Dynamics of Associative Polymers with High Density of Reversible Bonds

SF Nian and S Patil and ST Zhang and M Kim and Q Chen and M Zhernenkov and T Ge and SW Cheng and LH Cai, PHYSICAL REVIEW LETTERS, 130, 228101 (2023).

DOI: 10.1103/PhysRevLett.130.228101

An associative polymer carries many stickers that can form reversible associations. For more than 30 years, the understanding has been that reversible associations change the shape of linear viscoelastic spectra by adding a rubbery plateau in the intermediate frequency range, at which associations have not yet relaxed and thus effectively act as crosslinks. Here, we design and synthesize new classes of unentangled associative polymers carrying unprecedentedly high fractions of stickers, up to eight per Kuhn segment, that can form strong pairwise hydrogen bonding of & SIM;20kBT without microphase separation. We experimentally show that reversible bonds significantly slow down the polymer dynamics but nearly do not change the shape of linear viscoelastic spectra. This behavior can be explained by a renormalized Rouse model that highlights an unexpected influence of reversible bonds on the structural relaxation of associative polymers.

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