Complexation Equilibrium Constants of Poly(vinyl alcohol)-Borax Dilute Aqueous Solutions – Consideration of Electrostatic Charge Repulsion and Free Ions Charge Shielding Effect

Equilibrium dialysis experiments of dilute poly(vinyl alcohol) (PVA) in borax aqueous solution (PVA concentration was 2 g/L and borax concentration ranged from 0.0 M to 0.05 M) were carried out to determine the concentration of free borate ions in equilibrium with the PVA-borate complex at 25°C, and hence the amount of borate bound to PVA. The binding isotherm of borate ion on PVA molecules was investigated. The concentration of borate ion bound on PVA was found to increase with increasing borax concentration and reached an asymptote at high borax concentrations. The complexation equilibrium constant between borate and PVA diol was found to decrease initially then increases and finally decreases with increasing borax concentration while PVA concentration was fixed in a constant value. The equlibrium constant of free borate ion with borate-PVA diol complex was a balance result of excluded volume of PVA molecular chains, electrostatic charge repulsion between free borate ions and borate-PVA diol complexes, and electro-shielding of free Na⁺ ions on negatively charged PVA-borate complexes. In this study, the electrostatic charge repulsion between free borate ions and borate-PVA diol complex ions and free Na⁺ ions shielding effect are considered in the estimation of equilibrium constants of PVA diol-borate complexation. A fixed value of equilibrium constant is obtained with increasing borax concentration while borax concentraion is below a critical concentration [borax]_crt. As borax cocentration is higher than [borax]_crt, a lots of PVA diols form complexes with borate ions and a high shielding of free Na⁺ ions on negatively charged borate-PVA diol complexes causes the PVA-borate complexes to behave like neutral polymers. Few free PVA diol binding sites are available for reaction with free borate ions while borax concentration is higher than [borax]_crt resulting in a decrease in equilibrium constant with increasing borax concentration.     

Light scattering and viscoelasticity study of poly(vinyl alcohol)-borax aqueous solutions and gels

Poly(vinyl alcohol)-borate (PVA-borate) aqueous solutions properties with PVA concentrations ranging from 2 to 60 g/L and borax concentrations of 0.0 and 0.2 M were investigated at room temperature using static and dynamic light scattering (SLS and DLS), and dynamic viscoelasticity measurements. Light scattering and viscoelasticity data revealed that all the PVA-borate aqueous systems, except those with [PVA]≥40 g/L and [borax]=0.2 M, behaved as solutions. For PVA-borate aqueous systems with [PVA]≥40 g/L and [borax]=0.2 M, light scattering data revealed that these systems behaved like gels, but viscoelasticity data showed that these systems were in flow states. The experimental data suggest that PVA-borate aqueous systems with [PVA]≥40 g/L and [borax]=0.2 M are thermoreversible gels with finite equilibrium life time of thermoreversible borate-PVA di-diol crosslinks. The thermoreversible crosslinks can be observed by the non-perturbing light scattering technique but not by the pertubing rheometric method. These results indicate the advantage of light scattering relative to rheometers for studying the physical or reversible crosslink gels.     

Transition of hydration states of poly(vinyl alcohol) in aqueous solution

A straightforward method for determination of the hydration number of polymer in aqueous solution based on ice-melting technique of DSC is proposed. The simple yet precise method has been applied to determine the hydration number of poly(vinyl alcohol) (PVA) in aqueous solution covering a wide range of concentrations, from 0.005 to 0.3 g(solute)/g(solution), for three samples with different molar masses. The hydration number of PVA maintains a constant lower value of 2.5 when the concentration exceeds 0.2 g(solute)/g(solution). It increases to a value of 7 when the concentration decreases to the overlap concentration C^∗ of the polymer, where C^∗ was estimated as the reciprocal of its intrinsic viscosity. For solutions of C < C^∗, the hydration number keeps constant again at the value of 7. This behavior evidently demonstrates that PVA has two hydration states, one occurs at the dilute regime and the other occurs at concentrated regime. The concentration dependent transition from one state to another is treated mathematically by a quantitative formula which involves two parameters: one denotes the transition concentration and the other denotes the width of the transition region. The transition concentration decreases linearly with increasing molar mass resembling the behavior of molar mass dependence of overlap concentration. The structural features for the two states of hydrated PVA are briefly discussed.     

