Preparation of carboxymethyl cellulose‐g‐poly (acrylamide)/montmorillonite superabsorbent composite as a slow‐release urea fertilizer

A superabsorbent composite was synthesized through free‐radical graft copolymerization of carboxymethyl cellulose, acrylamide, and montmorillonite by means of a crosslinker such as N,N′‐methylenebisacrylamide and potassium persulfate as an initiator. The preparation mechanism was proposed, and the composite structures were confirmed by using Fourier transform infrared spectroscopy, X‐ray diffraction, thermal gravimetric analysis, and scanning electron microscope. The factors influencing the swelling capacity of the composite were determined to accomplish the highly swelling capacity. The composition (15 wt% carboxymethyl cellulose, 5.4 wt% montmorillonite, 82 wt% acrylamide, 0.07 wt% N,N′‐methylenebisacrylamide, and 1.1 wt% potassium persulfate) exhibited high swelling capacity; it was selected to be loaded with urea fertilizer, and the release was investigated by measuring the conductivity. The results showed that the new controlled release system has good slow release properties.     

Preparation and Properties of Biodegradable Slow-Release PAA Superabsorbent Matrixes for Phosphorus Fertilizers

Biodegradable superabsorbent matrixes for a slow-release fertilizer were prepared by using crosslinked acrylic acid and water-soluble granular phosphorus fertilizer KH₂PO₄. The effects of the amount of crosslinker, initiator and phosphorus fertilizer concentration on water absorption were investigated and optimized. The products show excellent slow release and water-retention capacity, being nontoxic in soil and environment-friendly, and could be useful especially in agricultural and horticultural applications. The results showed that the hydrogel structure and swelling capacity was affected by various factors, such as concentration of crosslinker and initiator, as well as by the amount of KH₂PO₄.     

Preparation and characterization of cellulose acetate‐coated compound fertilizer with controlled‐release and water‐retention

A novel cellulose acetate‐coated compound fertilizer with controlled‐release and water‐retention (CAFCW) was prepared, which possessed the three‐layer structure. Its core was water‐soluble compound fertilizer granular, the inner coating was cellulose acetate (CA), and the outer coating was poly(acrylic acid‐co‐acrylamide)/unexpanded vermiculite (P(AA‐co‐AM)/UVMT) superabsorbent composite. The effects of the amount of acrylamide, crosslinker, initiator, degree of neutralization of acrylic acid (AA), and unexpanded vermiculite concentration on water absorbency were investigated and optimized. The water absorbency of CAFCW was 72 times its own weight if it was allowed to swell in tap water at room temperature for 90 min. Element analysis and atomic absorption spectrophotometer results showed that the product contained 11% nitrogen, 6% phosphorus (shown by P₂O₅), 9% potassium (shown by K₂O), 1% calcium (shown by CaO), and 0.4% magnesium (shown by MgO). Swelling rate, slow‐release, and water‐retention properties of CAFCW were also investigated. This product with good controlled‐release and water‐retention capacity, being degradable in soil and environmentally friendly, could be especially useful in agricultural and horticultural applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and swelling behavior of thermosensitive hydrogels based on N-substituted acrylamides and sodium acrylate

A series of hydrogels based on N-isopropylacrylamide, sodium acrylate, and N-tert-butylacrylamide were synthesized by free radical polymerization in a mixture of dioxane and water with tetra(ethylene glycol) diacrylate as the crosslinker and benzoyl peroxide as the initiator. The swelling behavior including the swelling rate of the crosslinked gels in water was studied with gravimetric method. The swelling ratio of the gel (0.1 mol% crosslinking) can reach 420 g/g at 20 °C and such a gel can release 96% of the water absorbed at 40 °C. The lower critical swelling temperature (LCST) of the copolymers can be adjusted by changing the chemical composition of the polymers. Such crosslinked gels can be potentially used as thermosensitive superabsorbent because of their high water uptake and thermal sensitivity.     

