A thermally regenerable composite sorbent of crosslinked poly(acrylic acid) and ethoxylated polyethyleneimine for water desalination by Sirotherm process

Interpenetrating polymer networks (IPNs) comprising weakly acidic and weakly basic cross-linked polymers, namely, poly(acrylic acid-co-ethyleneglycol dimethacrylate) (XPAA) and 80% ethoxylated polyethyleneimine (EPEI) cross-linked with glutaraldehyde, were prepared by the copolymerization of acrylic acid (AA) and ethyleneglycol dimethacrylate by a free-radical method, in the presence of calculated amounts of EPEI in methanol solution, followed by cross-linking with glutaraldehyde. The resulting IPNs, containing carboxylic acid groups and weakly basic tertiary amine groups in close proximity in the same resin bead, exhibited thermally regenerable desalination properties [e.g., sorption of salt at 30 °C and desorption at higher temperatures (80 °C)], simulating the behavior of the well-known Sirotherm resins. For NaCl and MgCl2, the maximum equilibrium sorption (∼0.5 mmol/g of dry resin in 0.1 M salt solution) was exhibited by an IPN with a carboxylic-to-amine (C/A) mole ratio in the range of 3−5. The equil...

A commercial acrylic fiber containing 92 wt % acrylonitrile was hydrolyzed to convert a part of its nitrile (CN) groups to carboxylic acid (COOH) groups and then was coated chemically with 80% ethoxylated polyethylenimine (EPEI) resin, followed by crosslinking with glutaraldehyde. The resulting sorbent, PAN(CO2H)(EPEI.XG), containing carboxylic acid groups and weakly basic tertiary amine groups in close proximity on the same fiber is found to simulate the well‐known Sirotherm™ resins used for partial desalination of brine solution by adsorbing the salt at ambient temperature and desorbing it at an elevated temperature in the same solution. The sorption behavior of the new sorbent was evaluated for solutes NaCl and MgCl2, showing saturation capacities of 0.797 and 0.877 meq/g (dry) sorbent fiber, respectively, at 30°C. The equilibrium sorption data show good agreement with both Langmuir and Freundlich isotherms for sorption from single‐component solutions and with Butler–Ockrent and LeVan–Vermeulen models for bicomponent sorption. Although the equilibrium uptake of NaCl reaches maximum in neutral solutions (pH ∼ 6.5), falling at both lower and higher pH, that of MgCl2 is augmented in alkaline pH due to additional sorption by cation exchange at the ionic sites formed at higher pH. The initial uptake of the salt, which is nearly instantaneous, exceeds the sorption value attainable at equilibrium. The high initial rate of salt uptake fits a shell‐core kinetic model for sorption on fiber of cylindrical geometry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 883–893, 2004

A study of the Schmidt reaction on several polymers with pendant carboxylic and ketone moieties was carried out. Four polymers were used as starting materials: (1) poly(methyl vinyl ketone), (2) poly(acrylic acid), (3) a copolymer of methyl vinyl ketone and acrylic acid, and (4) a copolymer of styrene and acrylic acid. Most reactions were conducted in an acetic acid medium with the exception of one reaction on poly(acrylic acid) which was done in dioxane and another on copolymer of styrene and acrylic acid done in chloroform. It was found that a Schmidt reaction on poly(acrylic acid) in acetic acid solution will lead to intermolecular reactions of the intermediate with the solvent in preference to reactions with neighboring carboxyl groups on the polymer backbone. A tendency of poly(acrylic acid) to form cyclic anhydrides under these reaction conditions interferes with the yield of acetamide units.

Hydrophobically modified polyelectrolytes (HMP) are polymers with a high content of ionizable groups bonded to hydrophobic groups. Copolymers of poly(acrylic acid) and Pluronic surfactants constitute a special class of HMP whereby poly(propylene oxide) segments act as hydrophobes. The poly(propylene oxide) segments possess temperature-dependent aqueous solubility and the solutions of the Pluronic-poly(acrylic acid) copolymers (MW > 3,000,000) undergo a sol-gel transition when kept at body temperature. Due to the presence of the poly(acrylic acid) segments, the Pluronic-poly(acrylic acid) copolymers are bioadhesive. We have examined the hypothesis that the in-situ gelling polymer formulations of Pluronic-poly(acrylic acid) copolymers may have an enhanced retention in the nasal cavity. The effects of putative bioadhesive (Carbomer 934P) and thermogelling (Pluronic F127) polymers on nasal clearance were compared with Pluronic-poly(acrylic acid) copolymers using a rat model. The enhancement of the residence time of fluorescent labels by the Pluronic-poly(acrylic acid) copolymers was shown to be 5-8-fold that of Carbomer, and 3-6-fold that of Pluronic F127. The results unequivocally demonstrate the superior retention of the HMP that combines bioadhesive and thermogelling capabilities over either a bioadhesive polyelectrolyte or a polymer of a low molecular weight that undergoes a sol-gel transition.

