Superabsorbent hydrogels from poly(aspartic acid) with salt-, temperature- and pH-responsiveness properties

Polyaspartic acid (PAsp) resin was synthesized by polysuccinimide (PSI), through chemical cross-linking using the cross-linking agent (diamine). The effects of reaction variables, such as PSI concentration and terminal pH on the water absorbent capacity have been studied. These phenomena were discussed according to structural parameters, which were confirmed by SEM. Water absorbencies were compared for the hydrogels at terminal pH 8 and 10. The water absorbent capacity enhanced with increasing terminal pH and decreasing PSI concentration. The swelling/deswelling kinetics of the super-absorbent hydrogels was investigated as well. It is found that the hydrogels showed ampholytic and reversible pH-responsiveness properties. The variational water absorbencies were attributed to swelling theory based on the hydrogel physical and chemical structure. The swelling was also extremely sensitive to the temperature, ionic strength and cationic kind. The reversible pH-responsiveness, salt- and temperature-sensitivity of the hydrogels make this intelligentized polymer had wider applications.     

Preparation of superabsorbent polymers by crosslinking acrylic acid and acrylamide copolymers

High water-absorbent copolymers comprising acrylic acid (AA) and acrylamide (AM) were prepared in the presence of a crosslinking agent, monofunctional aldehyde, by a solution polymerization technique using a redox initiation system. Such copolymers have very high water absorbency and absorbing kinetics to the distilled water. The copolymer formed which absorbed about 900 g water/g dry copolymer was used to study the influence of sodium chloride on the absorption capacity at 24°C. The swelling of this copolymer was studied in alcohol/water mixtures of increasing alcohol content at 294, 304, and 314 K. The main transition for ethanol/water and methanol/water mixtures is a rapid decrease of the retention capacity of the copolymer at 50–60 vol % ethanol and 55–65 vol % methanol, respectively. Swelling in distilled water at different temperatures (T) and the effect of solvent composition were also studied. Among the variables examined were initiator concentration, polymerization temperature, and amount of AM in the copolymer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1345–1353, 1997     

Controlling degradation and physical properties of chemical sand fixing agent‐poly(aspartic acid) by crosslinking density and composites

Poly(aspartic acid) (PASP) hydrogel crosslinked with 1,6‐ hexamethylene diamine was applied as sand fixing agent. The effect of crosslinking density of sand fixing agent on sand fixing property was studied. The relations between the degradation time and crosslinking density, sand fixing property, molecular weight, and mass loss were measured. It was found that the sand fixing property relied on the PASP crosslinking density and degradation time. The crust attained the maximal mechanical strength when the PASP crosslinking agent concentration was 0.0325 mol/L and the PASP hydrogel mass loss was 97.9% after 18 days. The composites added into PASP could increase mechanical property and prolong the degradation time when compared with the control. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of hydroxyl poly(aspartic acid)/organic bentonite superabsorbent composite

A novel hydroxyl poly(aspartic acid)/organic bentonite (HPAsp/OB) superabsorbent composite has been synthesized by the non-water suspension method using polysuccinimide and OB as raw materials,ethanolamine as modifiers and hexamethylenediamine as cross-linking agent. Organic bentonite used in this work is cetyl trimethyl ammonium bromide intercalated bentonite with the interlayer distance of 2.12 nm. The effects of the OB and ethanolamine contents on swelling ratios of the superabsorbent composites have been investigated. The largest swelling ratios in distilled water and in 0.9 wt% NaCl were 491 and 82 g/g, respectively, both at OB and ethanolamine contents of 3 wt% and 15 mol%, correspondingly. The salt resistance of the superabsorbent composites was investigated in KCl (aq.), CaCl₂ (aq.) and FeCl₃ (aq.). The temperature- and pH-sensitivities of the superabsorbent composites has also been studied. The structures and morphologies of the superabsorbent composites have been characterized by Fourier transform infrared spectroscopy, X-ray diffraction, high resolution-TEM and optical microscopy techniques. The results indicated that introduction of OB and ethanolamine increased the swelling ratio of the superabsorbent composites. Compared with poly(aspartic acid), hydroxyl poly(aspartic acid) and poly(aspartic acid)/organic bentonite, the swelling properties of HPAsp/OB superabsorbent composites are obviously improved under the same experimental conditions.     

