Swelling behavior of chitosan/poly(acrylic acid) complex

This study investigates the improved swelling behavior of chitosan/poly(acrylic acid) complex by solvent (methanol, ethanol, and acetone) extraction. The complex is developed by photoinitiated free‐radical polymerization of acrylic acid in the presence of chitosan. The swelling ratio of the complexes depends on the cosolvency effect of poly(acrylic acid) to the extracted solvent, which in turn affects the polymer network structure and ionic states characterized by dynamic force microscopy (DFM), Raman, and FT‐IR spectroscopy. The DFM investigation displays the improved structural changes of the polymer network structure after solvent extraction and its relation to the improved swelling property of the chosen system in different environmental conditions (pH, solvent, and salt concentration) are discussed. A high swelling ratio of about 600 times its dry weight is observed in water as well as in low salt and solvent concentration after methanol extraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2930–2940, 2004     

Moisture sorption of polyelectrolyte complex between poly(acrylic acid) and poly(4-vinylpyridine)

Successive differential sorptions have been measured for the system polyelectrolyte complex of poly(acrylic acid)/poly(4-vinylpyridine) + water vapor. The sorption data revealed that the sorption process of water vapor in the complex is controlled not only by diffusion mechanism but also by relaxation mechanism of polymer chains. It has been considered that the complex is composed of a loosely crosslinked, slightly ionized, and relatively homogeneous network structure. The sorption–desorption kinetics have also been investigated for the region of intermediate and high vapor pressures. The interval sorption–desorption curves demonstrated that the complex has the nature of the hysteresis effect in sorptions. It has been concluded that the appearance of sorption hysteresis is due to the depression of mobility of polymer chains resulting from crosslinks between carboxyl groups and pyridine rings.     

Synthesis and characterization of chitosan/poly(acrylic acid) polyelectrolyte complex

Polyelectrolyte complex based on chitosan and acrylic acid monomer by photoinitiated free‐radical polymerization in the absence of crosslinker showed a large transition in swelling in response to changes in pH of surrounding medium. Their ability to swell arises from polyelectrolyte interactions and molecular structure of the complex. The main properties of interest that related to the molecular structure, swelling volumes, glass transition temperature, and elastic modulus of the complex were investigated. The effect of water content, the only variable in the sample component, played an important role in molecular structure of the complex and as a consequence, the extent of intermolecular linkage, especially amide bonds which in turn governed the degree of swelling of the polyelectrolyte complex in this study. The decreased degree of swelling and higher temperature shift of glass transition temperature was found with increased water content, whereas increased modulus of elasticity of dry complex was found in lower water content of synthesis component. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1025–1035, 2002     

Synthesis and characterization of new poly(butadiene-co-acrylic acid(g) acrylic acid) and poly(butadiene(g) acrylic acid)

Synthetic crosslinked polymers from oligomers of butadiene-co-acrylic acid (Mw 5000) or oligomers of butadiene (Mw 6000) and acrylic acids were obtained after grafting reactions using varying reactant ratios. Characterization of the new crosslinked polymers were carried out by use of FTIR, H-NMR, and ¹³C-NMR in the solid state and also with the swollen products in D₂O, DMF D7, or DMSO D6. Determinations of swelling in distilled water for the different synthesized hydrogels showed increase in the V/Vo ratios as the concentrations of anions (carboxylate) became higher. These values were sensitive to different pH values and changes in the concentrations of electrolytes. Different behavior was observed for the polymers obtained from mass and from synthesis in benzene. SEM analysis of the surfaces of the polymers obtained in mass showed a fibrous structure (with lower contents of carboxylic groups, and more swellable and with greater capacity to retain albumin). A porous surface was observed for products obtained in benzene (with higher content of carboxyl groups and capacity to retain cations such as copper and malachite green).     

Ultrasonic degradation of poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water‐soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates—potassium persulfate, ammonium persulfate, and sodium persulfate—were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The intrinsic viscosity of poly(acrylic acid) and partially neutralized poly(acrylic acid) by isoionic dilution

The isoionic dilution method has been used to measure the intrinsic viscosity, [η], of a poly(acrylic acid) (PAA) sample as a function of neutralization degree, i, at low ionic strength, I = 1.0 × 10. The results obtained for the counterion activity are in close agreement with Manning's theory for counterion condensation. The influence of the ionic strength, I, on [η] and on the Huggins coefficient, k', was also examined and the exponents of the scaling laws relating these two parameters with I were found.     

Studies on chitosan and poly(acrylic acid) interpolymer complex. II. Solution behaviors of the mixture of water-soluble chitosan and poly(acrylic acid)

Water-soluble chitosan with a 50% deacetylation degree was prepared according to the literature. The mixtures of water-soluble chitosan and poly(acrylic acid) (PAA) in water was studied by various experimental techniques, such as viscometry, potentiometry, and transmittance measurements. The results showed that water-soluble chitosan may complex with PAA through electrostatic attraction. This polyelectrolyte complex exists steadily at about an equimolar unit composition. © 1996 John Wiley & Sons, Inc.     

