Superabsorbent polymeric materials. VI. Effect of sulfobetaine structure on swelling behavior of crosslinked poly(sodium acrylate‐co‐sulfobetaines) in aqueous salt solutions

A series of xerogels based on sodium acrylate (SA), N,N‐dimethyl(acrylamidopropyl) ammonium propane sulfonate (DMAAPS) or dimethyl(methacryloyloxy ethyl) ammonium propane sulfonate (DMAPS), and N,N′‐methylene bisacrylamide (NMBA) was prepared by inverse suspension polymerization. The water absorbencies or swelling kinetic behaviors for these xerogels in water or various saline solutions were investigated. The swelling behaviors of these absorbents were related to their chemical structures, their compositions, and the nature of external salt solutions. The water absorbencies of these two copolymeric gel series in deionized water or in various salt solutions would be improved effectively by copolymerizing SA with a small amount of zwitterionic monomer (DMAAPS or DMAPS). The water absorbency of the gel containing DMAPS is larger than that of the gel containing DMAAPS when the amount of zwitterionic monomer in the copolymeric gel is <0.8 mol %, but a contrary result is observed when the zwitterionic monomer content is >0.8 mol %. The tendency of the absorbency for these gels in dilute solution is in the order Cu²⁺ > Zn²⁺ > Co²⁺ > Ni²⁺ for CuCl₂, ZnCl₂, CoCl₂, and NiCl₂ aqueous solution, respectively. The absorbency and initial absorption rate for those gels are related with gel compositions and salt concentrations. Finally, the adsorption of cupric ion by these gels is also investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1221–1232, 1999     

Superabsorbent polymeric materials VIII: Swelling behavior of crosslinked poly[sodium acrylate‐co‐trimethyl methacryloyloxyethyl ammonium iodide] in aqueous salt solutions

A series of xerogels based on sodium acrylate (SA), cationic comonomer, trimethyl methacryloyloxyethyl ammonium iodide (TMMAI), and N,N‐methylene‐bis‐acrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency and the swelling behavior for these high absorbent polymers in deionized water and various saline solutions were investigated. Results indicated that the water absorbency for the present copolymer gel increased when a small amount of TMMAI monomer was introduced into the SA gel, then decreased with increase in TMMAI content. The water absorbency was 583 g H₂O/g for a gel sample in deionized water containing 2.5 × 10⁻³ molar fraction TMMAI. But a contrary result was observed for initial absorption rate, that is, the initial absorption rates increased with an increase of TMMAI in deionized water and 0.9 wt % NaCl solution. The absorbency in the chloride salt solution decreased with an increase in the ionic strength of the salt solution. Finally, the adsorption of copper ion by these gels was also investigated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1665–1674, 2001     

Superabsorbent polymeric materials. XII. Effect of montmorillonite on water absorbency for poly(sodium acrylate) and montmorillonite nanocomposite superabsorbents

A series of novel xerogels based on sodium acrylate (NaA), montmorillonite (MMT), and N,N′‐methylene‐bisacrylamide (NMBA) were prepared by inverse suspension polymerization and water solution polymerization. The influences of pure MMT, intercalated MMT, the method of polymerization, and the content of the MMT in the copolymeric gels on the water absorbency and the initial absorption rate in deionized water and various salt solutions were investigated. Results showed that the water absorbency was increased by adding a small amount of the pure MMT into the copolymeric gels, but decreased by adding intercalated MMT into the gels. In addition, the water absorbency of the gels prepared by water solution polymerization was lower than that prepared by inverse suspension polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3422–3429, 2004     

pH‐reversible hydrogels. IV. Swelling behavior of the 2‐hydroxyethyl methacrylate‐co‐acrylic acid‐co‐sodium acrylate copolymeric hydrogels

A series of 2‐hydroxyethyl methacrylate (HEMA) and sodium acrylate (SA50) copolymeric gels were prepared from HEMA and the anionic monomer SA50 with various molar ratios. The influence of SA50 on the copolymeric gels on their swelling behavior in deionized water at different temperatures and various pH buffer solutions was investigated. Results indicated that the poly(2‐hydroxyethyl methacrylate) (PHEMA) hydrogels exhibited an overshooting phenomenon in their dynamic swelling behavior. The maximum overshooting value decreased with increasing of the temperature. The same results were also found in the HEMA/SA50 copolymeric gels with a lower SA50 content. On the contrary, the overshooting phenomenon for HEMA/SA50 copolymeric gels with a higher content of SA50 was exhibited only under higher temperature (over 35°C). These copolymer gels were used to assess drug release and drug delivery in this article. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1360–1371, 2001     

