Solvent-programmable organocatalyzed group transfer copolymerization (O-GTcP) of muconate esters: from statistical control to copolymerization-induced self-assembly.

Developing sustainable polymer platforms requires simultaneous control over micro- and macromolecular structures, material properties, and end-of-life fate. Herein, we report the one-pot organocatalyzed group transfer copolymerization (O-GTcP) of dioctyl and diethyl muconates (DOM and DEM), achieving statistical copolymuconates with tunable properties and composition-dependent self-assembly. In homogeneous media (THF and toluene), phosphazene-mediated O-GTcP proceeds very rapidly at room temperature (<15 min), yielding statistical copolymers with controlled composition and tunable glass-transition temperatures. These materials undergo efficient thermal depolymerization, regenerating the parent muconate monomers, which can be directly repolymerized without monomer purification to close the polymer-monomer-polymer cycle. Remarkably, conducting the same copolymerization in isododecane leads to a distinct assembly regime. While poly(DOM) remains soluble in this nonpolar medium, increasing DEM incorporation progressively reduces copolymer solubility and ultimately triggers