Gelation in physically associating polymer solutions - art. no. 188301

Simulations were performed on solutions of associating polymers, where the pairing energy between "stickers" is comparable to thermal energy, to gain insights into the nature of reversible gelation. At high temperatures, inte rchain associations relax over microscopic time scales, so that geometrical percolation is unrelated to macroscopic gelation. However, with decreasing temperature, the stickers undergo a clustering "transition," resulting in a transient localization of stickers and hence the chains. These findings i mply a close similarity between the dynamics of associating polymer solutio ns and vitrification of glass-forming liquids, in agreement with many exper imental results.