Supramolecular
polymers are based on noncovalent interactions,
which impart unique properties such as dynamic behavior, concentration-dependent
degree of polymerization, and environmental responsiveness. While
linear supramolecular polymers are ubiquitous and have been extensively
studied, branched polymers that are based exclusively on supramolecular
interactions are much less abundant, and a fundamental understanding
of their molecular-level structure is still lacking. We report on
the preparation of branched, all-supramolecular polymers based on
a combination of a bisureidotoluene building block [N,N′-2,4-bis((2-ethylhexyl)ureido)toluene
(EHUT)], which is associated with four-point hydrogen bonding, and
three anionic co-monomers featuring one, two, or three sulfonate groups.
The co-monomers were designed to serve as a chain stopper, a bifunctional
linear co-monomer, and a branch point. Whereas combination of EHUT
with the singly functionalized co-monomer led to linear supramolecular
chains, diffusion and viscosity data indicate that branched supramolecular
polymers were obtained when EHUT was combined not only with the triply
functionalized molecules but also with the doubly functionalized molecules.
Theoretical analysis based on an adaptation of Flory’s theory
of branched polymers suggests that in both cases, the interaction
of certain EHUT units with the multiply functionalized co-monomers
converted these EHUT units into branch points, which led to substantially
reduced viscosities in these systems. The insights gained from this
study enable tuning the properties of supramolecular polymers not
only by concentration and temperature but also by introducing appropriately
designed molecular additives. This may lead to the development of
sophisticated smart materials.