Synthesis and water absorbency of crosslinked superabsorbent polymers

A series of novel copolymer superabsorbents based on monomer acrylamide (AM), potassium methacrylate (KMA), and 2‐hydroxyethyl methacrylate (HEMA) were prepared by copolymerization using ammonium persulfate (APS) as an initiator and N,N‐methylenebisacrylamide (MBA) as a crosslinking agent. The synthetic variables (the monomer concentration, crosslinker concentration, and initiator concentration) were also studied. The experimental results of superabsorbent polymers (SAPs) show a better absorbency in both water and NaCl solutions. The copolymers were characterized by IR spectroscopy. The water retention in the soil was enhanced using the above superabsorbents. The use of SAPs for the growth of groundnut plants was also investigated. SAPs can be considered for water‐managing materials for agriculture and horticulture purposes in desert and drought‐prone areas. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1795–1801, 2002     

Photo,thermal, and ultrasonic degradation of EGDMA-crosslinked poly(acrylic acid-co-sodium acrylate-co-acrylamide) superabsorbents

Superabsorbent polymers (SAPs) based on acrylic acid (AA), sodium acrylate (SA), and acrylamide (AM) were synthesized by inverse suspension polymerization using ethylene glycol dimethacrylate as the crosslinking agent. The equilibrium swelling capacities and the rates of swelling of SAPs varied with the AM content and followed first-order kinetics. The photodegradation of SAPs in their equilibrium swollen state was carried out by monitoring their swelling capacity and the residual weight fraction. The SAPs degraded in two stages, wherein the swelling capacity increased to a maximum and then subsequently decreased. Thermogravimetric analysis of the SAPs indicated that the copolymeric superabsorbents had intermediate thermal stability between the homopolymeric superabsorbents. The activation energies of SAPs with 0, 20, and 100 mol % AM content were determined by Kissinger method and were found to be 299, 248, and 147 kJ mol⁻¹, respectively. The ultrasonic degradation of the superabsorbents was carried out in their equilibrium swollen state, and the change in the viscosity with ultrasonication time was used to quantify the degradation. The ultrasonic degradation of AA/SA superabsorbent was also investigated at various ultrasound intensities. The degradation rate coefficients were found to increase with the intensity of ultrasound. The ultrasonic degradation of AA/SA/AM (20% AM) was also carried out, and degradation rate was found to be more than that of the AA/SA superabsorbent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of AA‐based superabsorbent interpenetrated with sodium PVA sulfate

An interpenetrating network of acrylic acid (AA)‐based superabsorbents and sodium PVA sulfate (SPS) were prepared by copolymerizing AA and N,N′‐methylene bisacrylamide as a crosslinking monomer in a solution of SPS with KPS, a radical initiator. The SPS was prepared through the sulfation of the hydroxyl groups of PVA with DMF‐SO₃ complex in DMSO. The AA‐based superabsorbent interpenetrated with SPS (SA‐IP‐SPS) showed superior properties such as higher water and saline absorbency, absorbency under load (AUL), and water retention value (WRV) compared with AA‐based superabsorbent due to the interpenetrated SPS. The maximum water and saline absorbency of SA‐IP‐SPS was 1753 and 125.6 g/g, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2525–2532, 2000     

Synthesis of novel superabsorbing copolymers for agricultural and horticultural applications

A series of novel superabsorbent copolymers (SAPs) based on monomers acrylamide, calcium acrylate and sodium acrylate have been prepared using ammonium persulfate as initiator and N,N‐methylene‐bis‐acrylamide (MBA) as crosslinking agent; the monomer concentration, MBA concentration and initiator concentration were varied. The experimental results show that the SAPs have good absorbency both in water and NaCl solutions. The copolymers were characterized by IR spectroscopy. Water retention in soil is enhanced by use of these superabsorbents. The effect of SAPs on the growth of bean plants is reported. SAPs may be of use as water management materials for agricultural and horticultural purposes in desert and drought‐prone areas. © 2001 Society of Chemical Industry     