Superabsorbent polymeric materials. XIII. Effect of oxyethylene chain length on water absorbency for the sodium acrylate and poly(ethylene glycol) methyl ether acrylate (PEGMEAn) copolymeric gels

In a previous study, we prepared a series of xerogels based on sodium acrylate (NaA) and 2‐hydroxyethyl methacrylate (HEMA, OE = 1) or poly(ethylene glycol) methacrylate (PEGMA, OE = 6) with different oxyethylene (OE) units. The effect of the contents of HEMA and PEGMA in the copolymeric gel on the swelling behavior in deionized water and various saline solutions was studied. Their results showed that the water absorbencies for these two series gels were effectively improved by adding a small amount of HEMA or PEGMA. In this article, a series of novel xerogels based on NaA and hydrophilic monomer poly(ethylene glycol) methyl ether acrylate (PEGMEA_n), which was synthesized from acryloyl chloride and poly(ethylene glycol) monomethyl ether with three oxyethylene (OE = 9, 16, 45) chain lengths, were prepared by inverse suspension polymerization. The effects of OE chain length in the copolymeric gel on the water absorption behavior and initial absorption rate for the present xerogels were investigated. Results showed that adding a small amount of PEGMEA_n could effectively increase the water absorbency of the gels. In addition, the water absorbency decreased with an increase of the OE chain length in PEGMEA_n. The initial absorption rate for the present copolymeric gels increased with increasing OE chain length in PEGMEA_n and the content of PEGMEA_n in the copolymeric gels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 927–934, 2006     

Superabsorbent polymeric materials. I. Swelling behaviors of crosslinked poly(sodium acrylate-co-hydroxyethyl methacrylate) in aqueous salt solution

A series of crosslinked poly(sodium acrylate-co-hydroxyethyl methacrylate) based on sodium acrylate (SA), 2-hydroxyethyl methacrylate (HEMA), and N,N′-methylene-bis-acrylamide (NMBA) are prepared by inverse suspension polymerization. The resultant crosslinking polymers are xerogellants. This work investigates not only the absorbency or swelling behavior for these xerogellants composed of different ratios of HEMA/SA in water, but also the effects of various salts and pH values on the swelling properties. Experimental results indicate that the absorbency in deionized water decreases with an increase in the HEMA in copolymeric gel, which is related to the degree of expansion of the network and the strength of the hydrophilic group. The absorbency in the chloride salt solutions decreases with an increase in the salt concentration (swelling is 50 times for the IA group chloride salt solutions, but is less than 5 times for the IIA group salt solution), owing to the osmosis of water and ions between the polymeric gel and the external solution. A decrease in the extent of swelling occurs for divalent and trivalent chloride salt solutions. For the salt solutions of the same ionic strength, the swelling amount has the following tendency: LiCl(aq) = NaCl(aq) = KCl(aq), CaCl₂(aq) < SrCl₂(aq) < BaCl₂(aq), and Fe³⁺ > Ca²⁺ > Zn²⁺ > Cu²⁺. These orders are related to the complexing ability between metallic cations and the carboxylate group in the polymeric chains. Finally, the adsorption of ferric ion by these gels is also investigated. © 1996 John Wiley & Sons, Inc.     

Superabsorbent polymeric materials VII: Swelling behavior of crosslinked poly[sodium acrylate‐CO‐trimethyl methacrylamido‐propyl ammonium iodide] in aqueous salt solutions

A series of xerogels based on sodium acrylate (SA), cationic comonomer trimethyl methacrylamidopropyl ammonium iodide (TMMAAI), and N,N‐methylene‐bis‐acrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency and the swelling behavior for these highly absorbent polymers in deionized water and various saline solutions were investigated. Results indicated that the water absorbency increased when a small amount of TMMAAI monomer was introduced into the SA gel. The water absorbency decreased with increase in TMMAAI content, but the contrary result was observed for initial absorption rate. Moreover, with more crosslinking agent, the water absorbency was lower. Finally, the adsorption of copper ion by these gels was also investigated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1749–1759, 2000     

Superabsorbent polymeric materials IX: Effect of cationic structure on swelling behavior of crosslinked poly(sodium acrylate‐co‐cationic monomers) in aqueous salt solutions