Poly[N‐isopropyl acrylamide]‐co‐polyurethane copolymers for controlled release of urea

A novel block copolymer of poly[N‐isopropyl acrylamide]‐co‐polyurethane was designed, synthesized, and applied as controlled release fertilizer coating. Structural confirmation of the copolymer was performed using FTIR and ¹H‐NMR spectra and elemental analysis. The coating process consists essentially of immersing urea granules in molten polymer and removing the coated urea from the melt by centrifugal action. The morphology of the coated urea was studied using scanning electron microscope (SEM). The polymer coat of the urea granules was found to swell in water forming pores and enabling the release of urea. The urea released from the granule, monitored using a mass spectroscopy technique, was found to be governed by pH of the aqueous medium. The study anticipates development of a beneficiary fertilizer coat in terms of improving controlled release over a period of time which can be tailored by soil temperature, pH and moisture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3236–3243, 2010     

Synthesis of crosslinked poly(butyl methacrylate‐co‐pentaerythritol triacrylate) gel by single electron transfer‐living radical polymerization and its oil‐absorbing properties

A novel high oil‐absorbing crosslinked gel was synthesized by copolymerization of butyl methacrylate (BMA) with a small amount of pentaerythritol triacrylate (PETA) crosslinker using single electron transfer‐living radical polymerization (SET–LRP) initiated with carbon tetrachloride (CCl₄) and catalyzed by Cu(0)/hexamethylenetetramine (HMTA) in N, N‐dimethylformamide (DMF). The polymerization followed first‐order kinetics as indicated by linear increase of monomer concentration with reaction time. Effects of reaction temperature, crosslinker, initiator, and catalyst on the oil‐absorbing properties of the crosslinked gel were investigated in detail. The oil absorptions of the crosslinked gel to chloroform, toluene could reach 51.9, 34.5 g/g, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,characterization and water absorbency properties of poly(acrylic acid)/sodium humate superabsorbent composite

A novel poly(acrylic acid)/sodium humate superabsorbent composite was synthesized by aqueous solution polymerization of acrylic acid using N, N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator in the presence of sodium humate. The effects on water absorbency such as initial monomer concentration, degree of neutralization of acrylic acid, amount of crosslinker, initiator and sodium humate, etc. were investigated. The water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with a sodium humate content of 20% exhibited an absorption of 1268 g H₂O/g sample and 93 g H₂O/g sample in distilled water and in 0.9 wt% NaCl solution, respectively. Swelling rate and water retention tests were also carried out. The results show that sodium humate, as a kind of functional filler, can enhance comprehensive properties of superabsorbent composite and reduce the product cost significantly. Copyright © 2005 John Wiley & Sons, Ltd.     

Highly absorbing superabsorbent polymer

Acrylic acid (AA)–acrylamide (AM) based superabsorbent polymers (SAP) were synthesized by inverse suspension polymerization using potassium‐persulfate as the initiator, N,N′‐methylene bisacrylamide (BIS) as a crosslinker, sorbitan monostearate (Span 60) as the dispersant, cyclohexane as the solvent, and bis(methacryloylamino)‐azobenzene as the hydrophobic surface crosslinker. The influence of the polymerization parameters on the properties of the SAPs, water absorption (Q), morphology of the SAPs, swelling kinetics, salt resistance, and the reversibility of water absorption were investigated. The prepared SAPs have excellent water absorption, rapid water uptake, and good resistance to NaCl solutions. Furthermore, they show better reversible water uptake than the previously reported SAPs. The average water absorbency is 2800 g/g and 181 g/g of liquid absorbance in 0.025M NaCl solution. The initial water uptake rate is 1357 g/g/min and the reversibility of water absorption is 200 g/g in the repeated fourth cycle. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1357–1364, 2008     

Third‐generation amphiphilic conetworks. I. Synthesis and swelling behavior of poly(N,N‐dimethyl acrylamide)/polydimethylsiloxane conetworks

A strategy has been developed for the synthesis of novel amphiphilic conetworks (APCNs) of poly(N,N‐dimethyl acrylamide) (PDMAAm) and polydimethyl‐siloxane (PDMS) segments crosslinked with polyhydrosiloxanes. The synthesis proceeds in three steps in one pot (see Figure 2 for reactions and abbreviations): (1) the preparation of a charge containing three components (an asymmetric–telechelic macromonomer, MA‐PDMS‐V, plus two symmetric–telechelic crosslinkers, MA‐PDMS‐MA and V‐PDMS‐V), (2) the free‐radical terpolymerization of N,N‐dimethyl acrylamide, MA‐PDMS‐V, and MA‐PDMS‐MA into a slightly crosslinked and soluble graft of a PDMAAm backbone carrying‐PDMS‐V branches, and (3) the crosslinking of PDMS branches with polyhydrosiloxanes. The effects of key experimental parameters (e.g., composition, molecular weights, and initiator and crosslinker concentrations) on synthesis details and swelling behavior have been studied. The water uptake/permeability of APCNs is significantly increased by the addition of homo‐PDMAAm to graft charges, crosslinking of the graft, and, after the desirable morphology is stabilized, removing the homo‐PDMAAm by water extraction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 295–307, 2007     

