Sequential Self‐Polymerization of Phenolic Compounds with Alkanedithiol Linkers as a Surface‐Independent and Solvent‐Resistant Surface Functionalization Strategy

Abstract A sequential self‐polymerization of phenolic compounds combined with alkanedithiol (ADT) crosslinkers is developed as a versatile surface‐independent coating and functionalization strategy. The resulting copolymer takes advantage of the diverse binding modes of catechol and gallol and the conformal substrate contact facilitated by the flexible aliphatic chain of ADT. Moreover, Michael addition and thiyl radical addition reactions between ADT and phenolic compounds produce crosslinked resulting polymer films, rendering solvent resistance to the surface coating. This approach is successfully employed using phenolic monomers, including dopamine, 3,4‐dihydroxybenzylamine, 4‐ethylcatechol, levodopa, tannic acid, caffeic acid, and 3,4‐dihydroxybenzylaldehyde, to functionalize glass (ceramic), aluminum (metal), polyethylene (polymer), and Teflon surfaces. The resulting copolymer prepared with a trifunctional thiol crosslinker demonstrated solvent resistance in NaOH (aq.), DMSO, and chloroform, overcoming the stability issues typically encountered by conventional surface coating from polydopamine derivatives.