Dilute solution properties of anionic poly(potassium-2-sulfopropylmethacrylate)

The dilute solution properties of an anionic polyelectrolyte, poly(potassium-2-sulfopropylmethacrylate) [poly(SPM)], are studied by measurements of polymerization rate, intrinsic viscosity, degree of binding, ionic strength, and critical micelle concentration. The polymerization of SPM in 0.5M NaCl aqueous solution proceeded more easily than that of SPM in pure water. The polymerization rate of SPM is found to pass through an extreme value as a function of pH. The intrinsic viscosity of this polyelectrolyte is related to the type and concentration of the salt added. The intrinsic viscosity for anionic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain is in contrast with the polyampholyte. The polyelectrolyte in a high concentration of NaCl has a low degree of binding, indicating that the proton ion (H⁺) is relatively difficult to bind to the sulfonate group (SO⁻₃) at the polymer end. An increase in ionic strength causes the pKa (dissociation constant) to decrease at the half-neutralization point. The monomer solutions exhibit a plot typical of those observed for detergents, with a break in the curve occurring at the critical micelle concentration. For the polymer solutions, no break in the equivalent conductance curve was found for the concentrations studied. The polymer is adapted for use as viscosity-controlling agents in secondary oil recovery operations by water flooding. We have the proposed models to account for the poly(SPM) solution viscometrics. © 1997 John Wiley & Sons, Inc.     

Retention of cadmium ions from aqueous solutions by poly(ammonium acrylate) enhanced ultrafiltration

Cadmium removal from aqueous solution by polyelectrolyte enhanced ultrafiltration (PEUF) with relatively low transmembrane pressure was investigated at varying conditions of polyelectrolyte and cadmium concentrations, transmembrane pressure, ionic strength and pH. The poly(ammonium acrylate), with two average molecular weights (8000 and 15 000 Da) were used as polyelectrolyte. Flux declines during ultrafiltration of polyelectrolyte solutions. An effort has been made to evaluate these resistances independently at different operating conditions. The hydraulic membrane resistance is higher for processing solutions of PAmA₈ than solutions of PAmA₁₅. The study of ionic strength effect demonstrates that it decreases the retention of cadmium ions and increases the permeate flux. More than 99% of cadmium was retained for a NaNO₃ feed concentration less than 5 × 10⁻² mol L⁻¹. The pH effect study on the cadmium recovery revealed a maximum retention around 98% for pH 4.     

Polyelectrolyte complex between chitosan and poly(2-acryloylamido-2-methylpropanesulfonic acid)

Summary A new polyelectrolyte complex between chitosan and poly(2-acryloylamido-2-methylpropanesulfonic acid) (PAMPS) was prepared by mixing aqueous solutions of its components or by free radical polymerization on chitosan template. The complex formation was sensitive to the ionic strength of the medium. The complex was stable in acidic and neutral medium and dissociated at pH > 8. Its composition did not depend on pH values of the medium and the way of preparation. The mixing dilute aqueous solutions of chitosan and PAMPS resulted in the formation of nanoparticles with mean particle diameter 250 nm and monomodal distribution. Received: 16 May 1999/Revised version: 18 June 1999/Accepted: 18 June 1999     

Dilute solution properties of anionic poly(potassium-2-sulphopropylacrylate)

The dilute solution properties of an anionic polyelectrolyte, poly(potassium-2-sulphopropylacrylate) (poly(SPA)) are studied by measurements of intrinsic viscosity, degree of binding, ionic strength and critical micelle concentration. The intrinsic viscosity of this polyelectrolyte is related to the type and concentration of the salt added. The intrinsic viscosity behaviour of an anionic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain is in contrast to that of a polyampholyte. The polyelectrolyte in high concentration of NaCl has a low degree of binding, indicating that the proton ion (H⁺) is relatively difficult to bind to the sulphonate group (SO⁻₃) at the polymer end. An increase in ionic strength causes the pK_a to decrease at the half-neutralization point. The monomer solutions exhibit a plot typical of those observed for detergents, with a break in the curve occurring at the critical micelle concentration. For the polymer solutions, no break in the equivalent conductance curve was found for the concentrations studied.     