Two series of xerogels based on sodium acrylate (SA), trimethyl methacrylamidopropyl ammonium iodide (TMMAAI), trimethyl methacryloyloxyethyl ammonium iodide (TMMAI), and N,N′‐methylene‐bis‐acrylamide (NMBA) as a crosslinker were prepared by inverse suspension polymerization. The water absorbency and swelling kinetic behavior for these xerogels in water or various saline solutions were investigated. The results showed that the swelling behaviors of these absorbents are related to their chemical structures, their compositions, and the type of external salt solutions. There would be effective improvement in the water absorbency of these two gel series by copolymerizing SA with a small amount of cationic monomer (TMMAAI or TMMAI). The initial absorption rates in deionized water were found to be faster for TM series gels than for TA series gels. The two series of superabsorbents had a tendency to absorb water in dilute nitrate aqueous solutions in the order: Fe³⁺, Ni²⁺, Ca²⁺, Cu²⁺, and Na⁺ for Fe(NO₃)₃, Ni(NO₃)₂, Ca(NO₃)₂, Cu(NO₃)₂, and NaNO₃ aqueous solution, respectively. The absorbency and initial absorption rate for these gels were related to the gel compositions and salt concentrations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1827–1837, 2001     

Superabsorbent polymeric materials III. Effect of initial total monomer concentration on the swelling behavior of crosslinked poly(sodium acrylate) in aqueous salt solution

A series of xerogels based on sodium acrylate (SA) and N,N′-methylene-bisacrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency or swelling behaviors for these hydrogels in water or various saline solutions was investigated. Experimental results indicate that the absorbency of poly(SA) in deionized water increases with decrease in the initial total monomer concentration. Results obtained from this study show that the water absorbency, respectively, exhibited a value of 992 g H₂O/g sample and 106 g H₂O/g sample in deionized water and a 0.9 wt % NaCl solution at an initial total monomer concentration of 3.03M. The absorbency in the chloride salt solutions decreases with increase in the ionic strength of the salt. For the same ionic strength of various salt solutions, the swelling amount has the following tendency: Co²⁺ > Ni²⁺ > Cu²⁺ for the higher ionic strength of 6.25 × 10⁻⁴ to 2.0 × 10⁻³M, and Co²⁺, Ni²⁺, and Cu²⁺ approximately have the same swelling amount for the lower ionic strength of < 6.25 × 10⁻⁴M. The influence of monovalent, divalent, and trivalent anions with a common cationic ion (Na⁺) on the water absorbency shows the tendency of monovalent < divalent < trivalent anions for the same ionic strength. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2371–2380, 1997     

Superabsorbent polymeric materials. XI. Effect of nonionic monomers on the swelling behavior of crosslinked poly(sodium acrylate‐co‐nonionic monomers) in aqueous salt solutions

A series of xerogels based on sodium acrylate, nonionic monomers such as 2‐hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol) methacrylate (PEGMA), and N,N′‐methylene bisacrylamide were prepared by inverse suspension polymerization. The results indicate that the water absorbencies for these two gel series were effectively improved by the addition of a small amount of nonionic monomer (HEMA or PEGMA). The initial absorption rates in deionized water were faster for the PEGMA gels than for the HEMA gels. Scanning electron microscopy showed that the spherical particle size was smaller for the PEGMA gels than for the HEMA gels. In addition, the water absorbency of the gels in various salt solutions decreased with increasing ionic strength, especially for the multivalent salt solutions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3666–3674, 2004     

Superabsorbent polymeric materials. XIV. Preparation and water absorbency of nanocomposite superabsorbents containing intercalated hydrotalcite

A series of novel xerogels, based on sodium acrylate (NaA), intercalated hydrotalcite (IHT), and N,N′‐methylene‐bisacrylamide (NMBA), were prepared by inverse suspension polymerization. The influences of the HT intercalated with acrylic acid (AA–IHT) and with 2‐acryloylamido‐2‐methyl propane sulfonic acid (AMPS–IHT), the content of the IHT in the poly(NaA) gel on the water absorbency, and the initial absorption rate in deionized water and various salt solutions were investigated. Results showed that adding a small amount of IHT could effectively increase the water absorbency of the gels, but adding excess IHT could decrease the water absorbency of the gels. In addition, the water absorbency of the gels containing AA–IHT was lower than that containing AMPS–IHT. The initial absorption rate, for the present gels, increased with increasing content of IHT in the copolymeric gels. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2417–2424, 2004     

Superabsorbent polymeric materials. IV. Swelling behavior of crosslinked poly [sodium acrylate-co-N,N-dimethyl (acrylamidopropyl) ammonium propane sulfonate] in aqueous salt solution

