Electrochemical procedure for constructing poly(phenylene sulfide) brushes on glassy carbon and stainless steel

Abstract

A simple electrochemical approach based on potential sweeping has been developed for growing poly(phenylene sulfide) (PPS) brushes from 4,4’‐disulfanediyldibenzenediazonium salt on glassy carbon and stainless steel. First, the diazonium salt becomes reduced at the substrate on the initial part of the sweep carried out in a negative direction to form a covalently bonded diphenyl disulfide film. Once sufficiently extreme potentials are reached the disulfide bridges are reductively cleaved to form a thin layer of covalently attached thiophenolates. These are prone to be involved in fast coupling reactions with the diazonium salt to form PPS brushes in a repetitive growth process. In this manner linear PPS brushes with thicknesses up to 150 nm are easily formed. In addition, exact control on the brush length may be exerted through the switching potential selected or the number of sweeps applied. The films are characterized by time‐of‐flight secondary ion mass spectrometry which shows that the film growth is accompanied by an increase in the intensity ratio of S−/ normalS2− in line with the proposed PPS structure. This structure was further supported by Raman spectra, exhibiting a high‐intensity C−S stretch band and no S−S stretch band. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 91–98

A post-functionalization toolbox for diazonium (electro)-grafted surfaces: review of the coupling methods

“…In the first one, by Lacroix et al, a combination of electroreduction of diazonium salts and electropolymerization of aniline has been used to functionalize glassy carbon electrodes. 234 In the second one, by Daasbjerg and coworkers, 235 repetitive voltammetric cycles were recorded in a 4,4 0 -disulfanediyldibenzene diazonium solution. This protocol led first to the diazonium reduction, producing a multilayered film, and second to the reductive cleavage of S-S bonds.…”

Why Synthesizing Poly(1,4-Phenylene Sulfide) through Oxidative Polymerization Has not so far Been Adopted as the Industrial Process

“…Poly (1,4-phenylene sulfide) (PPS) is an industrially important and attractive engineering thermoplastic because of its high mechanical strength, high solvent resistance and high thermal stability [1]. We are doing a lot to investigate or improve some of its performances or even apply it [2][3][4][5][6][7][8][9]. Commercial PPS has been produced from 1, 4-phenylene sulfide and sodium sulfide (called Sodium Sulfide method or Phillips' method) since 1960s [10][11][12].…”