Bioartificial materials based on blends of collagen and poly(acrylic acid)

The interactions between soluble collagen (C) from calf skin and poly(acrylic acid) (PAA) were studied. Mixing aqueous solutions of collagen and PAA, at various pH values (2.5–4), leads to the formation of complexes that precipitate in the form of insoluble aggregates. The effects of mixture composition, pH, and ionic strength on C/PAA complex formation were investigated by gravimetric, turbidimetric, and conductometric analysis. The experimental results indicate that the complexes form through electrostatic interactions. Homogeneous solid films with variable C/PAA ratios were obtained by casting from solutions in which the pH was adjusted just over the isoelectric point of collagen, thus avoiding the attractive ionic interactions responsible for the complexation of collagen and PAA molecules. A relevant result obtained is related to the possibility of restoring the ionic interactions between the two polymers inside the solid films. Mixture composition and pH appear to influence the thermal properties of both complexes and films. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 971–976, 1999     

Structure and properties of the polyelectrolyte complex of chitosan with poly(methacrylic acid)

The structure and properties of the polyelectrolyte complex composed of chitosan (CS) and poly(methacrylic acid) (PMAA) were studied in aqueous solutions using UV‐visible transmittance measurements, a fluorescence probe technique, and transmission electron microscopy. The thermal properties of the solid complex were measured using differential scanning calorimetry. The results showed that the complex optimum molar ratio (in monomer unit) of CS to PMAA is 1:4 at pH = 4.0, that is, there is an optimum complex between CS and PMAA when the feed ratio (in molar monomer unit) of CS to PMAA is 1:4 and an ionic bond between the amino ion group and carboxylate group can be formed on average every four carboxylate (or carboxyl) groups. The conformation of PMAA changed from a hypercoiled to a loose coil on complexation, and the pH‐ and salt‐sensitive range of the polyelectrolyte complex was obviously different from that of CS or PMAA. The formation process of the complex under various external conditions is discussed in detail. Transmission electron microscopy revealed that the sizes of CS–PMAA complex particles increased with increasing pH or salt concentration, and a change in morphology of the complex was observed. Thermal analysis further revealed that there was a change of structure and properties on blending in aqueous solutions. Copyright © 2007 Society of Chemical Industry     

Studies on chitosan and poly(acrylic acid) interpolymer complex. I. Preparation,structure, pH-sensitivity,and salt sensitivity of complex-forming poly(acrylic acid): Chitosan semi-interpenetrating polymer network

A novel semi-interpenetrating polymer network (semi-IPN) membrane composed of crosslinked chitosan(cr-CS) and poly(acrylic acid) (PAA) was prepared. Evidence from infrared spectra proved the formation of polyelectrolyte complex through electrostatic interaction between groups from CS and COO⁻ groups from PAA. The semi-IPN membrane swelled at high pH and at low pH exhibited a typical pH-sensitivity. Its swelling degrees in different salt solutions with the same ionic valence and equal ionic strength were on similar levels. Under certain ionic strength (I = 1.5 mol/L), the degree of swelling increased with increased metal ionic valence. Furthermore, the elongation of the semi-IPN membrane could vary reversibly by immersion into CaCl₂ solution and KCl solution alternately. Reasons for the chemomechanical behavior are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1445–1450, 1997     

Micelles of polyisobutylene-block-poly(methacrylic acid) diblock copolymers and their water-soluble interpolyelectrolyte complexes formed with quaternized poly(4-vinylpyridine)

The micellization of ionic amphiphilic diblock copolymers, polyisobutylene-block-poly(methacrylic acid) (PIB-b-PMAA), with a constant degree of polymerization of the non-ionic block and various degrees of polymerization of the polyelectrolyte block was examined in aqueous media by means of fluorescence spectroscopy using pyrene as a polarity probe. The molar values of the critical micellization concentration (cmc) were found to be around 2×10⁻⁶ mol/l, being nearly independent of the length of the polyelectrolyte block as well as pH (in the range 6-9) and ionic strength (≤0.5 M NaCl) while the specific cmc values varied from 20 to 100 mg/l. Small-angle neutron scattering (SANS) and dynamic light scattering (DLS) experiments provided evidence that aggregation numbers and hydrodynamic radii of the formed copolymer micelles are sensitive to variations of pH and ionic strength, indicating that these micelles might be ‘dynamic’ rather than ‘frozen’ ones. It was also shown by means of a combination of turbidimetry, analytical ultracentrifugation, fluorescence spectroscopy, SANS, and DLS that the formed copolymer micelles mixed with a strong cationic polyelectrolyte, poly(N-ethyl-4-vinylpyridinium bromide) at charge ratio Z=[+]/[−] not exceeding a certain critical value Z_M<1, generate peculiar water-soluble micellar complex onion-like species, each containing a two-phase hydrophobic nucleus and a hydrophilic corona. The nucleus consists of a PIB core and a shell assembled from the fragments of water-insoluble interpolyelectrolyte complex. The corona is formed by the excess fragments of poly(sodium methacrylate) blocks not involved in complexation with poly(N-ethyl-4-vinylpyridinium bromide).     