Synthesis of boronate-containing copolymers of N,N-dimethylacrylamide, their interaction with poly(vinyl alcohol) and rheological behaviour of the gels

Cross-linking of polyvinylalcohol (PVA) by boronate-containing copolymer of N,N-dimethylacrylamide (DMAA, 1) was studied and compared to cross-linking of PVA by borate buffers in weakly alkaline solutions. The copolymer of M_w=19,000 g mol⁻¹ containing 9 mol% N-acryloyl-m-aminophenylboronic acid (NAAPBA, 2) was prepared by free radical polymerization of the monomers, exhibiting copolymerization constants r₁=0.84 and r₂=2.2. Due to multipoint interaction of the copolymer with PVA via monodiols, the intermolecular cross-linking required for seven-fold and 10-fold lower boron concentrations as compared to borate buffers of pH 8.6 and 7.5, respectively. In rheological measurements, PVA-copolymer gels exhibited storage moduli (G′_max) comparable to those of PVA-borate gels prepared at 7.5-fold higher boron concentration and the same pH 8.6, what testified to the similar concentration of cross-links in the gels. Therefore, DMAA-NAAPBA copolymer is a more effective cross-linker of PVA than borate. The PVA-copolymer gel exhibited much higher relaxation time (97 s) compared to PVA-borate gels (≤20 s) indicating a longer lifetime of junction zones. The ‘shape stability’ of the gel is suggested to originate in the structure of junctions, containing several boronate-diol complexes, between the macromolecules of PVA and the copolymer.     

Synthesis and rheological properties of hydrophobically modified poly(vinyl alcohol)

A novel series of water-soluble hydrophobically modified poly(vinyl alcohol) (HMPVA) with various hydrophobe contents was prepared by grafting poly(vinyl alcohol) (PVA) using 1-dodecanol and toluene-2,4-diisocyanate as hydrophobic monomer and coupling agent, respectively. The chemical structure of HMPVA was analyzed by Fourier Transform Infrared Spectrometer (FTIR) and ¹H NMR. Rheological properties of the aqueous solutions also confirmed the incorporation of hydrophobic groups into PVA. In dilute concentration regime, HMPVAs exhibited lower intrinsic viscosity than PVA, suggesting that HMPVA molecules were more shrunken. While the aqueous solution viscosity was enhanced due to hydrophobic modification at a high concentration, and HMPVAs with higher hydrophobe contents exhibited lager values of apparent viscosities. Over a frequency range of 1 to10² rad/s, the dynamic storage modulus of PVA solution was smaller than the dynamic loss modulus whereas the dynamic storage modulus of HMPVAs solutions was greater than the dynamic loss modulus, indicating the evolution of viscoelastic solid properties in HMPVAs solutions. The yield stress of PVA was nearly zero whereas that of HMPVAs represented positive values, implying that networks were present in HMPVAs solutions.     

Molecular size and aggregation behavior of Erwinia gum in aqueous solution

Erwinia (E) gum, a stabilizer and thickening agent of food, is composed of glucose, fucose, galactose, and glucuronic acid (1 : 0.1 : 0.05 : 0.3 by molar ratio). The apparent weight‐average molecular weight M_w and intrinsic viscosity [η] in 0.2 M NaCl aqueous solution were measured to be 7.83 × 10⁵ and 268 mL g⁻¹, respectively, by light scattering and viscometry. The aggregation behavior of E gum in aqueous solution was investigated by gel permeation chromatography (GPC) and dynamic light scattering. The results showed that 7.5% E gum exists as an aggregate, whose diameter is 12 times greater than single‐stranded chain, in aqueous solution at 25°C, and the aggregates' content decreased with increasing temperature or decreasing polymer concentration. The aggregates at higher temperature were more readily broken than in exceeding dilute solution. GPC analysis proved that a significant shoulder, corresponding to a fraction of higher molecular weight due to chain aggregation, appeared in the chromatogram of E gum in 0.05 M KH₂PO₄/5.7 × 10⁻³ M NaOH aqueous solution (pH 6.0) at 35°C, and decreased with increasing temperature, finally disappeared at 90°C. The disaggregation process of E gum in aqueous solution can be described as follows: with increasing temperature, large aggregates first were changed into the middle, then disrupted step by step into single‐stranded chains. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1083–1088, 2000     

Aggregation behavior of poly(methacrylic acid) with cucurbit[7]uril and the effect of ammonia ions on aggregation

