Dilute solution properties of naphthalene-labeled cationic poly(dimethyl sulfate quaternized acrylamide/N,N-dimethylaminopropylmaleimide copolymer)

The properties of a novel cationic, naphthalene-labeled cationic poly(dimethyl sulfate quaternized acrylamide/N,N-dimethylaminopropylmaleimide copolymer), poly-(DSQADMAPM)/NA in aqueous solution are examined in this study, measuring intrinsic viscosity, reduced viscosity, and ionic strength. This cationic poly(DSQADMAPM)/NA’s intrinsic viscosity is dependent on the type and concentration of salt added to the aqueous solution. The intrinsic viscosity behavior of the cationic poly(DSQADMAPM)/NA resulting from the electrostatic repulsive force of the polymer chain is contrasted with polyampholyte. Smaller anions such as F⁻ with a common cation (K⁺) are found to be the most difficult to be bound to the end group, indicating that a higher intrinsic viscosity of the poly(DSQADMAPM)/NA would be in KF salt aqueous solution. Smaller cations such as Li⁺ with a common anion (Cl⁻) are found to be the most difficult to be bound to the quaternary ammonium group, indicating that a higher intrinsic viscosity of the poly(DSQADMAPM)/NA would also be in LiCI salt aqueous solution. Models are proposed to account for the poly(DSQADMAPM)/NA solution viscometrics.     

Dilute solution properties of poly(3-dimethyl acryloyloxyethyl ammonium propiolactone)

The aqueous solution properties of an ampholytic poly(3-dimethylacryloyloxyethyl ammonium propiolactone), poly(DMAEAPL), are examined in this study by measuring reduced viscosity, intrinsic viscosity, degree of binding and dynamic light scattering. This polyampholyte's intrinsic viscosity is related to the type and concentration of the salt added. The intrinsic viscosity behaviour for the polyampholyte resulting from the associations of the polymer chains is in contrast with cationic and anionic polyelectrolyte. The polyampholyte in high concentration of NaCl has a low degree of binding, indicating that the proton ion (H⁺) has difficulty in binding to the carboxylate group (COO⁻) at the polymer end. The carboxybetaine, DMAEAPL, has a higher degree of binding than the corresponding sulfobetaine, DMAPS. Dynamic light scattering measurements indicate that the poly(carboxybetaine) diffusion coefficients decrease and the chain dimensions increase with an increasing salt concentration. The models proposed in this study can account for the poly(DMAEAPL) solution viscometrics and the degree of binding. © 1997 Elsevier Science Ltd.     

Viscometric Study of Dilute Poly(Acrylonitrile–Ammonium Itaconate) Solutions

The intrinsic viscosity of dilute poly(acrylonitrile–ammonium itaconate) copolymer solution in dimethyl sulfoxide was studied by viscometry. Abnormal phenomena of the η_sp/c versus c curves of poly(acrylonitrile–ammonium itaconate) were found. Owing to the effect of NH₄ ⁺, there were three anomalistic turning points in the curve of the Huggins dependence compared with other polyacrylonitrile copolymers.     

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.     

Intermolecular interactions between bovine serum albumin and certain water‐soluble polymers at various temperatures

Viscometric behaviors of dextran (Dx), poly(N‐vinyl‐2‐pyrrolidone) (PVP), and poly(ethylene oxide) (PEO) with bovine serum albumin (BSA) in aqueous solutions have been studied at 25, 30, and 35°C. The reduced viscosity and intrinsic viscosity have been experimentally measured for the polymer/water and polymer/BSA/water systems by classical Huggins equation. Measurements of reduced viscosities of the Dx, PVP, and PEO in water have been calculated and all intrinsic viscosities of PEO([η]_PEO) are larger than that of Dx([η]_Dx), and PVP([η]_PVP) in aqueous solutions, at all temperatures. The intrinsic viscosities of PVP, PEO, and Dx were found to be dependent on the concentration of BSA. The presence of BSA (0.05, 0.10, and 0.30 wt %) led to a decrease in the intrinsic viscosities of polymers, at 25, 30, and 35°C. The concentration difference of BSA (Δ[BSA]) is most effective in decreasing the intrinsic viscosities of Dx at 25°C and PEO at 30 and 35°C. In other words, Δ[η] (%) order followed as Dx > PEO > PVP at 25°C and PEO > Dx > PVP at 30 and 35°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1554–1560, 2006     