Synthesis of superabsorbent copolymers as water manageable materials

Strongly water‐absorbing polymers based on the monomers acrylamide, potassium acrylate and magnesium methacrylate were prepared by copolymerization using ammonium persulfate as initiator and N,N‐methylene‐bisacrylamide (MBA) as crosslinking agent. The copolymers are synthesized by varying monomer, crosslinker and initiator concentrations. The experimental results shows that superabsorbents (SAPs) have good absorbency both in water and NaCl solutions. The copolymers are characterized by IR spectroscopy. Water retention in soil is enhanced by use of these superabsorbents. The SAPs use for the growth of sunflower plants is also investigated. The water retention capacity of the SAPs was carried out at 60 °C and 100 °C. Copyright © 2003 Society of Chemical Industry     

Saline solution absorbency and structure study of poly (AA-AM) water superabsorbent by inverse microemulsion polymerization

A series of novel copolymer superabsorbents based on acrylamide (AM), acrylic acid(AA) were prepared by inverse microemulsion copolymerization using ammonium persulfate (APS) as the initiator and N,N-methylenebisacrylamide (MBA) as the crosslinking agent and OP-10 and SDS as complex surfactants. The synthetic variables (amount of crosslinking agent and initiator, water/oil ratio, monomer/surfactant ratio and AA/ Am ratio) and their effects on the absorbencies of the synthesized superabsorbents were investigated. The experimental results of superabsorbent polymers (SAPs) showed the maximum saline solution absorbency of 130 g/g within 75 min, and the saline solution absorbency of 111 g/g within 30 min. FTIR indicated the structure of the acrylic acid and acrylamide copolymer. SEM indicated that the particles prepared with higher crosslinker content (0.03%) showed smaller pore sizes and less porous structures compared with those with less crosslinker content (0.01%) and the number of the micropores largely decreased with the water/oil ratio increasing from 8% to 14%.     

羽毛蛋白接枝聚丙烯酸-丙烯酰胺树脂的合成与吸水性能

以改性羽毛蛋白(MFP)、丙烯酸（AA）和丙烯酰胺(AM)为主要原料,N,N′-亚甲基双丙烯酰胺为交联剂,硫酸钾-亚硫酸氢钠为引发剂,采用溶液聚合法制备了羽毛蛋白接枝聚丙烯酸-丙烯酰胺高吸水树脂［P(MFP-g-AA/AM)］,并对其吸水性能及其影响因素进行了考察。结果表明,P(MFP-g-AA/AM)制备的最适宜工艺条件为W_AA∶W_AM=70∶30,丙烯酸的中和度为90％,W_MFP∶W_AA+AM=10%,W_initiator∶W_AA+AM=0.8%,W_crosslinker∶W_AA+AM=0.10%,反应温度为60℃,反应时间为2 h。在此条件下合成的P(MFP-g-AA/AM)树脂在去离子水中的饱和吸水倍率为578.0 g•g^-1,吸盐水（0.9％NaCl）倍率为78.6 g•g^-1,吸人工尿液倍率为75.1 g•g^-1,均高于羽毛蛋白接枝丙烯酸树脂。     

Synthesis and Swelling Behavior of Superabsorbents Cross-Linked with N-Maleyl Chitosan

A kind of superabsorbent based on the monomers maleic anhydride (MA) and acrylic acid (AA) was prepared by solution polymerization using ammonium peroxodisulfate (AP) and sodium bisulfite (NaHSO₃) as initiator, and N-maleyl chitosan (N-MACH) as cross-linker. Effects of process parameters such as the amount of cross-linker, mass ratio of MA to AA, and neutralization degree of AA on the water absorbency of superabsorbents are discussed. The results indicated the water absorbency of superabsorbents increased and then decreased with the increase of MA content, the amount of the N-MACH cross-linker, and the neutralization degree of AA. Under the optimal conditions, the water absorbency of superabsorbents could reach l560.42 g/g and 83.7 g/g in distilled water and in 0.9% NaCl solution, respectively. In addition, to enhance the water absorbency of superabsorbents in 0.9% NaCl solution, polyvinyl alcohol (PVA) was introduced as interpenetrating polymer in the network and 2-acrylamido-2-methyl propane sulfonic acid (AMPS) was introduced as comonomer. It was proved that PVA and AMPS could effectively improve the water absorbency of superabsorbents both in distilled water and 0.9% NaCl solution.     