Viscometric studies: Interpolymer complex formation between poly(styrene-b-ethylene oxide) block copolymers and poly(acrylic acid)

Summary Interpolymer complex formation between poly(styrene-b-ethylene oxide) block copolymers (PS-PEO) and poly(acrylic acid) (PAA) has been studied by viscometry using THF-water mixture of several compositions as solvent.Unlike alternating and random copolymers, composition of the complex formed between (PS-PEO) and PAA does not seem to be affected by the molecular characteristics of the copolymer and the solvent composition. However the nature of the reduced viscosity curves during complex formation was found to be dependent on solvent composition and this has been interpreted in terms of preferential solvation, conformation and micellization of the block copolymer molecules.     

Sorption behavior of water vapor into polyelectrolyte complex of poly(acrylic acid)/poly(4-vinylpyridine)

The sorption of water vapor into the polyelectrolyte complex of poly(acrylic acid)/poly(4-vinylpyridine) has been investigated. The sorption isotherm was evaluated on the basis of various theories; BET equation, Flory–Huggins interaction parameter χ₁, and cluster function G₁₁/v₁. The behavior of the BET plot, χ₁, and G₁₁/v₁ was considered in terms of the structure of the complex, while the crosslink density and charge density were determined from the carbonyl absorption in IR spectra. The reasonable conclusion drawn from the available data is as follows. The interaction of water with specific polymer sites plays an important role in the sorption. The sorbed water plasticizes this material, and it enables the expansion of the network. The large amounts of water incorporated by the expansion cannot be dispersed homogeneously in the network, and indicate clustering tendency.     

Interpolymer complexation between poly(ethylene oxide) and poly(acrylic acid)

Summary Solution and solid state properties of the interaction between poly(acrylic acid) and poly(ethylene oxide) have been studied in the presence and absence of CaSO₄ in water or in methanol systems. The association in solution has been investigated by viscosity measurements and NMR spectroscopy. The solid state of the systems has been studied using DSC, IR, X-RAY and 13-C-CPMAS-NMS. Complex formation is also clearly indicated.     

Hydration of poly(acrylic acid) potassium salts

Summary Drying and water uptake of poly(acrylic acid) potassium salts with different degrees of neutralization were studied. The slowing down of drying speed in solid state was not due to Tg but due to the difficulty of the release of water molecule bound to two metal carboxylates or carboxyls. The equilibrium water uptake decreased below 25% neutralization, whereas it increased linearly with neutralization beyond 25%. The bending in the plot of equilibrium water uptake was explained by the appearance of vacant sites in bodycentered cubic coordination. The initial decrease was attributable to the sum of the two opposite effect, that is, the decrease of free carboxyl groups and the increase in dielectric nature. The results were discussed in connection with those for sodium salts described in the preceding paper.     

Spatial inhomogeneity in poly(acrylic acid) hydrogels

The crosslink density distribution in gels known as the spatial gel inhomogeneity has been investigated in poly(acrylic acid) (PAAc) gels with the static light scattering measurements. PAAc gels were prepared at a fixed chemical crosslink density but at various initial monomer concentrations. The gels were characterized by swelling and elasticity tests as well as by light scattering measurements. PAAc gels exhibit a maximum degree of spatial inhomogeneity at a critical monomer concentration . shifts toward higher concentrations as the gel swells beyond its dilution degree after preparation. Depending on the polymer concentration in gels, swelling reduces or enhances the extent of the spatial inhomogeneities. It was shown that the apparent degree of the spatial gel inhomogeneity is determined by the combination of three effects, namely the effects of the effective crosslink density, charge density and segment density. The relative magnitudes of these effects vary depending on the polymer concentration and lead to the appearance of a maximum degree of spatial inhomogeneity at a critical concentration.     

Polypropylene fibers grafted with poly(acrylic acid)

An effective method for the grafting of poly(acrylic acid) on polypropylene fibers has been developed, using diphenyl and a dispersing agent (NNO) in the grafting bath as additives to facilitate the grafting process. The method makes it possible to obtain high grafting degrees of poly(acrylic acid) on polypropylene fibers with a minimal quantity of homopolymer as a side product. The effect of grafting degree on the moisture absorption and swelling of the modified fibers has been examined and described with mathematical equations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2295–2299, 2002     

Hydration of poly(acrylic acid) sodium salts

Summary Drying and water uptake of poly(acrylic acid) sodium salts with different degrees of neutralization were studied. The slowing down of drying speed in solid state was not due to Tg but due to the difficulty of the release of water molecule bound to two metal carboxylates or carboxyls. The equilibrium water uptake remained almost constant below 33 % neutralization, whereas it increased linearly with neutralization beyond 33 %. This was explained by the appearance of vacant sites in octet coordination.     