A novel poly(acrylic acid)/montmorillonite superabsorbent composite with a water absorbency of 1100 times its own weight was synthesized by the graft copolymerization of acrylic acid with a cross‐linking agent in the presence of montmorillonite ultrafine powder. The influence of the amount of crosslinker and montmorillonite on water absorbency has been investigated. It was found that a crosslinker concentration of 0.03 wt% and 30 wt% montmorillonite gave the best results. The collaborative absorbent effect of sodium carboxylate and carboxylic acid groups was superior to that of sodium carboxylate or carboxylic acid groups alone, and the composite with a ratio of about 2/3 for sodium carboxylate to carboxyl acid groups possessed the highest water absorbence.© 2001 Society of Chemical Industry

We report here our results on the investigation of the chain dynamics of poly(acrylic acid) in aqueous solution. The concentration of poly(acrylic acid) was approximately 3.8×10−4 mol/L, two orders of magnitude higher than that reported in the literature. The pH value of the solution was 3.9, and the hydrogen bonds between the intrinsic and ionized carboxylic acid groups formed dynamic networks, which captured aggregation-induced emission-active molecules (a tetra-quaternary ammonium modified tetraphenylethene derivative) inside the polymer coils and induced fluorescence emission. The hydrogen bonds can be classified as intra- or intermolecular; both can be probed based on the emission change of the tetra-quaternary ammonium modified tetraphenylethene probes. The effects of different external stimuli on the polymer chain dynamics were investigated using different metal cations (including Na+, Li+, Zn2+, Ni2+, Ca2+, and Co2+), different cation concentrations (1×10−6 to 4×10−4 mol/L), different poly(acrylic acid) molecular weights (5, 240, and 450 kDa), and different copolymers. The experimental results indicate that the long poly(acrylic acid) chains (high molecular weight) tend to form dense globular coils and exclude the probe molecules outside, which are robust and unsusceptible to water-soluble metal cations. However, the shorter poly(acrylic acid) chains tend to form intermolecular hydrogen bonds, which are helpful in capturing more probe molecules inside the networks, thus inducing stronger emission. Because of the dual functions of forming hydrogen bonds with carboxylic groups and acting as an acceptor of protons from the carboxylic acid group to form cationic species, copolymerization with acrylate amide [poly(acrylic acid)-co-poly(acrylamide)] can greatly affect the chain dynamics of poly(acrylic acid) segments, which is reflected by the drastically decreased emission intensity from the fluorescent probes.

Polyacrylic acid was synthesized in water by persulfate-initiated polymerization (solution polymerization) of glacial acrylic acid in the absence of a chain-transfer agent. The final product is odorless and colorless. Chelation for calcium ions using a calcium electrode show that our poly(acrylic acid) has a higher chelation capacity than that of existing commercial poly(acrylic acids). A design of experiments was performed to optimize the synthesis conditions to obtain poly(acrylic acid) with a high maximum chelation value. These studies also helped us to gain insight into its high chelation capacity. The chelation capacity for calcium reaches its highest values when polymerization near isothermal conditions is done ∼ 95°C with an acrylic acid concentration of ≤21 wt % and an addition time >1 h. These conditions favor higher molecular weight poly(acrylic acid) with a polydispersity ∼ 4. The dispersion properties of our poly(acrylic acid) are similar to those of the commercial ones. This dual capability of chelation and dispersion is absent in commercial chelants such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and their analogs. At pH > 7, chelation of calcium by our poly(acrylic acid) is much higher than that observed with EDTA. Characterization by NMR, Raman, FTIR, and molecular modeling are included in an attempt to understand structural features that can explain the higher chelation capacity of our atactic poly(acrylic acid).

Trypsin inhibition, calcium and zinc ion binding of starch– g-poly(acrylic acid) copolymers and starch/poly(acrylic acid) mixtures for peroral peptide drug delivery

Poly(methyl acrylate) and amphiphilic copolymer of butyl acrylate and acrylic acid were prepared in the presence of 1,1-diphenylethene (DPE) by γ-irradiation-induced polymerization. The influences of polymerization time, amounts of DPE in system on conversion, molecular weight (MW), and its distribution (Mw/Mn) were studied. The results indicate that the polymerization in the presence of DPE and initiated by γ-irradiation shows the character of controlled radical reaction. The prepared copolymer was used as the polymeric emulsifier in the emulsion polymerizations of butyl acrylate (BA) and styrene (St), respectively, to assess the possibility of making monodisperse latices of relatively high solids content (∼ 35–45%) in an one-step batch process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