Poly(sulfobetaine)s and corresponding cationic polymers. XI. Synthesis and aqueous solution properties of a cationic poly(methyl iodide quaternized ethyl vinyl ether/N,N‐dimethylaminopropyl maleamidic acid) copolymer

A copolymer prepared by the copolymerization of ethyl vinyl ether and maleic anhydride underwent amidoacidation with N,N‐dimethylaminopropylamine. The obtained ethyl vinyl ether/dimethylaminopropyl maleamidic acid copolymer was then reacted with methyl iodide to yield poly(methyl iodide quaternized ethyl vinyl ether/N,N′‐dimethylaminopropyl maleamidic acid) (MIQEDMAPMA). The greatest difference from other polyelectrolytes was the carboxylic group on the polymer chain unit of MIQEDMAPMA. Its aqueous solution properties in various salts and at various pH values were studied by measurements of the reduced viscosity and intrinsic viscosity. The reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the types and concentrations of the added salts. The tendency of the salt effect was similar to that of other polyelectrolytes; that is, soft salt anions were more easily bound to the quaternary ammonium (R₄N⁺) of MIQEDMAPMA than hard salt anions. Some salt ions strongly attracted the quaternary ammonium of the cationic polymeric side chain for the agglomeration of the polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2261–2269, 2003     

Poly(sulfobetaine)s and corresponding cationic polymers. VIII. Synthesis and aqueous solution properties of a cationic poly(methyl iodide quaternized styrene–n,n‐dimethylaminopropyl maleamidic acid) copolymer

A cationic poly(methyl iodide quaternized styrene–N,N‐dimethylaminopropylmaleamidic acid) copolymer was synthesized through amidoacidification reaction of styrene‐maleic anhydride copolymer with N,N‐dimethylaminopropylamine (ring‐opening reaction). Its properties in various aqueous salt solutions and pH solutions were studied by measurements of reduced viscosity and intrinsic viscosity. The results indicated that the reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the type and concentration of the added salts and the results also showed a contrary tendency in some salts with monovalent acid groups to polyelectrolyte. At the same time, some salt ions were observed to strongly attract the quaternary ammonium group of the cationic polymeric side chain and resulted in agglomeration of the polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1619–1626, 2001     

Miscibility of polystyrene with poly(ethylene oxide) and poly(ethylene glycol)

The intrinsic viscosity of polystyrene–poly(ethylene oxide) (PS–PEO) and PS–poly(ethylene glycol) (PEG) blends have been measured in benzene as a function of blend composition for various molecular weights of PEO and PEG at 303.15 K. The compatibility of polymer pairs in solution were determined on the basis of the interaction parameter term, Δb, and the difference between the experimental and theoretical weight-average intrinsic viscosities of the two polymers, Δ[η]. The theoretical weight-average intrinsic viscosities were calculated by interpolation of the individual intrinsic viscosities of the blend components. The compatibility data based on [η] determined by a single specific viscosity measurement, as a quick method for the determination of the intrinsic viscosity, were compared with that obtained from [η] determined via the Huggins equation. The effect of molecular weights of the blend components and the polymer structure on the extent of compatibility was studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1471–1482, 1998     

Aqueous solution properties of poly(trimethyl acrylamido propyl ammonium iodide) [poly(TMAAI)]

The aqueous solution properties of a cationic poly(trimethyl acrylamido propyl ammonium iodide) [poly(TMAAI)] were studied by measurements of reduced viscosity, intrinsic viscosity, and flocculation test. The reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the types and concentration of added salt. “Soft” salt anions were more easily bound on the quaternary ammonium (R₄N⁺) of poly(TMAAI) than those of “hard” salt anions. Halide anions are hard anions; consequently, hard cations were more easily attracted to halide anions for reducing the binding degree of halide anion on the quaternary ammonium group (R₄N⁺). Some salt ions were observed to strongly attract the quaternary ammonium of the cationic polymeric side chain for coagulation of the polymers. This effect would make the polymeric aqueous solution become turbid. The intrinsic viscosity behavior for cationic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain is contrasted with polyampholyte. A comparison of various flocculants as to the effect of flocculation was also studied. © 1994 John Wiley & Sons, Inc.     