Synthesis and properties of clay-based superabsorbent composite

A novel superabsorbent composites based on acrylic acid, acrylamide, and inorganic clay mineral-attapulgite were synthesized through a solution polymerization to improve water and saline absorbencies. The superabsorbent composite was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The effects of saline solutions, amount of initiator, crosslinker and attapulgite on the water absorbency of superabsorbent composites were investigated. The water retention test of superabsorbent composites were also carried out. The superabsorbent composite exhibited improved water and saline absorbencies compared with that of crosslinked poly(acrylic acid-co-acrylamide) superabsorbent polymer. The water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% reaches more than 1400 g H₂O/g and 110 g H₂O/g in distilled water and 0.9% NaCl solution, respectively.     

Synthesis and characterization of a novel controlled release nitrogen-phosphorus fertilizer hybrid nanocomposite based on banana peel cellulose and layered double hydroxides nanosheets

In the present study, a novel environment-friendly hybrid nanocomposite of Banana Peel Cellulose-g-poly(acrylic acid)/PVA (BPC-g-PAA/PVA) hydrogel and Layered double hydroxides (LDH) nanosheets was developed using in situ graft polymerization for slow release of NP (nitrogen, phosphorous) fertilizers and water retention. The hybrid nanocomposite hydrogel containing NP fertilizers was characterized using FTIR, and SEM. The effects of pH changes and different saline solutions on the swelling behavior, fertilizer release and water retention properties of the nanocomposite were investigated.The nanocomposite hydrogel showed a pH dependent swelling, as in the pH range of 7–10, the hydrogel had higher water absorbency. However, pH had opposite effects on the release of fertilizers. Phosphorus release had an increasing trend from pH 2 to 7 and it reached its maximum value at normal pH while nitrogen had a higher release rate at acidic pH and by increasing pH from 2 to 7, the release of nitrogen decreased gradually. Water absorption and fertilizer release of hydrogel was influenced by different cations in the order of Ca²⁺ < K⁺ < Na⁺. Water retention study in loamy sand soil showed that the nanocomposite hydrogel significantly improved the water retention of the soil for a longer period of time, compared to neat BPC-gPAA. This result indicated that incorporation of LDH nanosheets in hydrogel matrix improved its water retention property. The obtained results revealed that the nanocomposite of BPC-g-PAA/PVA hydrogel and LDH nanosheets can be a promising controlled release fertilizer formulation with enhanced water retention properties for agricultural applications.     

Phosphate‐Loaded Hydrogel Nanoparticles for Sepsis Prevention Prepared via Inverse Miniemulsion Polymerization

Local depletion of intestinal phosphate triggers changes in bacterial phenotypes that adversely affect the health of the host. This article describes a process for encapsulating phosphates in crosslinked poly(ethylene glycol) diacrylate (PEGDA) nanoparticles using inverse miniemulsion polymerization as a drug delivery approach for sustained release of phosphates to the intestinal epithelium. The effects of crosslinker, PEGDA co‐monomer, N‐vinyl pyrrolidone, (NVP) and surfactant concentrations on the nanoparticle size distribution, swelling ratio and monomer conversion are investigated. Increased surfactant and PEGDA concentrations result in smaller particle size and swelling ratio. A copolymerization model of crosslinking is used to predict conversion and gelation dynamics as a function of polymerization conditions. The model assumes that bulk polymerization can be used to approximate inverse miniemulsion polymerization with an aqueous‐phase initiator. The initiator efficiency is used as an adjustable parameter to simulate the conversion dynamics, thus accounting for radical confinement effects and interaction with emulsifier molecules.     