Optimization of the preparation of a poly(aspartic acid) superabsorbent resin with response surface methodology

A poly(aspartic acid) superabsorbent resin was synthesized with polysuccinimide through chemical crosslinking with a crosslinking agent (diamine). The optimization of its preparation was investigated with response surface methodology. According to the Plackett–Burman design, the crosslinking temperature, drying temperature, and dissolving time of polysuccinimide had significant influences on the swelling ratio of the poly(aspartic acid) resin, which was the criterion for describing the water absorption capacity. Central composite design and response surface analysis were employed subsequently to further optimize the three aforementioned factors. A maximum swelling ratio greater than 500 g/g was attained; this was more than a 60% increase in comparison with previous results. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2616–2622, 2006     

Rapid swelling and deswelling of semi‐interpenetrating network poly(acrylic acid)/poly(aspartic acid) hydrogels prepared by freezing polymerization

Hydrogels with semi‐interpenetrating networks composed of poly(acrylic acid) (PAAc) and poly(aspartic acid) (PASP) have great potential for pharmaceutical and biomedical applications. In this study, we aimed to synthesize semi‐interpenetrating PAAc/PASP hydrogels with improved swelling–deswelling properties via two‐step polymerization, in which the first step of polymerization was performed at 37 °C for 15 min and the second step, the freezing polymerization, was performed at ?20 °C for 24 h. The synthesized hydrogels were characterized with field emission scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The swelling and deswelling behaviors of the hydrogels in response to the ionic strength of the buffer solution were investigated. The Schott's swelling kinetic model was used to elucidate the swelling behavior of the hydrogels. The swelling and deswelling rates of the hydrogels prepared via freezing polymerization were faster than those of the hydrogels prepared via conventional polymerization. This was attributed to the large mean pore size of the freeze‐polymerized hydrogels. The PAAc/PASP hydrogels that underwent freezing polymerization had better swelling–deswelling characteristics than the PAAc hydrogels. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43515.     

Preparation of a kaolinite–poly(acrylic acid acrylamide) water superabsorbent by photopolymerization

A novel kaolinite–poly(acrylic acid acrylamide) water superabsorbent with a water absorbency and salt solution absorbency of 433 and 108 g/g, respectively, was successfully synthesized by the photopolymerization of acrylic acid with acrylamide in the presence of kaolinite powder under 30 min of ultraviolet irradiation at room temperature. The results showed a synergetic effect of the mixed photoinitiators (Michler's ketone and benzophenone) on the water absorbency, and the incorporation of less than 10 wt % kaolinite into the water superabsorbent slightly improved the water absorbency and salt solution absorbency and obviously upgraded the water retention, as demonstrated by retention testing as well as thermogravimetric analysis and differential scanning calorimetry. Fourier transform infrared spectroscopy verified the structure of the kaolinite composite superabsorbent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2875–2881, 2006     

Preparation and characterization of microporous sodium poly(aspartic acid) nanofibrous hydrogel

A novel biodegradable sodium poly(aspartic acid) (PASP) hydrogel with microporous structure was manufactured using electrospun polysuccinimide (PSI) nanofibers. PSI is the intermediate of sodium PASP and could be electospun into nanofibers easily. Firstly, PSI nanofibers were prepared from PSI/N, N-dimethylformamide solution. Then the PSI nanofibrous mats were crosslinked and hydrolyzed to obtain biodegradable microporous sodium PASP nanofibrous hydrogels. The chemical structures, morphologies and pore sizes of PSI nanofibrous mats and microporous sodium PASP nanofibrous hydrogels were investigated. Moreover, the properties of PSI electrospinning solutions, and the swelling ratio and biodegradability of sodium PASP hydrogels were also examined. The results showed that the swelling ratio of microporous sodium PASP nanofibrous hydrogels achieved to 21.0–24.3 g/g and were obviously higher than that of the sodium PASP casting film, reporting a swelling ratio of only 4.6 g/g. When the microporous sodium PASP nanofibrous hydrogel was immersed in water, it exhibited quick absorption and morphological robustness. The microporous sodium PASP nanofibrous hydrogel showed 83 wt% weight loss after 7 days of trypsin catalyzed biodegradation, and the SEM analysis demonstrated the significant morphology change of the microporous sodium PASP nanofibrous hydrogel during the biodegradation.     