Miscibility studies of polymer blends by viscometry methods

The intrinsic viscosities of blends of poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN), and poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (EVA/SAN) have been studied in cyclohexanone as a function of blend composition. In order to predict the compatibility of polymer pairs in solution, the interaction parameter term, Δb, obtained from the modified Krigbaum and Wall theory, and the difference in the intrinsic viscosities of the polymer mixtures and the weight average intrinsic viscosities of the two polymer solutions taken separately are used. © 1994 John Wiley & Sons, Inc.     

Effect of inorganic salts on viscosifying behavior of a thermoassociative water-soluble terpolymer based on 2-acrylamido-methylpropane sulfonic acid

The effect of different inorganic salts on aqueous solution viscosifying behavior of a thermoassociative water-soluble terpolymer, poly(acrylamide-co-2-acrylamido-2-methylpropane sulfonic acid)-g-poly[acrylamide-co-N-(1,1-dimethyl-3-oxobutyl)acrylamide] (PADAS) was examined in comparison with a nonthermoassociative sulfonated copolymer, poly(acrylamide-co-2-acrylamido-2-methylpropane sulfonic acid) (PAMS). With increasing salt concentration, thermoviscosifying ability of PADAS was clearly evidenced and the magnitude of thermoviscosifying effect was largely enhanced. The ability of cations and anions to enhance the viscosity of PADAS aqueous solution follows the orders Na⁺ > K⁺ > Mg²⁺ > Ca²⁺ and SO₄²⁻ > Cl⁻ > Br^- > NO₃⁻, respectively. Under the same conditions, PAMS shows only thermothinning behavior and viscosity loss. The thermoviscosifying capability of PADAS is relevant to the change in the polarity of aqueous solution and the electrostatic shield effect of counterion for the repulsion between the sulfonate anions on the polymer, and depends mainly on the competition of these two effects. Cryo-TEM observation demonstrates that the microstructure changes of polymers in the electrolyte solution lead to the changes of the viscosifying behavior. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Solution properties of ionic hydrophobically associating polyacrylamide with an arylalkyl group

Copolymers of acrylamide, 2‐acrylamide‐2‐methylpropanesulfate (AMPS), and hydrophobic monomer N‐arylalkylacrylamide (BAAM) were synthesized by free‐radical micellar copolymerization. The effects of the copolymer, BAAM, AMPS, and NaCl concentrations and the pH value on the apparent viscosity of the copolymers were studied. The solution viscosities increased sharply when the copolymer concentration was higher than the critical associating concentration. The apparent viscosities of aqueous solutions of poly(N‐arylalkylacrylamide‐co‐acrylamide‐co‐2‐acrylamide‐2‐methylpropanesulfate) (PBAMS) increased with increasing BAAM and AMPS concentrations. PBAMS exhibited good salt resistance. With increasing pH, the apparent viscosities first increased and then decreased. Dilute PBAMS solutions exhibited Newtonian behavior, whereas semidilute aqueous and salt solutions exhibited shear‐thickening behavior at a lower shear rate and pseudoplastic behavior at a higher rate. Upon the removal of shear, the aqueous solution viscosities recovered and became even greater than the original viscosity, but the salt solution viscosities could not recover instantaneously. The elastic properties of PBAMS solutions were more dominant than the viscous properties, and this suggested a significant buildup of a network structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 316–321, 2005     

Polysulfobetaines and corresponding cationic polymers. VI. Synthesis and aqueous solution properties of cationic poly(methyl iodide quaternized acrylamide–N,N-dimethylaminopropylmaleimide copolymer) [poly(MIQADMAPM)]

