Solution properties of ionomers. I. Counterion effect

Hara, M.; Lee, A. H.; Jian, Wu

doi:10.1002/polb.1987.090250704

Cited by 68 publications

(54 citation statements)

References 24 publications

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“…For the sulfonate system, the order of counterion binding was Li + > Na + > K + > Ca 2+ . These types of behavior were in concurrence with that observed for polystyrene sulfonate ionomers by Hara, Wu, and Lee [180,181].…”

Section: Dilute Solution Propertiessupporting

confidence: 85%

Synthesis, Physicochemical Characterization, and Applications of Polyurethane Ionomers: A Review

Ramesh¹,

Kannan²,

Mahesh³

et al. 1998

Journal of Macromolecular Science, Part C: Polymer Reviews

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Section: Dilute Solution Propertiessupporting

confidence: 85%

Synthesis, Physicochemical Characterization, and Applications of Polyurethane Ionomers: A Review

Ramesh¹,

Kannan²,

Mahesh³

et al. 1998

Journal of Macromolecular Science, Part C: Polymer Reviews

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“…Until now, the counterion binding to polyion has been interpreted in terms of the size of counterion 14 and/or the state of hydration of both polyion and counterions. 15 phobic EBS -to the hydrophilic polymer such as P AAH + seems to be much less than Cl -. Therefore, when amounts of NaEBS added to the aqueous PAAH+c1-(a constant concentration) solution without NaCl are relative small, many Cl -'s coexisting prevent an effective approach of EBS -'s to the polyion moieties.…”

Section: +·mentioning

confidence: 94%

Binding of Hydrophobic Counterions by Polyelectrolyte and Their Hydrophobic Association around Polyion

Itaya

Ueda

Ochiai

et al. 1993

Polym J

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ABSTRACT:The binding of p-ethylbenzenesulfonate ions (EBS-'s) by poly(allylammonium) cation (PAAH+) and their hydrophobic association around PAAH+ have been investigated in aqueous solutions through 1 H NMR and c1-activity measurements. At a constant PAAH+c1-concentration, all 1 H NMR signals of EBS-exhibited up-field shift (ring current shift) with the increase in the NaEBS concentration. However, any chemical shift change did not observe in each signal of PAAH+. These results show that EBS-'s atmospherically bound to PAAH+ associate each other due to their hydrophobic interaction. The association of EBS-'s is depressed by the decrease in the charge density of the polyion and broken by the addition of another simple salt (NaCl) to the PAAH+c1-;NaEBS system. Moreover, it was found that the counterion exchange from CJ-'s to EBS-'s around PAAH+ is efficiently promoted by the association of EBS-'s.KEY WORDS Poly(allylammonium) Cation / Hydrophobic Counterion / Atmospherical Binding / Association of Hydrophobic Counterions / Counterion Exchange / The properties of polyelectrolyte solutions depend, very much, on the electrostatic interactions between charges fixed along the polymer backbone. These interactions are also very sensitive to the presence of counterions. The addition of electrolyte to the medium screens out the repulsive interactions between charges through the counterion binding and/or condensation around the polyion with a high electrostatic potential. This counterion binding (condensation) is an important feature of polyelectrolyte solutions. 1 Thus, the solution properties are considerably modified accompanying the changes in the chain conformation, water structure, degree of hydration around the polyion, and so on. On the one hand, when hydrophobic salt is used as an added electrolyte, z-4 the hydrophobic counterion, which has both hydrophilic and hydrophobic moieties, may have a different influence upon these electrostatic interactions. Especially, interactions among hydrophobic counterions should be also taken into account when polyion/hydrophobic counterion system is examined, although this interaction would be negligible in the absence of polyion. 5 In the previous work, 6 the interaction of three hydrophobic ions, i.e., benzenesulfonate (BS-), p-methylbenzenesulfonate (MBS-), pethylbenzenesulfonate (EBS-) with PAAH+ cation was investigated by 1 H NMR and viscosity measurements. It was found that EBS -'s accumulated electrostatically around the polyion can associate each other through their hydrophobic interaction. But, BS -and MBS-, which are slightly less hydrophobic than EBS -, did not show any sign of such hydrophobic association. This indicates that the hydrophobicity of counterion plays an important role in the association of counterions 545

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“…The pKa values of benzoic acid, phenylphosphonic acid, phenylphosphonic acid monomethyl ester, and phenylsulfonic acid as model compounds of PCPA, PPPA, PEPPA, and poly-1 are 4.19, 47 1.83 (pKa 1 ) and 7.07 (pKa 2 ), 48 2.97, 49 and 0.7, 47 respectively. Therefore, in the poly-1-chiral amine complexation, the free ions (sulfonate and ammonium ions) should be predominant in DMSO, [50][51][52] and the dissociated free ions derived from a chiral amine (R)-2 could not effectively interact with poly-1, thus showing a very weak ICD (a and b in Figure 2A). …”

Section: Resultsmentioning

confidence: 99%

Helicity Induction on a Poly(phenylacetylene) Derivative Bearing a Sulfonic Acid Pendant with Chiral Amines and Memory of the Macromolecular Helicity in Dimethyl Sulfoxide

Hasegawa

Maeda

Ishiguro

et al. 2006

Polym J

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ABSTRACT:A stereoregular poly(phenylacetylene) derivative bearing a sulfonic acid residue (poly-1) as the pendant was found to form a predominantly one-handed helix upon complexation with various chiral amines through noncovalent acid-base interactions in dimethyl sulfoxide (DMSO). In sharp contrast to analogous poly(phenylacetylene)s bearing relatively weak carboxy and phosphonic acid residues as the pendants, the poly-1-amine complexes exhibited a weak induced circular dichroism (ICD) in the UV-visible region of the polymer backbone. However, in the presence of a strong acid, such as p-toluenesulfonic acid (TosOH), the ICD intensity significantly increased, resulting from a favorable ion pair formation between the sulfonic acid residues of the poly-1 and chiral amines, leading to an increase in the helical sense excess of poly-1. Moreover, the macromolecular helicity of poly-1 induced by chiral amines in the presence of TosOH was ''memorized'' after the chiral amines and their salts were completely removed and replaced with an achiral diamine, i.e., ethylene diamine, in DMSO, while no memory effect was observed for a helical poly-1 induced by the same chiral amines in the absence of TosOH.

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Solution properties of ionomers. I. Counterion effect

Cited by 68 publications

References 24 publications

Synthesis, Physicochemical Characterization, and Applications of Polyurethane Ionomers: A Review

Synthesis, Physicochemical Characterization, and Applications of Polyurethane Ionomers: A Review

Binding of Hydrophobic Counterions by Polyelectrolyte and Their Hydrophobic Association around Polyion

Helicity Induction on a Poly(phenylacetylene) Derivative Bearing a Sulfonic Acid Pendant with Chiral Amines and Memory of the Macromolecular Helicity in Dimethyl Sulfoxide

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