Evaluation of two chemical crosslinking methods of poly(vinyl alcohol) hydrogels for injectable nucleus pulposus replacement

Low back pain caused by intervertebral disc degeneration is one of the most common spinal disorders among patients seeking medical treatment. The most common surgical treatments are spinal fusion and total disc arthroplasty, both of which are very invasive surgical procedures. Nucleus pulposus replacement is an earlier stage intervention for disc degeneration. One of the material classes being studied for this application is hydrogels: a three‐dimensional hydrated network of polymer(s), which mimics the mechanical and physiological properties of the nucleus. Poly(vinyl alcohol) (PVA), poly(vinyl pyrrolidone) (PVP), and poly(ethylene glycol) (PEG) hydrogels have previously been shown to be great candidate materials for injectable nucleus pulposus replacement, but have experienced issues with swelling and mass retention. The addition of chemical crosslinking to the PVA/PVP/PEG hydrogel system will allow tailoring of the swelling, mechanical, injectability, and mass loss properties of the hydrogel network. Two chemical crosslinking methods were evaluated for the PVA/PVP/PEG hydrogel system by characterizing the hydrogels with compression, swelling, and spectroscopy experiments. The results of these experiments led to the selection of the difunctional crosslinking strategy using PEG functionalized with terminal epoxide group (PEG diglycidyl ether) as the preferred crosslinking method. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40843.     

Gelation and crosslinking characteristics of photopolymerized poly(ethylene glycol) hydrogels

The gelation and crosslinking features of poly(ethylene glycol) (PEG) hydrogels were scrutinized through the UV polymerization processes of poly(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) mixtures. The real‐time evolutions of the elastic moduli of the prepolymerized mixtures with different crosslinking ratios of PEGMA and PEGDMA and the photoinitiator concentrations were measured during photopolymerization. The rheological properties were compared with other properties of the PEG hydrogels, including the relative changes in the C?C amounts in the mixtures before and after UV irradiation, water swelling ratio, gel fraction, mesh size, and mechanical hardness. As the portion of PEGDMA as a crosslinker increased, the final elastic modulus and gel fraction increased, whereas the swelling ratio and scratch penetration depth at the hydrogel film surface decreased because of the formation of compact networks inside the hydrogels. These results indicate that there was a good correlation between the rheological analysis for predicting the crosslinking transition during photopolymerization and the macroscopic properties of the crosslinked hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41939.     

Preparation and swelling behavior of macroporous poly(acrylamide‐co‐sodium methacrylate) superabsorbent hydrogels

Macroporous superabsorbent hydrogels (SAHs) composed of acrylamide (AAm) and sodium methacrylate (NMA) were prepared by aqueous solution polymerization in the presence of a glucose solution. Their swelling capacity was investigated as a function of the concentrations of the glucose solution, sodium methacrylate, crosslinker, initiator, and activator. The porosity of the poly(acrylamide‐co‐sodium methacrylate) superabsorbent hydrogels was confirmed using scanning electron microscopy. The SAHs were characterized by IR spectroscopy. To estimate the effect on the swelling behavior, three types of crosslinkers were employed: N,N′‐methylenebisacrylamide, 1,4‐butanediol diacrylate, and diallyl phthalate. Network structural parameters such as initial swelling rate, swelling rate constant, and maximum equilibrium swelling were evaluated by water absorption measurement. The equilibrium water content (EWC%) of the AAm–NMA macroporous SAHs was found to be in the range of 93.31–99.68, indicating that these SAHs may have applications as biomaterials in the medicinal, pharmaceutical, and veterinary fields. Most of the SAHs prepared in this investigation followed non‐Fickian‐type diffusion, and few followed a case II– or super–case II‐type diffusion. The diffusion coefficients of these macroporous SAHs were investigated. Further, the swelling behavior of these SAHs also was investigated at different pHs and in different salt solutions and simulated biological fluids. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3202–3214, 2006     

High‐temperature resistant superabsorbent based on poly(acrylic acid) with triallylammonium chloride as crosslinking agent

A novel high‐temperature resistant superabsorbent was prepared by solution polymerization of partially neutralized acrylic acid (AA), using triallylammonium chloride as crosslinker, potassium persulfate as initiator. The factors that influence the water‐absorbing capacity at 25 and 200°C such as mass concentration of monomer, mass ratio of crosslinker to AA, mass ratio of initiator to AA, and neutralization degree were investigated. The structure of the superabsorbent was characterized by Fourier transform infrared, thermogravimetric analysis, and scanning electron microscopy. The optimum conditions were obtained and the swelling ratios in distilled water and 1 wt % of NaCl solution could reach 841 and 74 g/g at 300°C, respectively. The superabsorbent also showed high swelling rate and good salt resistance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41243.     