The interaction between poly(methacrylic acid) (PMAA) and cucurbit[7]uril (CB[7]) in aqueous solution were investigated by dynamic light scattering (DLS), fluorescence techniques, UV-spectrophotometer, and resonance light scattering (RLS). The experimental results show that the aggregates were formed between CB[7] and H⁺ of PMAA by the hydrogen bonding interaction that increases with increasing the concentration of CB[7], which leads to the formation of the larger aggregates. Interestingly, PMAA has temperature sensitivity with the addition of CB[7] by UV-spectrophotometer and DLS. The pH of the solution of PMAA appears a inflection point with increasing the concentration of CB[7] comparing with the increase of the electrical conductivity all the time with the addition of CB[7]. In addition, in order to investigate the effect of cation on the size of the aggregates and avoid the effect of other anions at the same time, the dilute ammonia was added into the solution of PMAA. The experimental data show that the size of the aggregates increases with adding CB[7] because CB[7] could combine with both NH₄⁺ by the electrostatic and iondipole interactions and H⁺ by the hydrogen bonding interaction, and a possible model is proposed to explain the host-guest interactions between PMAA and CB[7].     

Electrostatic self-assembly of thermally responsive zwitterionic poly(N-isopropylacrylamide) and poly(ethylene oxide) modified with ionic groups

The electrostatic self-assembly of thermally responsive copolymers of N-isopropylacrylamide (NIPAM) containing up to 10 mol% of the sulfobetaine monomer 3-[N-(3-methacrylamidopropyl)-N,N-dimethyl]ammoniopropane sulfonate) (SPP) and poly(ethylene oxide) modified with terminal cationic or anionic groups (IMPEO) was studied in methanol and aqueous solutions by static light scattering, turbidimetry, viscometry, and rheological measurements. The formation of graft-like complexes at stoichiometric dipole-ion ratio and their self-association was detected in the dilute and semidilute regime at temperatures below and above the lower critical solution temperature (LCST). The ability of the graft-like complexes to associate below the LCST depended on the sulfobetaine content of the copolymers, the functionality of IMPEO, and the polymer concentration. The effect of the IMPEO terminal group on the solution behavior of the graft-like complexes was less pronounced. With increasing temperature their semidilute aqueous solutions form gels, stable over a wide temperature range.     

Potential applications of poly(vinyl alcohol)‐congo red aqueous solutions and hydrogels as liquids for hydraulic fracturing

The authors report on the viscoelastic characterization of guar hydrogels obtained through complexation reactions with borax ions. These gels are compared with hydrogels obtained from poly(vinyl alcohol) of different degree of hydrolysis through complexation reactions with congo red. The effect of the degree of hydrolysis and both, the concentration of PVA and the concentration of congo red, on the viscoelastic properties of the hydrogels is analyzed. The potential use of the PVA‐based hydrogels as hydraulic fracturing liquids is discussed in relation to the commonly used fracturing liquid based on the guar–borax system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The role of solvation on the conformational change during repeated freezing-thawing treatment to an extremely dilute aqueous solution of poly(vinyl alcohol)

The effect of solvation-desolvation process on the conformational change of poly(vinyl alcohol) in an extremely dilute aqueous solution during the repeated freezing-thawing treatment was investigated by a differential refractometer. It was found that the hydrodynamic volume of PVA decreased regularly and smoothly with the number of freezing-thawing cycles treatment increasing, as the intra-molecular entanglement points made the polymer chain contract, and even in a full compacted globule state, there were still some solvent molecules in the chain. The extraordinary phenomenon was successfully explained and treated by a quantitative theory in terms of accompanying solvation-desolvation process during the macromolecular chain having contracted.     

Investigation of the complexation of proteins with neutral water soluble polymers through model analysis method

In the current research, the complexation of bovine serum albumin (BSA) with poly(N-isopropylacrylamide) (PNIPAM) is studied in an aqueous system (pH 7) which contains NaCl as its supporting salt, and based on the electric charge conservation law a mathematical model used to quantitatively characterize the complexation between proteins and neutral polymers is established. This model, which is set up on the assumptions that there exists a dynamic equilibrium of absorption and desorption among free proteins, complexes and free polymers in the aqueous complex system and the complexation sizes of proteins with neutral water soluble polymers are not uniform, better reveals the actual state of complexation. By means of dynamic light scattering (DLS), fluorescence spectrophotometer and zeta potential analyzer, all necessary parameters of the mathematical model have been acquired accurately without destroying the dynamic equilibrium of the aqueous complex system. The calculated results demonstrate that, with the rise of mixing ratio (r_mixing, molar ratio of PNIPAM to BSA), both the average number of bound BSA per PNIPAM (n_b) and the diameters of complexes (R_h) decrease gradually, while the zeta potential (ζ) and the concentration of free PNIPAM ([PNIPAM]_free) increase. In addition, the average number of PNIPAM in the complexes (φ) and the molecular weight of the complexes (M_w) can also be calculated by this mathematical model. The changing pattern of M_w with r_mixing is in accordance with the results of static light scattering (SLS). This analysis method, which interprets the interaction between neutral polymers and proteins in an aqueous system, is a new way to calculate the complex parameters and study the complexation mechanism between proteins and polymers.     