The copolymer prepared by copolymerizing with acrylamide and maleic anhydride was imidized with N,N-dimethylaminopropylamine. The obtained acrylamide–N,N-dimethylaminopropylmaleimide (ADMAPM) copolymer was then reacted with methyl iodide to yield a poly(methyl iodide quaternized acrylamide–N,N-dimethylaminopropylmaleimide) copolymer [poly(MIQADMAPM)]. Its aqueous solution properties were studied by measurements of reduced viscosity, intrinsic viscosity, and flocculation test in this study. The reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the types and concentration of the added salt. “Soft” salt anions were more easily bound to the quaternary ammonium cation (R₄N⁺) of poly(MIQADMAPM) than were “hard” salt anions. Halide anions are hard anions; consequently, hard cations were more easily attracted to halide anions and reduced the binding degree of halide anion on the quaternary ammonium group (R₄N⁺). The intrinsic viscosity behavior for cationic polyelectrolyte resulting from the electrostatic repulsive force of the polymer chain was contrasted with polyampholyte. The effect of various flocculants on flocculation in different pH values was accessed in this study. © 1996 John Wiley & Sons, Inc.     

Interpretation of intrinsic viscosity/temperature data for solutions of poly(phenyl acrylate) and poly(ethylene oxide)

Measured intrinsic viscosities ([η]) at several temperatures (T) within the interval 280–350 K have been found to increase with T for solutions of poly(phenyl acrylate) (PPA) in ethyl lactate. A decrease of [η] with T was observed for aqueous solutions of poly(ethylene oxide) (PEO) at several temperatures within the range 276–358 K. The results have been treated on the basis of eight excluded volume theories, among which the best consistency was afforded by those of Kurata-Stockmayer-Roig, Fixman, and Stockmayer (Padé). These yielded values of ?3.4 × 10^?3 to ?4.7 × 10^?3 deg^?1 and ?0.9 × 10^?3 to ?2.4 × 10^?3 deg^?1 for the temperatur coefficient of the unperturbed dimensions of PPA and PEO, respectively. The derived θ-temperatures were 287 K as the upper critical solution temperature for PPA in ethyl lactate and 365–382 K as the lower critical solution temperature for aqueous PEO.     

Studies of linear polymer dimensions of poly(4-chlorostyrene) in various solvents around the θ temperatures by intrinsic viscosity

Intrinsic viscosities of poly(4-chlorostyrene) solutions in isopropyl-benzene and n-propylbenzene at temperatures above and below the theta (θ) temperatures of these solvents were measured using a capillary viscometer. The viscosity measurements were performed on three poly(4-chlorostyrene) samples having molecular weights (M?;_v) 1.75 × 10⁶, 6.5 × 10⁵ and 2.7 × 10⁵. A smooth and continuous contraction below the θ temperatures was observed for both solvents. The temperature dependence of [/eta] can be represented by a master curve in a plot of α³/eta|/tau|M^1/2 (g^1/2 mol^?1/2) versus |/tau|M^1/2 (g^1/2 mol^?1/2), where α/eta = [/eta(T)]/[/eta(θ)]^1/3 is the expansion factor and /tau = (T - θ)/T is the reduced temperature. A universal plot of reduced viscosity size (α/eta) versus reduced blob parameter (N/N_c) shows the achievement of collapsed state for T<θ. The prediction of thermal blob theory is also verified for T > θ. The temperature dependence of intrinsic viscosity, both below and above the θ temperature, exhibits similar behaviour to the temperature dependence of dipole moments for both of these solvents.     

Synthesis,characterization, and flocculation properties of poly(acrylamide‐methacryloxyethyltrimethyl ammonium chloride‐methacryloxypropyltrimethoxy silane)

A novel hydrophobically modified and cationic flocculant poly(acrylamide‐methacryloxyethyltrimethyl ammonium chloride‐methacryloxypropyltrimethoxy silane) (P(AM‐DMC‐MAPMS)) was synthesized by inverse emulsion polymerization. The molecular structure of hydrophobically cationic polyacrylamide (HCPAM) was characterized by FTIR and ¹H‐NMR. The effects of DMC and MAPMS feed ratio on intrinsic viscosity and solubility were measured. The effects of hydrophobically cationic flocculants on reactive brilliant red X‐3B solution and kaolin suspension were studied. It was found that the introduction of MAPMS could increase the intrinsic viscosities of P(AM‐DMC‐MAPMS) and enhance the flocculation properties to anionic dye solution and kaolin suspension, but reduced their water‐solubility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(sulfobetaine)s and corresponding cationic polymers. X. Viscous properties of zwitterionic poly(sulfobetaine) derived from styrene–(N,N‐dimethylaminopropyl maleamidic acid) copolymer in aqueous salt solutions