A novel superabsorbent from raw corn straw and poly(acrylic acid)

A superabsorbent (CS/PAA SAR) for agriculture based on raw corn straw was prepared by free radical polymerization of acrylic acid (AA) in the presence of corn straw (CS) powder, which was used as received without any treatments. The water absorbency (WA) of SAR was investigated. The results show that SAR possesses a maximum WA of 663 g/g in distilled water and 61 g/g in 0.9 wt% NaCl solution. The structure of SAR was studied by Fourier transforms infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, and differential scanning calorimeter, respectively. And the results indicate that the CS/PAA SAR possesses an interconnecting polymer network and sea‐island type phase separated structure, and the crystallinity decreases compared with the native cellulose because of the decreased content of CS. POLYM. COMPOS., 38:1353–1362, 2017. © 2015 Society of Plastics Engineers     

Photoinitiated synthesis of poly(poly(ethylene glycol) methacrylate-co-diethyl amino ethyl methacrylate) superabsorbent hydrogels for dye adsorption

Random copolymers of poly(ethylene glycol) methacrylate (PEGM), and diethyl amino ethyl methacrylate (DEAEM) were synthesized at low, and high conversions by photoinitiation. Crosslinked poly(PEGM-co-DEAEM) samples were obtained, and characterized by FTIR, SEM, DSC, TGA, and elemental analyses. Swelling behavior of the copolymers revealed that the copolymers acted as superabsorbent hydrogels. The monomer reactivity ratios were calculated using Fineman Ross, Extended Kelen Tüdøs , and Mayo Lewis methods that gave r₁(PEGM) = 0.90, r₂(DEAEM) = 0.14 at low conversions. At high conversions r₁ and r₂ values were calculated as 1.01 and 0.40, respectively. Adsorption isotherms of methyl orange (MO) onto hydrogels were studied using Langmuir, Freundlich, and Temkin models. The experimental data fitted well with the Langmuir equation. The maximum adsorption capacity for MO was 212.7 mg g⁻¹ at pH = 3. The adsorption data gave best fit with the pseudo-second order kinetic model. Thermodynamic evaluation showed spontaneous nature for MO adsorption onto poly(PEGM-co-DEAEM) hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47707.     

Preparation and characterization of poly(acrylic acid)/pillared clay superabsorbent composite

Pillared clay-based superabsorbents (PILC-SA) were synthesized by using Al pillared-montmorillonite K10 and KSF via graft copolymerization reaction of acrylic acid (AA). Swelling behavior of pillared clay-based superabsorbent films in distilled water and at different pH values were investigated at room temperature. It was also obtained that Al-KSF and Al-K10 based superabsorbents were pH dependent and showed a reversible swelling behavior. Water absorbency of Al-KSF based superabsorbent was higher than that of Al-K10 based one. SEM, FTIR, and XRD analysis were conducted for further characterization of the PILC-SA. FTIR analyses lead to ester formation between PILC and SA. XRD revealed the basal spacing of the pillared clays before and after in situ incorporation indicating that the morphology of the superabsorbent was exfoliated and the layers of clay dispersed on the composite.     

