Direct Electrodeposition of Superhydrophobic and Highly Oleophobic Poly(3,4‐ethylenedioxypyrrole) (PEDOP) and Poly(3,4‐propylenedioxypyrrole) (PProDOP) Nanofibers

Abstract

Inspired by surface properties in nature, we develop for the first time nanofibers of poly(3,4‐ethylenedioxypyrrole) (PEDOP) and poly(3,4‐propylenedioxypyrrole) (PProDOP) with superhydrophobic and highly oleophobic properties via electropolymerization. This was achieved by grafting fluorinated chains onto the alkylenedioxy cycle of PEDOP and PProDOP, while keeping NH groups free. We use a novel strategy to prepare EDOP and ProDOP with a hydroxyl group on the cycle by reaction with epibromohydrin, which is followed by grafting of fluorinated chains. The highest surface properties are obtained with the shortest fluorinated chains (C4F9) due to the formation of nanofibers and the dimension of these nanofibers can be controlled by changing the base monomer (EDOP or ProDOP). This work can be of interest to researchers working in many fields such as the control of wetting properties but also in the development of conducting polymers, membranes, and sensors. For example, EDOT and ProDOT are actually the most‐employed monomers to obtain conducting polymers and here we show that EDOP and ProDOP derivatives have similar electropolymerization properties, which shows the importance of this manuscript for the scientific community. Moreover, the possibility to substitute on the NH groups will be another possiblity to obtain multifunctional polymers, while the NH groups can also be used to obtain pH‐sensitive polymers.

Formation of Nanofibers with High Water Adhesion by Electrodeposition of Films of Poly(3,4‐ethylenedioxypyrrole) and Poly(3,4‐propylenedioxypyrrole) Substituted by Alkyl Chains

“…The monomer oxidation potentials were first determined by cyclic voltammetry and were found to be approximately 0.9 V (vs. SCE) for the EDOP derivatives and 1.1 V (vs. SCE) for the ProDOP derivatives. These oxidation potentials are consistent with previous results reported in the literature . In these experiments, the alkyl chain length did not significantly influence the monomer oxidation potential because they are distant from the polymerizable sites.…”

“…The monomers were synthesized according to literature procedures . The key intermediates were ProDOP‐OH and EDOP‐OH, which were obtained in eight steps from iminodiacetic acid (Scheme ).…”

“…Among the many possibilities, members of the 3,4‐alkylenedioxypyrrole (XDOP) family, such as 3,4‐ethylenedioxypyrrole (EDOP) and 3,4‐propylenedioxypyrrole (ProDOP), are exceptional monomers for their ultra‐low potential and polymerize to give materials with unique opto‐electronic properties, including high conductivity, multicolor cathodic and anodic electrochromism, and rapid redox switching . In order to obtain nanofibers using XDOP with high hydrophobicity, it is preferable to position the substituent on the bridge (not on the nitrogen atom) in order to keep the NH group free and favor the formation of nanofibers by hydrogen bonding . Previously, a method was found to obtain EDOP and ProDOP derivatives with hydroxy groups on the bridge using epibromohydrin .…”

“…In order to obtain nanofibers using XDOP with high hydrophobicity, it is preferable to position the substituent on the bridge (not on the nitrogen atom) in order to keep the NH group free and favor the formation of nanofibers by hydrogen bonding . Previously, a method was found to obtain EDOP and ProDOP derivatives with hydroxy groups on the bridge using epibromohydrin . The formation of nanofibers containing fluorinated chains was studied.…”

Surfaces Bearing Fluorinated Nucleoperfluorolipids for Potential Anti-Graffiti Surface Properties

“…These blocks are then self-assembled or polymerized. In this work, we focus on a particular bottom-up approach: the conductive polymer electrodeposition [21]. This approach has been reported as an efficient and unexpensive way to prepare highly hydrophobic surfaces in one step.…”