Intramolecular micelles and intermolecular crosslinks in thermoreversible gels of associating polymers

Abstract

This paper studies theoretically and computationally the effect of small loops on the sol/gel transition with multiple crosslink junctions in associating polymer solutions. In the case of telechelic associating polymers, the problem is shown to be mathematically equivalent to the mixture of monofunctional polymers and bifunctional ones. The gelation concentration changes with a parameter describing the probability of single loop formation. Relative population of chains belonging to six fundamental types of association is derived as a function of the total polymer concentration with special attention to the formation of flower micelles. Phase diagrams including flower micelles, sol/gel transition and phase separation are derived. The effect of shear flow on the flower micelles is studied by Monte Carlo simulation, paying special attention to the shear thickening phenomena.