We present an overview on synthesis of amphiphilic ionic block-gradient copolymers of styrene and acrylic acid by means of one step direct Nitroxide Mediated Polymerization (NMP) and their characterization. The copolymers comprise a block of poly(acrylic acid) and one or two terminal blocks that include co-monomer units of styrene and acrylic acid in variable proportion. Using 1H NMR the gradient sequence of the poly(acrylic acid-co-styrene) copolymer block has been confirmed. In contrast to diblock copolymers of styrene and acrylic acid, that are known to form in aqueous environment “frozen” aggregates with glassy poly(styrene) core, the novel block gradient copolymers exhibit stimuli-responsive aggregation behavior, as was demonstrated by subsequent studies. This feature makes them very promising for design of a large variety of smart functional materials.

We report on the synthesis of novel pH- and electro-responsive polyelectrolyte brushes from a gold substrate by direct one-step nitroxide-mediated polymerization of acrylic acid (AA) or copolymerization of AA and styrene (S). In the latter case, amphiphilic brushes of block-gradient copolymers PAA-b-(PAA-grad-PS) comprising one PAA block and one block with the gradient sequence of AA and S were obtained. The block-gradient copolymers are initiated from the surface by the start of the PAA block. The brushes were characterized by XPS and ellipsometry. (1)H NMR confirmed the gradient sequence of the PAA-grad-PS copolymer block. The pH- and electro-responsive properties of the brushes were studied by quartz crystal microbalance with dissipation monitoring (QCM-D) in combination with electrochemistry. This method provides evidence of swelling of the PAA brushes proportional to the contour length of the chains at elevated pH, whereas the response functions of the block-gradient copolymers are more complex and point to intermolecular aggregation in the brush at low pH. Monitoring of the changes in resonance frequency and dissipation of the QCM-D also demonstrates that application of negative voltage to the substrate leads to swelling of the brush; application of a positive voltage provokes only a transient collapse of the brush in proportion to the applied voltage.

ABSTRACTStructural and dynamic properties of aqueous solution of atactic poly(acrylic) acid (PAA) in dilute, semi-dilute and concentrated regimes were studied by fully atomistic molecular dynamics simulations with explicit solvent description, as a function of polymer concentration c (i.e. volume fraction φp) and charge density f. PAA size (Rg, R) decreases with φp in semi-dilute and concentrated regimes, due to increase in counter-ion condensation. For all values of f, in dilute regime (c < c*) chains are expanded and in semi-dilute regime (c*< c < c**) chains are in contact with each other, while for c ≅ c** aggregates comprising of few PAA chains occur (at f = 0.2, 0.4 and 0.7). Number of PAA intrachain h-bonds is greater than PAA–PAA interchain h-bonds at all values of f and φp. The number of h-bonds between carboxylic acid groups and carboxylate groups remain unaffected by φp. The Na+ ion self-diffusion coefficient shows linear decrease with concentration for f < 1 and exponential decrease for f = 1. The PAA self-diffusion coefficient shows power law decrease with concentration for f < 1 and exponential decrease for f = 1. Aggregation of chains is favoured due to PAA–PAA interactions with increase in concentration. Our simulation results are in agreement with experiments and coarse-grained simulations in the literature.

Mechanistic approaches on the antibacterial activity of poly(acrylic acid) copolymers

Poly(acrylic acid) is a synthetic polymer that is polymerized from acrylic acid monomers. Poly (acrylic acid) is a high molecular weight polymer having good water solubility. Poly(acrylic acid) also exists in the cross-linked forms. Poly(acrylic acid) is an important polymer for making polymeric blends and nanocomposites. This state-of-the-art review is an endeavour to define the unique capabilities of poly (acrylic acid) to form high performance nanocomposites. The nanofiller nanomaterials including carbon nanotube, graphene, nanodiamond, and inorganic nanoparticles are promising nanofillers for a poly(acrylic acid) matrix. Consequently, the article discusses the following categories: poly(acrylic acid)/carbon nanotube, poly(acrylic acid)/graphene, poly(acrylic acid)/nanodiamond, and poly(acrylic acid)/inorganic nanoparticle nanocomposites. The nanocomposite characteristics are significantly enhanced with the added nanoparticles. Especially, the nanoparticles influenced the electrical conductivity, thermal stability, strength, biocompatibility, adsorption, and anti-bacterial features of the poly(acrylic acid) nanocomposites. Their high performance was related to the interface interactions between the matrix and the nanofillers. The poly (acrylic acid) derived nanocomposites have been used to form advanced hybrid materials for batteries, sensors, antibacterial, and water filters.

Synthesis of cellulose-g-poly(acrylic acid) with high water absorbency using pineapple-leaf extracted cellulose fibers