Preparation and characterization of photoreactive copolymers containing curable pendants for positive photoresist

tert‐Butyl methacrylate (TBMA) was copolymerized with various comonomers that were selected from methyl methacrylate (MMA), n‐butyl acrylate (NBA), acrylic acid (AA), and 2‐hydroxyethyl methacrylate (HEMA). From film physical properties, poly(TBMA‐co‐HEMA) and poly(TBMA‐co‐AA‐co‐NBA), were selected as resin binders. To introduce unsaturated double bonds onto the side chain of copolymers, they were further functionalized with acryloyl chloride and glycidyl methacrylate. Copolymers synthesized in this investigation were all identified by using FTIR and NMR. The thermal decomposition temperature of functionalized poly(TBMA‐co‐HEMA) showed obvious difference before and after crosslinking. Adding a small amount of EGDMA as the crosslinking agent could increase the degree of crosslinking and obviously improve the physical properties. Functionalized poly(TBMA‐co‐HEMA) was used as a binder resin and composed with a photoacid generator for positive photoresists. From exposure characteristics, the optimal lithographic condition was achieved when exposed for 90 s, PEB at 100°C for 2.5 min, and developed in 10 wt % Na₂CO₃ developer for 30 s. After completing the lithography process, the residual pattern of positive photoresist was further treated at 140°C for 30 min to cure the pendant unsaturated groups. The resolution of the positive photoresist was analyzed by an optical microscope and SEM technique. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 328–333, 2001     

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     

Kinetics of adsorption of methylene blue and rhodamine 6G on acrylic acid‐based superabsorbents

Superabsorbent polymers (SAPs) of acrylic acid, sodium acrylate, and acrylamide (AM), crosslinked with ethylene glycol dimethacrylate, were synthesized by inverse suspension polymerization. The equilibrium swelling capacities of the SAPs were determined and these decreased with increasing AM content. The adsorption of the two cationic dyes, methylene blue and rhodamine 6G, on the dry as well as equilibrium swollen SAPs was investigated. The amount of the dye adsorbed at equilibrium per unit weight of the SAPs and the rate constants of adsorption were determined. The amount of the dye adsorbed at equilibrium by the SAPs decreased with increasing mol % of AM in the SAPs. The amount of the dye adsorbed at equilibrium was almost equal for the dry and equilibrium swollen SAPs. However, the equilibrium swollen SAPs adsorbed dyes at a higher rate than the dry SAPs. The higher rate of adsorption was attributed to the availability of all the anionic groups present in the fully elongated conformation of the SAPs in the equilibrium swollen state. The effect of initial dye concentration on the adsorption was also investigated and the adsorption was described by Langmuir adsorption isotherms. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Adsorption of cationic dyes on poly(acrylic acid‐co‐sodium acrylate‐co‐acrylamide) superabsorbents

Inverse suspension polymerization was carried out to synthesize poly(acrylic acid‐co‐sodium acrylate‐co‐acrylamide) superabsorbent polymers (SAPs) crosslinked with ethylene glycol dimethacrylate (EGDMA). The equilibrium swelling capacities of the SAPs, determined by swelling them in DI water, were found to vary with the acrylamide (AM) content. The SAPs were used to adsorb four cationic dyes (Acriflavine, Auramine‐O, Azure‐I and Pyronin‐Y). The effect of AM content in the SAPs on the adsorption of the cationic dyes was investigated. Different initial concentrations of Azure‐I were used with the same amount of the SAP to explore the effect of initial dye concentration on the adsorption. The effect of the adsorbent amount was investigated by taking different amounts of SAP with a fixed initial concentration of Acriflavine. The kinetics of the dye adsorption was modeled by a first order model and the equilibrium amount of the dye adsorbed, adsorption rate coefficients, removal efficiency and partition coefficients were determined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Syntheses,characterization, and antibacterial activity of chitosan grafted hydrogels and associated mica‐containing nanocomposite hydrogels