Correlation between crosslinking efficiency and spatial inhomogeneity in poly(acrylamide) hydrogels

Summary Elasticity and light scattering measurements were carried out on poly(acrylamide) (PAAm) hydrogels prepared from acrylamide (AAm) and N,N’-methylenebisacrylamide (BAAm) monomers under various reaction conditions. Elasticity tests showed that the crosslinking efficiency of BAAm ε_xl, that is the fraction of BAAm forming effective crosslinks decreases as the initial monomer concentration C_o is decreased. At C_o=3%, ε_xl was found to be 10^-2–10^-3, indicating that 99 to 99.9% of BAAm used in the hydrogel preparation are wasted in elastically ineffective links. Debye-Bueche analysis of the light scattering data showed that, irrespective of the gel synthesis conditions, the correlation length ξ, that is, the extension of inhomogeneities in the hydrogels is 10¹ nm. The extent of frozen concentration fluctuations in the hydrogels represented by 〈η²〉 decreases with increasing crosslinking efficiency of BAAm. The combination of the light scattering and the elasticity data of gels shows a direct correlation between the fraction of wasted crosslinker molecules during gelation and the spatial gel inhomogeneity.     

pH sensitivity and swelling behavior of partially hydrolyzed formaldehyde-crosslinked poly(acrylamide) superabsorbent hydrogels

Poly(acrylamide) superabsorbent hydrogel was synthesized through crosslinking method. Formaldehyde was used as a crosslinking agent. To achieve a hydrogel with high swelling capacity, the resulted hydrogels were saponified using NaOH solution at high temperature. During saponification, ammonia gas is produced from hydrolysis reaction of amide groups. The arising of ammonia produces porous structure in hydrogels, which is confirmed using scanning electron microscopy. The conversion of amide groups to carboxylate groups was identified by FTIR spectroscopy. The reaction variables in both crosslinking and hydrolysis reactions that affect the swelling of hydrogels were optimized. The swelling of the hydrogels in various salt solutions with various valencies and radii was studied. Also, the absorbency under load was measured. The hydrogels exhibited pH-sensitivity characteristics. A sharp swelling change was observed in lieu of pH variations in a wide range (1–13). The swelling variations were explained according to the swelling theory based on the hydrogel chemical structure. The pH-reversibility and on–off switching behavior makes the intelligent hydrogels as good candidates for considering as potential drug carries. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and physical properties of N‐defunctionalized derivatives of poly(aspartic acid)

A number of N‐substituted poly(aspartic acid)s was prepared under mild conditions using the silylation–alkylation technique. Their physical properties were studied. Free swelling capacity (FSC) tests were performed for polymers obtained by crosslinking the parent poly(aspartic acid) as well as its defunctionalized derivatives. The hypothesis that H‐bonding is critical in superabsorbency was demonstrated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 85–90, 2001     

Preparation of high-strength poly(vinyl alcohol) fibers by crosslinking wet spinning

High-strength poly(vinyl alcohol) (PVA) fiber was obtained by the crosslinking wet-spinning technique, which is an improved technique of the conventional non-crosslinked type wet-spinning of PVA. High tensile strength as well as high Young's modulus was achieved by introduction of the borate ion-aided crosslinks during the coagulation process. The drawability of the as-spun fiber greatly depends on the fiber thickness. The thinner the fiber, the higher the drawability. Since thinner fiber is subject to a very high shear rate on extrusion, the crosslinks introduced are believed to maintain topological memory of the oriented chains, which have a low density of entanglements. This allows drawing the fiber to a higher draw ratio. The strength and Young's modulus of the resultant highly drawn PVA fiber were achieved to be 22 g/d (2.3 GPa) and 430 g/d (50 GPa), respectively. The mechanism of the spinning was discussed and the spinning condition was carefully examined in order to optimize the final mechanical properties of the PVA fibers.     

表面强化交联聚(N-异丙基丙烯酰胺) 水凝胶的温敏和浓缩分离性能

为了提高聚(N-异丙基丙烯酰胺)(PNIPA)凝胶粒子的浓缩分离效果,以过硫酸铵/N,N,N,N,-四甲基乙二胺为引发体系,N,N′-亚甲基双丙烯酰胺(BIS)和二乙烯苯(DVB)为复合交联剂,通过反相悬浮聚合合成了表面强化交联的PNIPA凝胶粒子.考察了凝胶颗粒形态、温敏特性及其浓缩分离聚乙二醇/水性能.发现得到的凝胶为紧密珠状粒子,低临界溶解温度为32℃;随着溶质聚乙二醇相对分子质量增大或浓度减小,凝胶对聚乙二醇/水的分离效率提高;增加合成PNIPA凝胶时的BIS用量,可提高凝胶对聚乙二醇/水的分离效率,但溶胀率显著下降;增加DVB用量,分离效率大幅提高,而凝胶溶胀率基本不变.