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  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Linear poly(1,4-piperazinediyl-1-oxotrimethylene) (1), in which amido and tertiary amino groups regularly alternate along the macromolecular chain, the isomeric poly[1-(1-piperazinyl-carbonyl)ethylene] (8) for polyvinylic structure and its N-methylated derivative, poly{1-[(4-methyl-1-piperazinyl)carbonyl]ethylene} (3), were prepared and characterized. Their protonation behaviour was investigated in aqueous solution by potentiometric and calorimetric techniques. In all cases the basicity constants were found to decrease linearly with α (the degree of protonation), whereas the enthalpy changes show a different behaviour toward protonation. The thermodynamic values indicate the important role of hydrophobic interactions.
    Additional Material: 2 Ill.
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  • 2
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Calorimetric data are reported for the enthalpy of protonation of pendant carboxylato groups in new polymers 1a-d containing amido and thioether moieties in their main chain. These data, together with potentiometric and viscometric data, afford a complete thermodynamic description of the protonation process of the new polyacids, which are water-soluble in a narrow range of α (degree of protonation) values. Comparison with the non-macromolecular model 2 revealed that the thermodynamic features are attributable to polyelectrolyte effects. In contrast with model 2, all polymers studied form stable hydroxocomplex species with copper(II) ion. The hypothesized [Cu(OH)2L2]2- (where L is the monomeric unit of the polymer) stoichiometry fits the potentiometric data well when processed with the ‘SUPERFIT’ program. The trend of the corresponding stability constant (log β) values is to decrease with increasing pH over a wide range.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 188 (1987), S. 1959-1971 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A linear poly(amido-amine) carrying a malonic acid moiety in the side chain of the repeating unit was synthesized and characterized. Its behaviour in aqueous solution was investigated by potentiometric, viscometric and calorimetric techniques. The basicity constant relative to the tertiary nitrogen atom decreases linearly by increasing the overall degree of protonation, while the tendency of each carboxylate ion to accept a proton is influenced by the presence of the neighbouring negative charge. The change of the basicity constants with the degree of protonation is due to entropic terms leading to energetics of protonation independent of the degree of protonation.
    Additional Material: 3 Ill.
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  • 4
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Synthetic poly(N-acryloylglycine) (poly[1-(carboxymethylcarbamoyl)ethylene], 1a) and poly-(N-acryloyl-6-aminocaproic acid) (poly{1-[5-(carboxypentyl)carbamoyl]ethylene}, 1b) were studied in aqueous solution by thermodynamic (potentiometry, calorimetry) and Fouriertransform infrared (FT-IR) spectroscopic methods. The values of the basicity constant (log K), calculated with the Henderson-Hasselbalch equation, relative to the protonation of the carboxylate group, decreases with increasing degree of protonation (a), while the enthalpy changes are “real” for both polymers. The increased length of the lateral aliphatic chain causes a decrease in the polyelectrolyte effect and a greater entropy change ΔS° of protonation due to liberation of water molecules. At low pH the FT-IR spectra reveal a strong band at 1 628 cm-1 for polymer 1b which does not occur in the spectra of polymer 1a. At this pH the more compact macromolecular structure of 1b may favour interactions among the amido groups of several monomeric units.
    Additional Material: 4 Ill.
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  • 5
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two linear vinyl polymers carrying amido and primary amino groups in the side chains were synthesized and characterized. Their behaviour in aqueous solution was investigated by potentiometric, viscometric and calorimetric techniques. In both cases, the basicity constants show a linear dependence on the degree of protonation α, while the enthalpy values of protonation do not. The thermodynamic results demonstrate the important role of hydrophobic interactions on the protonation process.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 7 (1996), S. 831-838 
    ISSN: 1042-7147
    Keywords: polyelectrolytes ; poly(N-isopropylacrylamide) ; copolymers ; protonation thermodynamics ; LCST ; hydrophobic interactions ; grafted membranes ; chemical valve system ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: A series of vinyl polymers with L-valine and L-leucine residues, and related copolymers with N-isopropylacrylamide, were studied in aqueous solution at different temperatures (25, 30 and 35°C) and at two ionic strengths (0.01 M and 0.1 M NaCl). The protonation behavior revealed great differences between the polymers that were attributed to the size of the hydrophobic lateral group. Macromolecular shrinkage, occurring above a critical degree of protonation β, was related to hydrophobic forces outweighing the electrostatic repulsions between COO - groups. Low salt concentrations increased the electrostatic potential while high temperatures increased the hydrophobic interaction at lower β. The release of fewer water molecules structured around the polymer chain, responsible for the lower critical solution temperature phenomenon, revealed lower entropy changes at higher temperatures. The reversible configuration of graft polymer chains instantly responded to changes in pH and temperature, modifying the water filtration rates through the pores of cellulose membranes.
    Additional Material: 11 Ill.
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