Abstract
Abstract This paper reviews recent theoretical and computational studies of thermoreversible gelation with multiple cross-link junctions in associating polymers. Paying special attention to the multiplicity and sequence length of the network junctions, we derive phase diagrams with coexisting gelation and phase separation. Local and global structures of the gel networks are studied. The conventional Eldridge–Ferry method is extended to allow for simultaneous evaluation of multiplicity and sequence length (or enthalpy of the cross-links), and applied to the experimental gel melting curves of poly(vinylalcohol) in water. On the basis of the Scanlan–Case criterion, we calculate the number of elastically effective chains and of dangling ends in the network as functions of polymer concentration and temperature. The effect of added surfactants on the formation of thermoreversible gels (surfactant-mediated gelation) in hydrophobically modified associating polymer solutions is also studied under the assumption of the existence of a minimum multiplicity required for stable cross-links. Competition between intramolecular micellization and intermolecular cross-linking is also studied with special attention to the formation of flower micelles.
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