Catechol Homopolymers and Networks through Postpolymerization Modification

Catechol-rich polymers are attractive for a plethora of applications but are difficult to synthesize in a controlled manner. Here, we describe a procedure for obtaining catechol homopolymers through the postpolymerization modification of RAFT-derived templates bearing active pentafluorophenyl esters. This protocol produces polymers with controllable molecular weight and low dispersity while suppressing the oxidation of the catechol units. The catechol homopolymers are electrochemically evaluated in both aqueous and organic media, where high reversibility of the catechol/quinone redox couple is observed. The procedure can be extended to cross-linked polymers by copolymerizing the template monomer with a divinyl unit, which leads to the formation of an insoluble network of active esters. This network can still undergo postpolymerization modification when swollen with a good solvent, and its reactivity is exploited to produce gels with catechol contents above 98%.