A series of xerogels based on sodium acrylate (SA), N,N-dimethyl(acrylamidopropyl)ammonium propane sulfonate (DMAAPS), and N,N′-methylene bisacrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency or swelling behavior for these xerogels in water or various saline solutions was investigated. Results obtained from this study revealed a water absorbency of 721 g H₂O/g sample in deionized water and 83 g H₂O/g sample in 0.9 wt % NaCl solution for a gel containing a 1.50 × 10 ⁻² molar fraction of DMAAPS. The absorbency in the chloride salt solutions decreased with an increase in the ionic strength of the salt. For the same ionic strength of various salt solutions, the swelling amount had the following tendency: Co ²⁺ > Ni ²⁺ > Cu ²⁺ for the higher ionic strength of 2.44 × 10 ⁻⁵–1.8 × 10 ⁻² M. The Co ²⁺, Ni²⁺, and Cu ²⁺ solutions induce approximately the same degree of swelling at the lower ionic strength of <2.44 × 10 ^minus;5 M. The pH effect on the water absorbency for these xerogels was also investigated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66:499–507, 1997     

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 XI: Effect of salt on the swelling properties of the (n‐isopropylacrylamide‐co‐sodium 2‐acrylamido‐2‐methylpropyl sulfonate) copolymeric hydrogels

The swelling behavior for a series of NIPAAm/NaAMPS copolymeric hydrogels with polyelectrolytic and thermosensitive properties was investigated in various saline solutions. The swelling ratios for the present copolymeric hydrogels were affected by the saline solution, which is the result of the neutralization of the cations in the external solution with the negative charges on the polymeric side chains. The adsorption of aniline by the gels increased when the temperature was higher than the gel transition temperature, and this result showed that, when the gels were in hydrophobic state, the hydrophobic organic molecules were more easily adsorbed onto the gels. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1675–1684, 2001     

Thermoreversible hydrogel. V. Synthesis and swelling behavior of the N-isopropylacrylamide-co-trimethyl methacryloyloxyethyl ammonium iodide copolymeric hydrogels

A series of N-isopropylacrylamide/trimethyl methacryloyloxyethyl ammonium iodide (NIPAAm/TMMAI) copolymeric gels are prepared from the various molar ratios of NIPAAm, cationic monomer TMMAI, and N,N′-methylene bisacrylamide (NMBA) in this article. The influences of the amount of the cationic monomer in the copolymeric gels on the swelling behavior in water, various saline solutions, and various temperatures are investigated. Results show that the swelling ratios of copolymeric gels are significantly larger than those of pure homopolymer NIPAAm gel, and the more the TMMAI content, the higher the gel transition temperature. In the saline solution, results show that the swelling ratio of pure NIPAAm gel has not significantly changed with an increase of the salt concentration until the salt concentration is larger than 0.1M. The swelling ratios for the copolymeric gels NIPAAm/TMMAI decrease with increasing salt concentration. In various saline solutions, results show that the anionic effects are greater than cationic effects in the presence of common anion, different cations and common cation, and different anions for these hydrogels. Finally, we also tested the reversibility of the NIPAAm/TMMAI copolymeric gels. The deswelling and reswelling kinetics are dependent on the temperature, which is below or above the gel transition temperature. The gel with little TMMAI content has a good reversibility. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1793–1803, 1998     

Synthesis of poly(sodium acrylate‐co‐sodium 1‐(acryloyloxy) propan‐2‐yl phosphate) and comparative study on its swelling properties with poly(sodium acrylate) and poly(sodium acrylate‐co‐2‐hydroxypropyl acrylate)

A new superabsorbent copolymer, poly(sodium acrylate‐co‐sodium 1‐(acryloyloxy) propan‐2‐yl phosphate) [P(SA‐co‐SAPP)], was synthesized by a novel prepared monomer, 1‐(acryloyloxy) propan‐2‐yl phosphoryl dichloride. The swelling properties of the superabsorbent were investigated by comparison with poly(sodium acrylate) (PSA) and the copolymer of poly(sodium acrylate‐co‐2‐hydroxypropyl acrylate) [P(SA‐co‐HPA)]. The results showed that (1) the superabsorbent containing sodium 1‐(acryloyloxy) propan‐2‐yl phosphate had higher water absorbency at general testing conditions; (2) the swelling properties of P(SA‐co‐SAPP) and PSA were obviously influenced by pH of solutions, which were different from that of P(SA‐co‐HPA); (3) the swelling process and the saturated water absorbency of all superabsorbents were remarkably affected by cations, especially multivalent ones, while barely affected by anions. POLYM. ENG. SCI., 47:728–737, 2007. © 2007 Society of Plastics Engineers.     

