Supramolecular Mimic for Bottlebrush Polymers in Bulk

A series of poly(tetrahydrofuran)s with molecular weights above entanglement molecular weight M e were synthesized, and one of their end-groups was functionalized with a supramolecular entity so that the corresponding polymers form a brushlike structure suitable for comparison with conventional irreversible bottlebrush polymers. To compare their relaxation mechanisms, linear rheology was employed and showed that a hierarchical relaxation, which is usually observed in bottlebrush polymers, occurs in these materials, too. The polymer chain segments close to the supramolecular backbone are highly immobilized due to strong association in the center of polymer brush and cannot relax via reptation mechanism, which is mainly responsible for linear entangled polymer relaxations. Therefore, disentanglement can take much longer through contour length fluctuations and arm retraction processes similar to covalent bottlebrush polymers and combs. The relaxed ends of polymers then act as solvent to let the remaining segments of the polymeric brush undergo Rouse-like motions (constraint release Rouse). At longer times, additional plateau appears, which can be attributed to the relaxation of the entire supramolecular bottlebrush polymer via hopping or reptative motions. With an increase of temperature, viscoelastic solid behavior turns into viscoelastic liquid due to reversible depolymerization of the supramolecular backbone of the bottlebrush polymer. The elastic modulus ( G ' in the order of kPa) was much less than the values found for the entanglement plateau modulus of linear poly(tetrahydrofuran) (in order of MPa). This low modulus value, which exists up to very low frequencies (high temperatures), makes them a good candidate for supersoft elastomers.