Solvent-programmable organocatalyzed group transfer copolymerization (O-GTcP) of muconate esters: from statistical...

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 in situ nanoparticle formation during copolymer chain growth. Stable dispersions are thus generated directly through one-pot copolymerization-induced self-assembly under organocatalytic conditions (O-GTcPISA), without block copolymer design or sequential polymerization steps. Together, these results establish O-GTcP as a solvent-programmable platform integrating rapid metal-free copolymerization, statistical sequence control, recyclable backbone chemistry, and nanoscale organization within a single synthetic framework.