Evaluation of the Hydrophilic Complexant N,N,N’,N’-tetraethyldiglycolamide (TEDGA) and its Methyl-substituted Analogues in the Selective Am(III) Separation

ABSTRACT

N,N,N’,N’-tetraethyldiglycolamide (TEDGA) is used in the French EXAm (extraction of americium) process to separate Am(III) from Cm(III) and Ln(III). In this study, the complexation behavior of TEDGA towards actinides(III) and lanthanides(III) was compared to its methyl-substituted derivatives Me-TEDGA and Me₂-TEDGA under experimental conditions applying to the EXAm process. Using the EXAm solvent, 0.6 mol/L N,N’-dimethyl-N,N’-dioctyl-hexylethoxymalonamide (DMDOHEMA) and 0.45 mol/L bis(2-ethylhexyl)-phosphoric acid (HDEHP), An(III) and Ln(III) distribution ratios increase in the order TEDGA < Me-TEDGA < Me₂-TEDGA. This is explained by differences in the strength of complexation in the aqueous phase: Conditional stability constants for the formation of [Cm(DGA)_x]³⁺ complexes decrease in the order TEDGA > Me-TEDGA > Me₂-TEDGA, as shown by time-resolved laser fluorescence spectroscopy (TRLFS). TRLFS measurements verified the exclusive existence of [Cm(DGA)₃]³⁺ complexes in the aqueous phase. Both the homoleptic [Cm(DMDOHEMA)_n]³⁺ and the heteroleptic [Cm(DGA)_x(DMDOHEMA)_y]³⁺ complexes were detected in the organic phase, as postulated in the literature.^[14]     

Effect of molecular architecture on the self-diffusion of polymers in aqueous systems: A comparison of linear, star, and dendritic poly(ethylene glycol)s

Star polymers with a hydrophobic cholane core and four poly(ethylene glycol) (PEG) arms, CA(EG_n)₄, have been synthesized by anionic polymerization. Pulsed-gradient spin-echo NMR spectroscopy was used to study the diffusion behavior of the star polymers, ranging from 1000 to 10,000 g/mol, in aqueous solutions and gels of poly(vinyl alcohol) (PVA) at 23 °C. The star polymers have a lower self-diffusion coefficient than linear PEGs at equivalent hydrodynamic radius. In water alone, the star polymers and their linear homologues have a similar diffusion behavior in the dilute regime, as demonstrated by the similar concentration dependence of the self-diffusion coefficients. In the semidilute regime, the star polymers tend to aggregate due to their amphiphilic properties, resulting in lower self-diffusion coefficients than those of linear PEGs. ¹H NMR T₁ measurements at 10-70 °C revealed that the PEG arms of the star polymers are more mobile than the core, suggesting the star polymers in solution have a conformation similar to that of poly(propylene imine) dendrimers.     

Static and dynamic light scattering study of strong intermolecular interactions in aqueous solutions of PVP/C60 complexes

The investigations of the dilute aqueous solutions of polyvinylpyrrolidone/fullerene (PVP/C₆₀) complexes by static (SLS) and dynamic (DLS) light scattering showed that strong intermolecular interactions, effective on the distances of about 45-50 nm, take place in the solutions. Two concentration ranges are well distinguished in these solutions. Above a critical concentration (c_cr) the fluctuations in the solutions are hindered and only one, diffusive, mode is observed in DLS experiments. Upon dilution (c<c_cr) this unified structure divides into large fragments (domains) and the slow mode attributed to long-range concentration fluctuations, gradually appears. The angular and concentration dependencies of the diffusion coefficient of the slow mode indicate the existence of strong intermolecular interactions.     