Hydration of poly(acrylic acid) lithium salts

Summary Drying and water uptake of poly(acrylic acid) lithium salts with different degrees of neutralization were studied. Though the equilibrium water uptake increased with increasing neutralization %, the slope of the plot above ca. 33 % neutralization was greater than that below this neutralization %.     

Thermal analysis of poly(acrylic acid)/poly(oxyethylene) blends

Blends between poly(acrylic acid) and two different poly(oxyethylenes), (1) polyethylene glycol (PEG-1000) and (2) poly(oxyethylene) (20) sorbitan monooleate (Tween-80), were studied by differential scanning calorimetry. The glass transition temperatures, T_g, of the various compositions of these blends were found to follow Fox's equation. At room temperature, blends containing no more than 60% PEG-1000 were amorphous and exhibited only a single glass transition. For these blends with PEG-1000, the glass transition temperatures for the annealed samples were higher than for the quenched samples due to the formation of a PEG crystalline phase. It was also found that addition of an amorphous polymer such as poly(acrylic acid) significantly reduced the degree of crystallinity of a semicrystalline polymer such as poly(oxyethylene). The Tween-80 systems did not show phase separation at room temperature. The compatibility between this poly(acrylic acid) and this poly(oxyethylene) was attributed to hydrogen bonding and to the lower crystalline lattice energy of this poly(oxyethylene) through its effect on its ideal solution solubility. © 1993 John Wiley & Sons, Inc.     

A supramolecular structured complex of poly(acrylic acid) and polystyrene‐block‐poly(vinylbenzyltrimethylammonium chloride)

Complexation of poly(acrylic acid) (PAA) by polystyrene‐block‐poly(vinylbenzyltrimethylammonium chloride) (PS‐b‐VB) results in a mesomorphously ordered material with a glass transition temperature of 71 °C. The complex is assumed to consist of hexagonally‐ordered ion‐rich cylindrical rods containing the PAA embedded in a polystyrene matrix. It has been shown by small‐angle X‐ray scattering (SAXS) analysis that the mesophase is characterized by sharp phase boundaries between ionic and non‐ionic regions. The structure parameters are evaluated by using a two‐dimensional interface distribution function resulting in an average cylinder radius in the range 3.0–3.5 nm and a lattice constant of 14 nm. The radius distribution is calculated to be relatively broad, which is found to be consistant with sharp phase boundaries. PS‐b‐VB‐PAA represents an example of a new type of polymeric hybrid material with a supramolecular ordered ionic–non‐ionic nanostructure. © 2000 Society of Chemical Industry     

Thermal behavior of poly(acrylic acid)–poly(vinyl pyrrolidone) and poly(acrylic acid)–metal–poly(vinyl pyrrolidone) complexes

Thermal analysis (TGA and DTA) of samples of PAA, PVP, PAA–PVP complexes, containing different weight fractions of PAA and ternary polymer–metal–polymer complexes, were studied. The activation energy parameters for the thermal degradation were also calculated. The study of the effect of FeCl₃, NiCl₂, and Ni(NO₃)₂ on the TGA and DTA curves of the complexes showed that the decompositions are dependent on the concentrations and the nature of the metal ions. The DTA traces of PAA–PVP complex containing FeCl₃, NiCl₂, and Ni(NO₃)₂ showed that the treatment of the complex with these metal ions causes considerable changes in the thermal decomposition of PAA–PVP complex. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4049–4057, 2006     

Study of the interaction of poly(acrylic acid) and poly(acrylic acid‐poly acrylamide) complex with bone powders and hydroxyapatite by using TGA and DSC

The thermo gravimetric analysis (TGA) and differential scanning calorimetric analysis (DSC) were used to study the thermal degradation of poly(acrylic acid) PAA and poly(acrylamide) PAAm as well as the compound obtained from their interactions. The examination of the thermal curves revealed that the characteristics of the curves of the compound resulting from the cooperative interactions are different from those of the constituent polymers. The differences in the characteristics of the thermal curves were attributed to the formation of an interpolymer complex resulting from the interaction of PAA with PAAm at low pH value. These two thermal techniques were also used to investigate the thermal behavior of the compounds obtained from the interaction of PAA and (PAA‐PAAm) mixture with bone powders (BP) and hydroxyapatite (HA). It was found that the TGA, DTG, and DSC curves do not show the peak of formation and degradation of PAA anhydride which provided strong evidence for the consumption of PAA in the reaction between the polymer and BP. The interaction between PAA and the thermally treated BPs and HA was investigated. Moreover the interaction between the mixture of PAA and PAAm at different pH values and the BPs and HA was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007