A styrene–[N,N‐dimethyl (maleamidic acid) propyl ammonium propane sulfonate] (SDMMAAPS) copolymer was synthesized through an amidoacidation reaction of styrene–maleic anhydride (SMA) alternating copolymer with N,N‐dimethylaminopropylamine (ring‐opening reaction), which was then reacted with propane sultone. The effect of various salt solutions on the intrinsic viscosity of this ampholytic ADMMAAPS copolymer was investigated. The results showed that the effect of counter ions on the intrinsic viscosity of SDMMAAPS was not entirely similar to that of other zwitterionic poly(sulfobetaine)s. The greatest difference from other poly(sulfobetaine)s is the carboxylic group on the polymer chain unit of SDMMAAPS. The Huggins constants for SDMMAAPS in aqueous salt solutions, however, were also quite different from those of other sulfobetaine copolymers, such as styrene–N,N‐dimethyl (maleimido propyl) ammonium propane sulfonate] (SDMMAPS) copolymer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 726–734, 2004     

Polysulfobetaines and corresponding cationic polymers. IV. Synthesis and aqueous solution properties of cationic poly(MIQSDMAPM)

A cationic poly(methyl iodide quaternized styrene-dimethylaminopropylmaleimide) copolymer [poly(MIQSDMAPM)] was synthesized by imidizing styrene-maleic anhydride (SMA) copolymer. Its aqueous solution properties were studied by measurements of reduced viscosity, intrinsic viscosity, and a flocculation test. The reduced viscosity and intrinsic viscosity of this cationic polyelectrolyte were related to the types and concentration of the added salt. “Soft” salt anions were more easily bound to the quaternary ammonium cation (R₄N⁺) of poly(MIQSDMAPM) than “hard” salt anions. Halide anions are hard anions; consequently, hard cations were more easily atracted to halide anions, and reduced binding degree of halide anion on the quaternary ammonium group (R₄N⁺). Some salt ions were observed to strongly attract the quaternary ammonium group of the cationic polymeric side chain and resulted in agglomeration of the polymers. A comparison of various flocculants as to the effect of flocculation was made in this study. © 1996 John Wiley & Sons, Inc.     

Aqueous solution properties of poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate]

The aqueous solution properties of an ampholytic poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate] [poly(DMAPS)] are studied by measurements of cloud point determination, intrinsic viscosity, degree of binding, and ionic strength. The minimum salt concentration and intrinsic viscosity of this polyampholyte are related to the type and concentration of added salt. Both the polymeric and monomeric betaines in the presence of NaCl have the lower degree of binding, indicating that the proton ion (H⁺) is relatively difficult to bind the SO^?₃ at the end of sulfobetaine. An increase in ionic strength causes the pK_a to decrease at the half-neutralization point.     

Electro-optical and viscometric behaviour of sodium polystyrene sulphonate in formamide

Unusual electro-optical signals have been recorded on sodium polystyrene sulphonate in formamide. It was shown that such signals largely arise from the positive birefringence of the solvent being superimposed on the negative birefringence of the polyion. On the basis of conductimetric experiments, the residual content of ammonium formate caused by hydrolysis of formamide was estimated. Commercial formamide of analytical grade was shown to contain rather large amounts (0.02 M) of ammonium formate, sufficient to very strongly decrease the polyelectrolyte effect. The persistence length in these conditions is equal to 80Å, quite similar to that determined in 2 × 10^?2 M NcCl aqueous solution. At a lower ammonium formate content (7 × 10^?4 M), the degree of extension of the polyion at infinite dilution, calculated from the relaxation time of the birefringence, is identical to that measured in 6 × 10^?4 M NaCl. The influence of the nature of the solvent and the ionic strength on the electric polarizability and the optical anisotropy factor was also analysed and compared with the results obtained in water. The latter parameter was discussed in terms of the so-called form anisotropy of the solvent and the intrinsic optical anisotropy of the polyion.