Formation of amphiphilic complexes of cationic polyelectrolyte carrying pendant saccharide residue with anionic surfactants

The formation of amphiphilic complexes of poly(allylammonium chloride) carrying pendant maltose residue (PAAHCl-Mal) with sodium alkylsulfonates (sodium octanesulfonate (NaOcS), sodium dodecanesulfonate (NaDoS), sodium hexadecanesulfonate (NaHeDeS)) in aqueous solution was studied by means of turbidimetry, fluorescence spectroscopy using pyrene, ¹H NMR and viscometry. In contrast to the complex of PAAHCl homopolymer with NaDoS, which precipitated at the ratio of the concentration of DoS to the concentration of ammonium group in the polymer, [DoS]/[NH₃⁺]=0.01, the complexes of PAAHCl-Mal(14) containing 14 mol% maltose residue with NaDoS are water-soluble over the whole range of compositions of the mixture, including the electroneutralized condition, [DoS]/[NH₃⁺]=1. In the mixture of PAAHCl-Mal(14) and NaDoS at [DoS]/[NH₃⁺]=1, the ratio (I₃/I₁) of the intensities of third and first vibrational bands of pyrene was 0.83, indicating that the complexation of PAAHCl-Mal(14) with NaDoS gives rise to a hydrophobic domain. In addition to these results, from ¹H NMR and viscosity measurements of the PAAHCl-Mal(14) and NaDoS system, it seems that these species form a micelle like aggregate with a hydrophobic core from the surfactants bound to the polymer and a hydrophilic outer shell from the maltose residues. Moreover, the effects of content of maltose residue in the polymer and alkyl chain length of surfactant on the complexation of PAAHCl-Mal with alkylsulfonates are discussed.     

Recovery of the N,N-Dibutylimidazolium Chloride Ionic Liquid from Aqueous Solutions by Electrodialysis Method

Ionic liquids (ILs), named also as liquid salts, are compounds that have unique properties and molecular architecture. ILs are used in various industries; however, due to their toxicity, the ILs’ recovery from the postreaction solutions is also a very important issue. In this paper, the possibility of 1,3-dialkylimidazolium IL, especially the N,N-dibutylimidazolium chloride ([C₄C₄IM]Cl) recovery by using the electrodialysis (ED) method was investigated. The influence of [C₄C₄IM]Cl concentration in diluate solution on the ED efficiency was determined. Moreover, the influence of IL on the ion-exchange membranes’ morphology was examined. The recovery of [C₄C₄IM]Cl, the [C₄C₄IM]Cl flux across membranes, the [C₄C₄IM]Cl concentration degree, the energy consumption, and the current efficiency were determined. The results showed that the ED allows for the [C₄C₄IM]Cl recovery and concentration from dilute solutions. It was found that the [C₄C₄IM]Cl content in the concentrates after ED was above three times higher than in the initial diluate solutions. It was noted that the ED of solutions containing 5–20 g/L [C₄C₄IM]Cl allows for ILs recovery in the range of 73.77–92.45% with current efficiency from 68.66% to 92.99%. The [C₄C₄IM]Cl recovery depended upon the initial [C₄C₄IM]Cl concentration in the working solution. The highest [C₄C₄IM]Cl recovery (92.45%) and ED efficiency (92.99%) were obtained when the [C₄C₄IM]Cl content in the diluate solution was equal 20 g/L. Presented results proved that ED can be an interesting and effective method for the [C₄C₄IM]Cl recovery from the dilute aqueous solutions.     

Study of solution properties of poly(deamino‐tyr‐tyr carbonate hexyl ester) by light scattering and viscometry in dilute and semidilute regime

The structure and properties of poly(deamino‐tyr‐tyr carbonate hexyl ester), in dilute and semidilute solutions, were studied using static, dynamic light scattering, and viscometry. The overlap concentration, c^* is determined by viscosity. The angular dependence of Zimm plots shows no downturn at low angles. In addition, bimodal distribution curves were computed from the quasielastic measurements. The radius of gyration and the second virial coefficient A₂ are found to be respectively 45.8 nm and 9.4 mol cm³ g^?2. The correlation and persistence lengths are discussed. The poly (deamino‐tyr‐tyr carbonate hexyl ester) or poly(DTH‐carbonate) chain in THF, at T = 20°C, behaves as a wormlike chain with persistence length. The persistence length obtained using light scattering is compared with that obtained using viscosity with good agreement. These values obtained from these measurements reflect a high degree of local chain persistence. The reduced viscosity in dilute regime provides a value of apparent viscosity hydrodynamic radius three times lower than obtained by static light scattering. POLYM. ENG. SCI., 50:1605–1612, 2010. © 2010 Society of Plastics Engineers     