Chitosan (CS) grafted poly[(acrylic acid)‐co‐(2‐hydroxyethyl methacrylate)] (CS‐g‐poly(AA‐co‐HEMA)) at different molar ratios of AA and HEMA, and the associated nanocomposite hydrogels of CS‐g‐poly(AA‐co‐HEMA)/mica were synthesized by radical copolymerization. The grafting positions at the amino or hydroxyl groups in the CS were identified by Fourier transform infrared spectroscopy. CS‐g‐poly(AA‐co‐HEMA) hydrogels were intercalated in the mica and the amount of hydrogel insertion did not affect the spacing of the silicate layers in mica. The higher mica loadings produced a rougher surface of the nanocomposite hydrogel. The water absorbency of the CS‐g‐poly(AA‐co‐HEMA)/mica nanocomposite hydrogels decreased with increasing levels of mica loading to a lower level than those of the CS‐g‐poly(AA‐co‐HEMA) hydrogels. Both CS‐g‐poly(AA) and CS‐g‐poly(AA‐co‐HEMA)/mica nanocomposite hydrogels exhibited a higher antiproliferative activity against Staphylococcus aureus than did the neat CS hydrogel with CS‐g‐poly(AA) revealing a very pronounced minimum inhibition concentration (MIC) of 1.56 mg mL^?1. The extent of mica loading in the CS‐g‐poly(AA‐co‐HEMA) nanocomposite hydrogels did not affect the MIC (12.5 mg mL^?1). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

新型改性高吸水树脂P(AA-AM)的合成及性能评价

以N,N’-亚甲基双丙烯酰胺为交联剂,过硫酸钾为引发剂,丙烯酸、丙烯酰胺为原料,合成出原位自交联高吸水树脂P(AA-AM)。通过正交实验得出最佳合成工艺为:n(丙烯酸)∶n(丙烯酰胺)=4.5∶1,单体浓度5%,中和度70%,交联剂0.12%,引发剂0.30%(以上均相对AM、AA总量而言);产物的最大吸液性能为:吸蒸馏水最大倍率QW=2 152.4 g/g,吸10%盐水最大倍率Q盐水=28.5 g/g;由于引入适量的AM,产物吸水率和吸盐率得到大幅度的提高,产物形态由最初的粘接颗粒变成分散颗粒。     

Homogeneous complex solution formed through interactions of poly(acrylamide‐co‐acrylic acid)/poly(acrylamide‐co‐dimethyldiallylammonium chloride) complex with M n+ hydration metal ions in aqueous media

A homogeneous complex solution, formed through inter‐polyelectrolyte complexation of poly(acrylamide‐co‐acrylic acid) (P(AM‐AA)) with poly(acrylamide‐co‐dimethyldiallylammonium chloride) (P(AM‐DMDAAC)) and interaction of the P(AM‐AA)/P(AM‐DMDAAC) complex with M ⁿ⁺ hydrated metal ion, was prepared and the structure and properties of the P(AM‐AA)/P(AM‐DMDAAC)/M ⁿ⁺ homogeneous complex solution were studied by UV spectrometry, dynamic light scattering and viscometry. The experimental results show that the homogeneous complex solution can be obtained by controlling the composition of the P(AM‐AA)/P(AM‐DMDAAC) complex and the M ⁿ⁺ metal ion content. Compared to the constituents, ie the P(AM‐AA) solution, the P(AM‐DMDAAC) solution and the P(AM‐AA)/P(AM‐DMDAAC) complex solution, the P(AM‐AA)/P(AM‐DMDAAC)/M ⁿ⁺ complex solution has a new peak at 270 nm in its UV spectrum, a larger hydrodynamic radius, and hence a higher solution viscosity, all of which indicate that there exist specific interactions between polymers and M ⁿ⁺ metal ions. These interactions lead to the formation of a network structure and hence an obvious increase not only in solution viscosity but also in resistance of the polymer solution to simple salts, to temperature changes and to shearing. © 2001 Society of Chemical Industry     

A novel polyacrylamide‐based superabsorbent with temperature switch for steam breakthrough blockage

