showed a convex‐upward function of pH; that is, SR of the PDMAEMA–10% CA gel first increased (pH 1.2–3.2) and then decreased (pH 3.2–11.9) with increasing pH. The pH‐stimulus‐responsive swelling behavior of the PDMAEMA–20% CA gel was similar to that of the PDMAEMA–10% CA gel except for the unique swelling behavior exhibited in the lower pH region. The unique decrease in SR in strong acidic solutions was attributed to aggregations driven by the hydrophobic interactions between CA molecules. Phase separation of the gel in strongly acidic solutions was observed; that is, the margin of the swollen gel was transparent and elastic (cellular structure), whereas the core of it was opaque (aggregated structure) as recorded by scanning electron microscopy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39998.     

Preparation and application in drug controlled delivery of pH‐sensitive P(CE‐co‐DMAEMA‐co‐MEG) hydrogel

A pH‐sensitive hydrogel [P(CE‐co‐DMAEMA‐co‐MEG)] was synthesized by the free‐radical crosslinking polymerization of N,N‐dimethylaminoethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether methacrylate(MPEG‐Mac) and methoxyl poly(ethylene glycol)‐poly(caprolactone)‐methacryloyl methchloride (PCE‐Mac). The effects of pH and monomer content on swelling property, swelling and deswelling kinetics of the hydrogels were examined and hydrogel microstructures were investigated by SEM. Sodium salicylate was chosen as a model drug and the controlled‐release properties of hydrogels were pilot studied. The results indicated that the swelling ratios of the gels in stimulated gastric fluids (SGF, pH = 1.4) were higher than those in stimulated intestinal fluids (SIF, pH = 7.4), and followed a non‐Fickian and a Fickian diffusion mechanism, respectively. In vitro release studies showed that its release rate depends on different swelling of the network as a function of the environmental pH and DMAEMA content. SEM micrographs showed homogenous pore structure of the hydrogel with open pores at pH 1.4. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40737.