Salt-, pH- and temperature-responsive semi-interpenetrating polymer network hydrogel based on poly(aspartic acid) and poly(acrylic acid)

In this study, a novel salt-, pH- and temperature-responsive semi-interpenetrating network (semi-IPN) hydrogel, composed of poly(aspartic acid) (PAsp) and poly(acrylic acid) (PAAc), was prepared. PAsp/PAAc semi-IPN hydrogel being ionic in nature, the swelling behavior was significantly influenced by various swelling medium. The structure of the triply responsive hydrogel was studied by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), and the salt-, temperature- and pH-sensitivities were investigated through measuring equilibrium swelling ratios in various environmental solutions. The results indicate that there is a structure of polyelectrolyte complex in the hydrogel, and that the responsive behaviors of this hydrogel to alternating changes in inorganic salt (different physiological bio-fluids), pH and temperature are improved because of the incorporation of PAsp. In addition, during the repeatable swelling and shrinkage period, the semi-IPN hydrogel shows suitable mechanical strength. The salt-, pH- and temperature-responsive hydrogel will have wider applications in biomedical areas.     

Well-defined multi-stimuli responsive fluorinated graft poly(ether amine)s (fgPEAs)

Well-defined multi-stimuli responsive fluorinated graft poly(ether amine)s (fgPEAs) were synthesized through nucleophilic substitution/ring-opening reaction of commercial poly(propylene glycol) diglycidyl ether and Jeffamine L100, followed by functionalization of hydroxyl groups in backbone by fluorinated alkyl carboxylic acid. fgPEAs are comprised of hydrophilic short poly(ethylene oxide) (PEO) and hydrophobic fluorinated alkyl chains, which are grafted on poly(propylene oxide) (PPO) backbone alternately to form well-defined structure. In aqueous solution, fgPEA11 and fgPEA12 self-assembled into multi-dispersed micelles, while fgPEA13 formed the uniform-sized micro-micelles with diameter of about 200 nm. These obtained micelles from fgPEAs were multi-responsive to temperature, pH and ionic strength with tunable cloud point (CP). It’s notable that CP of fgPEAs aqueous solution increased with the increasing amount of graft fluorinated alkyl chains.     

Interpolymer complexes of poly(acrylamide) and poly(N-isopropylacrylamide) with poly(acrylic acid): a comparative study

The interpolymer complexation, through successive hydrogen bonding, between poly(acrylamide) (PAAm) and poly(N-isopropylacrylamide) (PNiPAAm) with poly(acrylic acid) (PAA) in aqueous solution has been viscometrically and potentiometrically investigated. The stoichiometry of the complexes formed was determined. By comparing the strength of the two complexes the very important contribution of the hydrophobic interaction in their formation has been indicated.     

Synthesis and swelling properties of pH‐sensitive hydrogels based on chitosan and poly(methacrylic acid) semi‐interpenetrating polymer network

A novel semi‐interpenetrating polymer network (semi‐IPN) hydrogel composed of chitosan and poly(methacrylic acid) was synthesized using formaldehyde as a crosslinker. The amount of crosslinker was searched and optimized. The structure of the hydogel was investigated by Fourier transform infrared (FTIR) spectroscopy. The spectrum shows that a structure of polyelectrolyte complex exists in the hydrogel. The effects of pH, ionic strength, and inorganic salt on the swelling behaviors of the hydrogel were studied. The results indicate the hydrogel has excellent pH sensitivity in the range of pH 1.40 to 4.50, pH reversible response between pH 1.80 and 6.80, and ionic strength reversible response between ionic strength 0.2 and 2.0M. The results also show that the hydrogel has a bit higher swelling capacity in a mix solution of calcium chloride (CaCl₂) and hydrochloric acid (HCl) solution than in a mix solution of sodium chloride (NaCl) and HCl. These results were further confirmed through morphological change measured by scanning electron microscope (SEM). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1720–1726, 2005     