Synthesis and characterization of a film‐forming,crosslinked, amphiphilic block copolymer of butadiene and acrylamide

An amphiphilic block copolymer of acrylamide and butadiene was synthesized by the polymerization of acrylamide in the presence of the crosslinker N,N′‐methylene bisacrylamide initiated by a hydroxyl‐terminated polybutadiene/V(V) macroredox initiator. The product had good film‐forming ability. It was characterized by IR and NMR spectroscopy, viscosity, swelling, and microhardness measurements, scanning electron micrography, and differential scanning calorimetry. A good film was obtained from the block copolymer with a greater proportion of butadiene; it had greater permeability for nonpolar solvents, and it was poorly permeable to water and other polar solvents. The film swelled in polar and nonpolar solvents and had almost the same capacity for the loading and release of hydrophilic and hydrophobic dyes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3290–3303, 2006     

Thermoresponsive hydrogel of poly(glycidyl methacrylate‐co‐N‐isopropylacrylamide) as a nanoreactor of gold nanoparticles

The synthesis of a thermoresponsive hydrogel of poly(glycidyl methacrylate‐co‐N‐isopropylacrylamide) (PGMA‐co‐PNIPAM) and its application as a nanoreactor of gold nanoparticles are studied. The thermoresponsive copolymer of PGMA‐co‐PNIPAM is first synthesized by the copolymerization of glycidyl methacrylate and N‐isopropylacrylamide using 2,2′‐azobis(isobutyronitrile) as an initiator in tetrahydrofuran at 70 °C and then crosslinked with diethylenetriamine to form a thermoresponsive hydrogel. The lower critical solution temperature (LCST) of the thermoresponsive hydrogel is about 50 °C. The hydrogel exists as 280‐nm spheres below the LCST. The diameter of the spherical hydrogel gradually decreases to a minimum constant of 113 nm when the temperature increases to 75 °C. The hydrogel can act as a nanoreactor of gold nanoparticles because of the coordination of nitrogen atoms of the crosslinker with gold ions, on which a hydrogel/gold nanocomposite is synthesized. The LCST of the resultant hydrogel/gold nanocomposite is similar to that of the hydrogel. The size of the resultant gold nanoparticles is about 15 nm. The hydrogel/gold nanocomposite can act as a smart and recyclable catalyst. At a temperature below the LCST, the thermoresponsive nanocomposite is a homogeneous and efficient catalyst, whereas at a temperature above the LCST, it becomes a heterogeneous one, and its catalytic activity greatly decreases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2812–2819, 2007     

Bioengineering functional copolymers. III. Synthesis of biocompatible poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrocomplexes and their thermostabilization effect on the activity of the enzyme penicillin G acylase

Stimuli‐responsive poly[(N‐isopropylacrylamide‐co‐maleic anhydride)‐g‐poly(ethylene oxide)]/poly(ethylene imine) macrobranched macrocomplexes were synthesized by (1) the radical copolymerization of N‐isopropylacrylamide and maleic anhydride with α,α′‐azobisisobutyronitrile as an initiator in 1,4‐dioxane at 65 °C under a nitrogen atmosphere, (2) the polyesterification (grafting) of prepared poly(N‐isopropylacrylamide‐co‐maleic anhydride) containing less than 20 mol % anhydride units with α‐hydroxy‐ω‐methoxy‐poly(ethylene oxide)s having different number‐average molecular weights (M_n = 4000, 10,000, or 20,000), and (3) the incorporation of macrobranched copolymers with poly(ethylene imine) (M_n = 60,000). The composition and structure of the synthesized copolymer systems were determined by Fourier transform infrared, ¹H and ¹³C NMR spectroscopy, and chemical and elemental analyses. The important properties of the copolymer systems (e.g., the viscosity, thermal and pH sensitivities, and lower critical solution temperature behavior) changed with increases in the molecular weight, composition, and length of the macrobranched hydrophobic domains. These copolymers with reactive anhydride and carboxylic groups were used for the stabilization of penicillin G acylase (PGA). The conjugation of the enzyme with the copolymers significantly increased the thermal stability of PGA (three times at 45 °C and two times at 65 °C). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1580–1593, 2003     

Proline‐based polymeric monoliths: Synthesis,characterization, and applications as organocatalysts in aldol reaction

Proline‐based polymer monoliths were synthesized via green protocol using lipase‐catalyzed esterification of methacrylic acid and 4‐hydroxyproline. Prolinyl methacrylate thus prepared was polymerized in situ as crosslinked monolith. The monolith was characterized by various techniques such as Fourier transform infrared, ¹H‐NMR, ¹³C‐NMR, scanning electron microscopy (SEM), X‐ray diffraction (XRD), and nitrogen analysis and used as catalyst in aldol reactions. The swelling behavior of the monolith was also studied as function of various external parameters like pH and temperature. The monoliths synthesized with 1% crosslinker was selected as candidate monolith for use as catalyst in aldol reaction, which was studied as a function of time, temperature, substrate structure, and amount of water:EtOH. The catalysts exhibited high efficiency in the cross aldol reaction, especially with the aromatic substrates having electron withdrawing substituent, and also good activity retention was observed when recycleability was studied up to five cycles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1007–1015, 2010     