Design of High-Relaxivity Polyelectrolyte Nanocapsules Based on Citrate Complexes of Gadolinium(III) of Unusual Composition

Through nuclear magnetic relaxation and pH-metry, the details of the complexation of gadolinium(III) ions with citric acid (H₄L) in water and aqueous solutions of cationic polyelectrolytes are established. It is shown that the presence of poly(ethylene imine) (PEI) in solution affects magnetic relaxation behavior of gadolinium(III) complexes with citric acid (Cit) to a greater extent than polydiallyldimethylammonium chloride (PDDC). A large increase in relaxivity (up to 50 mM⁻¹s⁻¹) in the broad pH range (4–8) is revealed for the gadolinium(III)–citric acid–PEI system, which is particularly strong in the case of PEI with the molecular weight of 25 and 60 kDa. In weakly acidic medium (pH 3–7), the presence of PEI results in the formation of two tris-ligand associates [Gd(H₂L)₃]³⁻ and [Gd(H₂L)₂(HL)]⁴⁻, which do not exist in aqueous medium. In weakly alkaline medium (pH 7–10), formation of ternary complexes Gd(III)–Cit–PEI with the Gd(III)–to–Cit ratio of 1:2 is evidenced. Using transmission electron microscopy (TEM) and dynamic light scattering techniques (DLS), the formation of the particles with the size of 50–100 nm possessing narrow molecular-mass distribution (PDI 0.08) is determined in the solution containing associate of PEI with tris-ligand complex [Gd(H₂L)₂(HL)]⁴⁻.     

Modification of non‐Newtonian flow behavior of aqueous solution of poly(vinyl alcohol) by conducting polypyrrole prepared by in situ polymerization of pyrrole

The rheological behavior of an aqueous solution of poly(vinyl alcohol) (PVA) and polypyrrole (PPY) dispersions prepared by ferric chloride (FeCl₃)‐catalyzed polymerization of pyrrole was investigated at 12°C using a coaxial rotational viscometer. The results show that the addition of a low dose of FeCl₃ to the PVA solution greatly influences its rheology. The prominent shear‐thickening (dilatant) nature of PVA turns significantly pseudoplastic (shear thinning) in the presence of FeCl₃. Polypyrrole‐loaded PVA was obtained in a stable, optically clear dispersion by in situ polymerization of pyrrole in an aqueous PVA solution (5%) using FeCl₃ as the oxidative catalyst at 12°C. The PPY dispersions in aqueous PVA systems having a low loading of PPY and low Fe⁺³ content retain the dilatant character of an aqueous PVA solution; however, for an aqueous PVA system having a relatively high PPY loading and also a high Fe⁺³ content, prominent pseudoplastic (shear thinning) behavior is exhibited. The odd novel rheological patterns exhibited by a PVA solution in the absence and presence of FeCl₃ and the PVA–PPY dispersions containing FeCl₃ under different sets of conditions are explained on the basis of the complexation of PVA by Fe⁺³ and related ions and also as a consequence of some degree of H‐bonding and chemical grafting between the support polymer PVA and the PPY formed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3737–3741, 2004     

Investigation of the interpolymer association between poly(vinyl alcohol) and poly(sodium styrene sulfonate) in aqueous solution

A viscosimetric method has been used to study the interpolymer association between poly(vinyl alcohol) (PVA) and poly(sodium styrene sulfonate) (PSSNa) in aqueous solution. At constant molecular weight of PSSNa, it was found that, the PVA and PSSNa associations were improved with the decrease of molecular weight of PVA and the decrease of its hydrolysis degree. The measurement of intrinsic viscosity [η] and the determination of Huggins associative coefficient K_H of different PVA samples were used to select the most appropriate PVA sample, which leads to homogeneous polymer–polymer mixtures (PVA with hydrolysis degree 87–89%, molecular weight 124,000–186,000 g/mol, intrinsic viscosity [η] = 1.02 dL/g, and Huggins associative coefficient K_h.ass = 0.76). The obtained results show that the interpolymer association between PVA and PSSNa, in aqueous solution, is mainly due to intermolecular hydrogen bonds between hydroxyl groups of PVA and sulfonate groups of PSSNa. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009