Overshooting effect of poly(dimethylaminoethyl methacrylate) hydrogels

An overshooting effect was observed during the swelling procedure of poly(dimethylaminoethyl methacrylate) (PDMAEMA) gel for the first time. The effects of the temperature, ionic strength, and pH on the overshooting effect of the PDMAEMA gel were investigated. We found that the overshooting effect of the gel could not be eliminated by changing the temperature; however, the overshooting effect was indiscernible in high‐concentration NaCl solutions (>0.2 mol/L) and basic (pH 11.9) and acidic solutions (pH = 2.1). The overshooting effect of the PDMAEMA gel was attributed to the dynamic conformational changes of the side chains of dimethylaminoethyl methacrylate (DMAEMA) units during the swelling of the gels. In the presence of NaCl or NaOH, the stretching of the macromolecular chains of the gels was disrupted. While in acidic solution, the protonation of tertiary amino groups in the DMAEMA units made the side chains of the DMAEMA units change from the cyclic conformation to the stretched one; this was analyzed with the aid of Fourier transform infrared spectroscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of strong polyelectrolyte hydrogels based on poly(vinyl alcohol)

Maleic anhydride (MA) was grafted onto both partially and fully hydrolyzed poly(vinyl alcohol) (PVA) in the presence of an initiator. Strong polyelectrolyte polymers were prepared by sulfonation of PVA–MA grafts. The sulfonation was completed by reaction of hydroxyl groups of PVA–MA grafts with two different sulfonating reagents (chlorosulfonic acid and pyridine sulfonic acid). The sulfonation degree was evaluated by acid–base titration and ¹H NMR analysis. The solution behaviour of the prepared grafts was evaluated from viscosity measurements. Four kinds of water‐insoluble PVA–MA and PVA–MA‐SO₃H hydrogels were prepared by heat treatment, physical gelation and chemical crosslinking with different weight ratios of N,N‐methylene bisacrylamide (MBA) crosslinker. The swelling parameters were measured for all prepared gels in deionized water and aqueous solutions at different pH values from 2 to 12 having constant ionic strength (I = 0.1). All gels exhibit a different swelling behaviour upon environmental pH changes. Copyright © 2004 Society of Chemical Industry     

Fabrication and stability of porous poly(allylamine) hydrochloride (PAH)/poly(acrylic acid) (PAA) multilayered films via a cleavable-polycation template

Porous films were fabricated from nonporous layer-by-layer multilayers composed of a blend of positively charged disulfide-containing polyamidoamine and poly(allylamine hydrochoride), and negatively charged poly(acrylic acid), followed by removal of cleavable disulfide-containing polycation after incubation in 1 mM DTT solution. The thickness of original multilayered films decreased with the increase of incubation time in DTT solution. Atomic force microscopy (AFM) measurements and electrochemical analysis demonstrated the formation of nanopores with sizes ranging from 50 to 120 nm. The formed porous films were stable in buffer solution at pHs ranging from 7.4 to 1.6, whereas they showed slight changes in pore number and pore size when incubated in PBS buffer at a pH of 10.0. This research might provide a universal method for the fabrication of noncrosslinked porous multilayered films.     

Interpolyelectrolyte complex of poly(2‐vinylpyridinium chloride) and poly(sodium phosphate)

A polyelectrolyte complex (PEC) was formed by mixing aqueous solutions of the polyanion poly(sodium phosphate) with the polycation poly(2‐vinylpyridinium chloride). Conductometric and potentiometric titrations indicated the electrochemical end point of each titration. In all cases the end point occurred at a unit molar ratio of polyanionic to polycationic groups that was approximately one. The stoichiometry was also confirmed by analysis of the supernatant liquid in conjunction with the weights of the initial components and complex. An analysis showed that the starting materials were regenerated after dissolution of the complex with a 2M HCl solution. The interaction of the bivalent cupric ions with PEC were also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3022–3028, 2002; DOI 10.1002/app.2332     

Infrared spectroscopy and electrical properties of ternary poly(acrylic acid)–metal–poly(acrylamide) complexes

