Accessible Electrodeposition of Vinyl-Based Polymer Networks for Tunable and Permselective Ultrathin Coatings Authors

Abstract

Electrodeposition of polymer networks (EPoN) has emerged as an effective method for forming conformal ultrathin polymer coatings through surface-confined electrochemically activated crosslinking under mild solution conditions. Here, we introduce a facile copolymer-based EPoN design in which a small fraction of comonomer units carries phenolic electrochemical crosslinkers, while the majority monomer composition defines the film properties. This design expands the range of polymer chemistries for EPoN to most vinyl-based polymers accessible by radical polymerization and avoids reliance on advanced synthetic equipment or knowledge. To demonstrate this broadly accessible fabrication concept, poly(methyl methacrylate) is obtained from free radical polymerization with a small fraction of glycidyl methacrylate co-monomer that is functionalized with phenolic side groups in a simple one-step procedure. This accessible design enables the electrodeposition of polymers as ultrathin and conformal network coatings on planar and porous conductive substrates with uniform thickness below 200 nm. We demonstrate that both thickness and small-molecule permeability of the polymer network coating are tunable by the phenol fraction in polymer, the deposition potential, and the polymer concentration, while the thin films are impermeable to macromolecules. This work advances EPoN as a versatile and accessible platform for ultrathin polymer coatings by decoupling deposition from film chemistry, thereby enabling broad compositional flexibility and application spaces.