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Sulfonated polyisobutylene telechelic ionomers. XIV. Viscoelastic behavior of concentrated solutions in nonpolar solvents
Author(s) -
Tant Martin R.,
Wilkes Garth L.,
Kennedy Joseph P.
Publication year - 1991
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1991.070420225
Subject(s) - viscoelasticity , viscosity , time–temperature superposition , polymer chemistry , intermolecular force , ionic bonding , solvent , materials science , ionic strength , telechelic polymer , dynamic mechanical analysis , ionomer , chemistry , thermodynamics , chemical engineering , molecule , composite material , polymer , copolymer , ion , organic chemistry , end group , aqueous solution , physics , engineering
The effect of molecular variables upon the dynamic viscoelastic behavior of solutions of sulfonated polyisobutylene telechelic ionomers in nonpolar solvents has been investigated. Intermolecular association of the ionic end groups in nonpolar media results in the formation of a transient ionic network which displays a viscous response at low frequencies and an elastic response at high frequencies. The frequency of the transition from viscous behavior to elastic behavior, as well as the plateau storage modulus, is dependent upon molecular variables such as architecture, molecular weight, neutralizing cation, and extent of neutralization. Variables which affect the strength of the ionic interactions, such as temperature and the type of solvent, also influence the viscoelastic response. Solutions of ionomers neutralized with cations of Groups IA and IIA, such as potassium and calcium, behave elastically over most of the experimentally accessible frequency range, while those neutralized with transition metals, such as zinc, display viscous flow over a rather wide range at low frequencies. As in previous studies of dilute solution viscosity behavior, the threearm star trifunctional species was found to form a more extensive network in nonpolar solvents than the linear difunctional species at equivalent concentrations. The failure of time–temperature superposition indicates that these solutions are thermoheologically complex.