Fourier transform infrared spectroscopy (FTIR) and electrical measurements were used for the characterization of the interpolymer complexation between poly(acrylic acid) (PAA) and poly(acrylamide) (PAAm) and also the ternary PAA–metal–PAAm complexes. The interpolymer complexes were prepared by adjusting the pH value of the mixture solutions at different PAA weight fractions (W_PAA). The ternary complexes were prepared by mixing metal chloride solutions (such as ErCl₃ and LaCl₃) with different concentrations to PAA–PAAm mixtures and adjusting the pH value for different W_PAA. It was found that the IR spectra of the interpolymer complexes showed absorption bands at shifted positions and of intensities different from those of the parent polymers. Also, the examination of the spectra of the ternary metal–polymer complexes revealed that they depend on the nature, lency, ionic radius, and concentration of the added metal chlorides. Analysis of the electrical results showed that the electrical conductivity of the interpolymer complexes are always lower than those of PAA and PAAm, which was attributed to the decrease in the mobility of the polymer chains as a result of the complexation. Also, the conductivity of the ternary metal complexes showed a dependence on the properties of the additives and were found to decrease with increasing their concentrations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2699–2705, 2002     

Thermodynamic Association Behaviors of Sodium Dodecyl Sulfate (SDS) with Poly(4-vinylpyridine <Emphasis Type="Italic">N</Emphasis>-oxide) (PVPNO) at Different pH Values and Ionic Strengths

The interaction of sodium dodecyl sulfate (SDS) with poly(4-vinylpyridine N-oxide) (PVPNO) at different pH values and ionic strengths has been studied by isothermal titration microcalorimetry, electrical conductivity and turbidity measurements. The solution pH significantly effects the formation of the PVPNO/SDS complex. At pH 1.5, the polymer PVPNO is a strong polycation, and the binding is dominated by electrostatic 1:1 charge neutralization with the anionic surfactant. At pH 6 and 8, the electrostatic attraction between SDS and PVPNO is weak, and the hydrophobic interaction becomes stronger. The effect of salt concentration on the interaction of SDS and PVPNO depends on the competition between the increase of interaction and the screening of interaction. This study based on the thermodynamic process gained deep insight into the effects of pH value and ionic strength on the interaction mechanism of surfactant with polyelectrolyte. We also constructed a simple model for the interaction of PVPNO and SDS system in different solution regions.     

Water-soluble polyelectrolyte complexes formed by poly(diallyldimethylammonium chloride) and poly(sodium acrylate-co-sodium 2-acrylamido-2-methyl-1-propanesulphonate)-graft-poly(N,N-dimethylacrylamide) copolymers

The formation of polyelectrolyte complexes (PECs) between the cationic homopolymer poly(diallyldimethylammonium chloride) (PDADMAC) and the anionic graft copolymers poly(sodium acrylate-co-sodium 2-acrylamido-2-methyl-1-propanesulphonate)-graft-poly(N,N-dimethylacrylamide) (P(NaA-co-NaAMPS)-g-PDMAM) was studied in aqueous solution in comparison with the PECs formed between PDADMAC and the graft copolymer backbone poly(sodium acrylate-co-sodium 2-acrylamido-2-methyl-1-propanesulphonate). The turbidimetric study of the PECs formed revealed that associative phase separation is prevented when the anionic polyelectrolyte is grafted with the nonionic hydrophilic poly(N,N-dimethylacrylamide) side chains. The PECs are formed through a charge neutralisation process and they adopt a compact structure, as shown by conductivity and viscometry measurements respectively. The water-insoluble PEC core seems to be stabilised by a hydrophilic PDMAM corona, leading to the formation of nanoparticles with a hydrodynamic radius of some decades of nanometers as determined by quasi-elastic light scattering measurements.     

Electrical conductivity of poly(vinyl alcohol)/carbon nanotube multilayer thin films: Influence of sodium polystyrene sulfonate mediated carbon nanotube dispersion

This investigation was aimed to enhance the dispersibility of multi-walled carbon nanotubes (MWCNT) using sodium polystyrene sulfonate (Na-PSS) polyelectrolyte. Subsequently, electrically conducting, multi-layer thin films are prepared utilizing layer by layer assembly method with poly(vinyl alcohol) as a host matrix. The highest extent of MWCNT dispersion was observed in MWCNT:Na-PSS ratio of 1:9 (wt/wt), which was estimated from UV-Vis spectroscopic analysis. Zeta potential measurements of Na-PSS modified MWCNT dispersion showed large negative potentials ranging from −52 to −64 mV in the most stable pH range of 4 to 10, suggesting the colloidal stability is due to the long-range repulsive nature of electrostatic interactions from negatively charged sulfonate groups. Complementary molecular dynamics simulations showed that adsorption of Na-PSS imparts a large negative potential to the carbon nanotube surface, which increases with an increase in Na-PSS concentration. The multi-layer thin film of (1:9) MWCNT:Na-PSS exhibited a DC electrical conductivity of 2.96 × 10² S/m.