Poly(N,N‐diethylacrylamide) microspheres by dispersion polymerization

Poly(N,N‐diethylacrylamide)‐based microspheres were prepared by ammonium persulfate (APS)‐initiated and poly(vinylpyrrolidone) (PVP)‐stabilized dispersion polymerization. The effects of various polymerization parameters, including concentration of N,N′‐methylenebisacrylamide (MBAAm) crosslinker, monomer, initiator, stabilizer and polymerization temperature on their properties were elucidated. The hydrogel microspheres were described in terms of their size and size distribution and morphological and temperature‐induced swelling properties. While scanning electron microscopy was used to characterize the morphology of the microspheres, the temperature sensitivity of the microspheres was demonstrated by dynamic light scattering. The hydrodynamic particle diameter decreased sharply as the temperature reached a critical temperature ～ 30 °C. A decrease in the particle size was observed with increasing concentration of both the APS initiator and the PVP stabilizer. The microspheres crosslinked with 2–15 wt % of MBAAm had a fairly narrow size distribution. It was found that the higher the content of the crosslinking agent, the lower the swelling ratio. High concentration of the crosslinker gave unstable dispersions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6263–6271, 2008     

Influence of crosslinker and ionic comonomer concentration on glass transition and demixing/mixing transition of copolymers poly(N-isopropylacrylamide) and poly(sodium acrylate) hydrogels

Hydrogels based on N-isopropylacrylamide and sodium acrylate as ionic comonomer were synthesized by free radical polymerization in water using N,N′-methylenebisacrylamide as crosslinker and ammonium persulfate as initiator. The glass transition of dried copolymers poly(N-isopropylacrylamide) (PNIPA) and poly(sodium acrylate) (SA) gels and demixing/mixing transition of PNIPA-SA hydrogels swollen with increasing amounts of water were studied using conventional differential scanning calorimetry. In the crosslinked polymers, the glass transition linearly increases, and the transition range becomes broader, with increasing crosslinker content. Increasing content of ionic comonomer also produces an increase of glass transition temperature, which moves to higher temperatures with higher sodium acrylate fraction. The influence of chemical structure of PNIPA-SA hydrogels on the lower critical solution temperature (LCST) of PNIPA-SA/water mixtures during heating and cooling was quantified as function of the content of the crosslinker and the ionic comonomer, as well as water content of the hydrogel in the range from 95 to 70 wt%. At parity of water content, the LCST occurs at higher temperatures for gels containing higher amounts of sodium acrylate. Similarly, the introduction of N,N′-methylenebisacrylamide causes an increase of the LCST, which grows with increasing of crosslinking degree of the hydrogel.     

Sodium alginate-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate)/montmorillonite superabsorbent composite: Preparation,swelling investigation and its application as a slow-release fertilizer

Sodium alginate-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate)/montmorillonite superabsorbent composites (SACs) were prepared by graft copolymerization of acrylic acid (AA) and 2-hydroxyethyl methacrylate (HEMA) onto sodium alginate (Na-Alg) in the presence of montmorillonite (MMT) using N,N′-methylenebisacrylamide (MBA) as a crosslinker and potassium persulfate (KPS) as an initiator in aqueous solution. The composite structures were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Thermal Gravimetric Analysis (TGA) and Scanning Electron Microscope (SEM). The effect of % initiator, crosslinker amount and clay ratio on the swelling capacity was investigated. The results indicated that the highest swelling capacity of the composites in distilled water was 752 g/g by using 1.25% KPS and 0.06% MBA, 75% AA, 6.25% HEMA and 12.5% Na-Alg. Different samples were loaded with urea to evaluate their release potentials, and the release was studied by measuring the conductivity. The amount of urea release increased with increasing MMT amount.     

Synthesis and Characterization of Crosslinked Polymers for Biomedical Composites

Three kinds of low molecular weight unsaturated polyesters containing carbon-carbon double bonds were synthesized by the reaction of poly (ε-caprolactone) diol or D,L-lactide and glycolic acid with maleic anhydride or fumaric acid. These functionalized polymers were thermally crosslinked in the presence of radical initiator to prepare the crosslinked polymers available as a matrix resin for biomedical composites. Hydrolysis of the crosslinked polyesters was investigated in buffer solution at 37°C.