Superabsorbent polymeric materials X: Effect of degree of neutralization on swelling behavior of crosslinked poly(sodium acrylate) in aqueous salt solutions

A series of xerogels based on different degrees of neutralizations (DN) of acrylic acid (AA) and N,N-methylene-bis-acrylamide (NMBA) were prepared by inverse suspension polymerization. The influence of the DN values of AA on water absorbency and swelling behavior for these highly absorbent polymers in deionized water and various saline solutions were investigated. Results indicate that the equilibrium-water absorbency (Q_eq) increases with an increase in the DN of AA until the DN value reaches 95% and then decreases at 100% of the DN value. However, the initial absorption rate for these gels decreases with an increase in the DN value of AA in both deionized water and 0.9 wt% NaCl solution. The adsorption of copper ions by these gels was also investigated.     

Thermoreversible hydrogels VI: Swelling behavior of the (N-isopropylacrylamide-co-diethyl methyl methacryloyloxyethyl ammonium iodide) copolymeric hydrogels in aqueous salt solutions

A series of N-isopropylacrylamide/diethyl methyl methacryloyloxyethyl ammonium iodide (NIPAAm/DEMMAI) copolymeric gels were prepared from blending NIPAAm, cationic monomer DEMMAI, and N,N′-methylene bisacrylamide (NMBA) in various molar ratios in this article. The effects of the amount of the cationic monomer in the copolymeric gels on the swelling behaviors in water and various saline solutions at various temperatures were investigated. Results showed that the swelling ratios of copolymeric gels were significantly larger than those of pure NIPAAm gel, and that the more the DEMMAI content, the higher the gel transition temperature. In the saline solution, results showed that the swelling ratio for pure NIPAAm gel had not changed significantly with an increase of the salt concentration until the salt concentration was larger than 0.1 M. The swelling ratios for the copolymeric gels NIPAAm/DEMMAI were decreased with increasing salt concentration. In various saline solutions, results showed that the anionic effects were greater than cationic effects in the presence of common anion with different cations and common cation with different anions for these hydrogels. Finally, we also tested the reversibility of the NIPAAm/DEMMAI copolymeric gels. The deswelling and reswelling kinetics were dependent on the temperature which was below or above the gel transition temperature. The gel with a small DEMMAI content has a good reversibility.     

Thermoreversible hydrogels XIII: Synthesis and swelling behaviors of [N-isopropylacrylamide-co-sodium 2-acrylamido-2-methylpropyl sulfonate-co-N,N-dimethyl(acrylamido propyl) ammonium propane sulfonate] copolymeric hydrogels

A series of copolymeric hydrogels were prepared from various molar ratios of N-isopropylacrylamide (NIPAAm), sodium-2-acrylamido-2-methylpropyl sulfonate (NaAMPS) and N,N′-dimethyl(acrylamido propyl) ammonium propane sulfonate (DMAAPS). The swelling behaviors of these copolymeric hydrogels were investigated in various saline solutions. The result showed that the phase transition temperatures of these gels changed insignificantly, and the thermosensitivity, in contrast, diminished. In addition, the copolymer gels exhibited polyelectrolytic behavior under lower salt concentration (10⁻⁵∼10⁻¹ M), exhibited a nonionic gel (like NIPAAm) behavior at the salt concentration from 0.1 to 0.4 M, and showed an antipolyelectrolytic behavior (polyzwitterionic effect) at a salt concentration over 0.4 M. Finally, the presented coplymeric gels are investigated for use in drug release application.     

Poly(2-hydroxyethyl methacrylate-co-sulfobetaine) hydrogels. II. Synthesis and swelling behaviors of the [2-hydroxyethyl methacrylate-co-3-dimethyl(methacryloyloxyethyl)ammonium propane sulfonate] hydrogels

A series of the 2-hydroxyethyl methacrylate/3-dimethyl-(methacryloyloxyethyl)ammonium propane sulfonate (HEMA/DMAPS) copolymeric gels was prepared from various molar ratios of HEMA and the zwitterionic monomer DMAPS. The influence of the amount of the zwitterionic monomer in the copolymeric gels on the swelling behaviors in water, various saline solutions, and temperature was investigated. The results indicate that the PHEMA hydrogel (D0) and lower DMAPS content of the HEMA/DMAPS copolymeric gel (D1) exhibit overshooting phenomena in the dynamic swelling behavior. The maximum overshooting value decreases with increase in temperature. In the equilibrium swelling ratio, the PHEMA hydrogel exhibits a minimum swelling ratio at 55°C. Then, the minimum swelling ratio diminishes gradually with increasing of the DMAPS content in the HEMA/DMAPS copolymeric gels. In the saline solution, the swelling ratios of HEMA/DMAPS copolymeric gels increase rapidly with increasing of concentration of the salt with a smaller ratio of the charge/radius. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2021–2034, 1998