A novel high‐temperature resistant superabsorbent polymer (SAP) with a temperature switch to control its water absorbency was prepared through solution polymerization of acrylamide (AM), using N,N‐methylenebisacrylamide (NMBA) and tetraallylammonium chloride (TAAC) as crosslinking agents. The SAPs were structurally characterized by Fourier transform infrared (FTIR) spectroscopy and energy dispersive X‐ray spectroscopy (EDX). The factors that influence the water absorbency such as total crosslinker concentration, molar ratio of NMBA to TAAC and temperature were investigated. The SAP with optimized crosslinker concentration showed a swelling ratio less than 10 g/g at 25°C, and drastically enhanced water absorption capacity (190 g/g) at 300°C. The water absorption characteristics can be tuned by varying the temperature. Swelling experimental results combined with crosslinking density study and morphology observation by scanning electron microscopy (SEM) clearly demonstrated that the hydrolysis of amide bonds on NMBA played a critical role in creating these previously unreported SAPs, and that the use of TAAC with an appropriate amount rendered the SAPs high‐temperature resistance. This kind of SAPs has high application potentials as plugging material for steam breakthrough and channeling in heavy oil reservoirs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42067.     

Synthesis and characterization of acrylamide‐based aluminum flocculant for turbidity reduction in wastewater

Polymeric flocculants of aluminum hydroxide‐poly[acrylamide‐co‐(acrylic acid)], AHAMAA, were prepared by solution polymerization using aluminum hydroxide as a coagulant in the presence of acrylamide (AM) and acrylic acid (AA) as a comonomer pair with N,N′‐methylenebisacrylamide as a crosslinking agent. The crosslinking was initiated by ammonium persulfate with N,N,N′,N′‐tetramethylethylenediamine as an initiator. The water absorbency of crosslinked poly[AM‐co‐AA] was always higher than that of AHAMAA and was found to be correlated to the storage modulus of the polymers, which was higher for AHAMAA than that of crosslinked poly[AM‐co‐AA]. The residual aluminum concentration of AHAMAA (0.09–0.2 mg L^?1) indicated the stability of the polymer flocculant which was in good agreement with the observed tan δ and the higher G′′ and G′ values. Both the crosslinked poly[AM‐co‐AA] and AHAMAA satisfactorily reduced the turbidity of kaolin suspensions, but the latter gave a better reduction performance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of super‐absorbent hydrogels based on hemicellulose

A kind of novel hemicellulose‐based hydrogel with excellent water absorbency was synthesized by the graft copolymerization of acrylic acid (AA), acrylic amide (AM) with hemicellulose. The various factors that influenced the water absorbency of the modified hemicellulose were studied, including AA content, hemicellulose content, neutralization degree of AA, and weight ratio (to monomer) of cross‐linker and initiator. The optimal conditions were found as follows: m(AA) : m(AM) : m(hemicellulose) = 15 : 3.5 : 1, the neutralization degree of AA was 75%, and weight ratio (to monomers) of the cross‐linker and the initiator was 0.03% and 1.0%, respectively. The maximum absorbencies toward distilled water and 0.9 wt % NaCl solution were 1128 g/g and 132 g/g, respectively. The characteristics of the hydrogels were also investigated by Fourier Transform InfraRed (FT‐IR), scanning electron microscope (SEM), and atomic force microscope (AFM). The results indicated that the undulant surface and broad network structure offer the hydrogels excellent water absorbency. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42441.     

Synthesis and characterization of functionalized acrylic‐acrylamide‐based superabsorbent gels

We have synthesized series of superabsorbent polymers (SAPs) by solution free radical polymerization of acrylic acid (AA), acrylamide (AM) with different functional monomers (FM). Three functional monomers including zwitterionic monomer [3‐(methacryloylamino) propyl] dimethyl (3‐sulfopropyl) ammonium (MPDSA), cationic monomer (3‐acrylamidopropyl) trimethylammonium chloride (APTAC) and anionic monomer 2‐acrylamidoglycolic acid monohydrate (AGAM) were selected to provide different charged groups on the superabsorbents. The effect of reaction parameters, such as degree of neutralization, content of initiator and crosslinker on the swelling capacity were assessed. The water absorbency of the superabsorbent were characterized in the distilled water, 0.9 wt % NaCl solution and the mixed solution containing 60 mg L^?1 CaCl₂ and 30 mg L^?1 MgCl₂, respectively. In addition, the swelling rate and water retention capacity in the soil were also investigated. Finally, the mechanism of different absorbency induced by the variety kinds of functional monomers was studied by XPS and FTIR, and tentative interpretation was presented as well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009