Chemical Polymerization of Hydroxymethyl and Chloromethyl Functionalized PEDOT:PSS

Abstract

Poly­(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer synthesized via oxidative chemical polymerization in the presence of polyelectrolyte poly­(styrenesulfonate) (PSS) can form water-dispersible conductive ink and has broad applications. However, the lack of functionality of PEDOT hinders the broader application of PEDOT:PSS. In this work, we introduced a hydroxymethyl (−MeOH) and a chloromethyl (−MeCl) functional group to the oxyethylene ring of EDOT to obtain hydroxymethylated 3,4-ethylene­dioxythiophene (EDOT–MeOH) and chlorylmethylated 3,4-ethylene­dioxythiophene (EDOT–MeCl) monomer, respectively. We applied oxidative chemical polymerization to synthesize PEDOT–MeCl:PSS and PEDOT–MeOH:PSS as well as PEDOT:PSS. For EDOT, we found that adding base to neutralize acidic PSS has a significant effect on the dispersibility, surface morphology, and electrical conductivity (9.06 × 10–4–1.17 × 10–1 S/cm) of PEDOT:PSS. For functionalized EDOT, the repulsive force between EDOT–MeCl monomer and PSS counterion strongly hinders the oxidation and doping process, resulting in a product with well-dispersed PSS-doped PEDOT–MeCl and nondispersible sulfate-doped PEDOT–MeCl clusters, rough thin film, and electrical conductivity of 1.68 × 10–3 S/cm. The hydrogen bonding between EDOT–MeOH monomer and PSS counterion as well as among EDOT–MeOH monomers makes the polymerization and doping processes easy, yielding a well-dispersed, homogeneous product, smooth thin film, and electrical conductivity of 1.17 × 10–3 S/cm. This study sheds light on the polymerization of PEDOT with functional groups and provides a guideline for the synthesis of functionalized PEDOT conducting polymers with polyelectrolyte counterions using oxidative chemical polymerization.

Thiophene-Based Aldehyde Derivatives for Functionalizable and Adhesive Semiconducting Polymers

“…Note that conductivity of EDOT-based materials is known to improve significantly upon addition in the dispersion of high-boiling polar solvents, , such as 1,4-dioxane. Moreover, the polar aldehyde side group is expected to have a positive impact on the conductivity of our EDOT:CHO-containing material, since such hydrogen-bonding side groups are reported in the literature to enhance the conductivity of PEDOT-based materials …”

“…Moreover, the polar aldehyde side group is expected to have a positive impact on the conductivity of our EDOT:CHO-containing material, since such hydrogen-bonding side groups are reported in the literature to enhance the conductivity of PEDOT-based materials. 42 3.3. Functionalization of the Films.…”

Boosting PEDOT energy storage with a redox anthraquinone dopant for a flexible hydrogel supercapacitor at sub-zero temperatures

“…1, the oxidative polymerization in the presence of AQS using persulfate and Fe 3+ readily afforded AQS–PEDOT complex in high yields, in which Fe 3+ ions in small quantities first oxidize monomers to form polymers, and the couples of Fe 2+ /Fe 3+ ions catalysed the decomposition of persulfate ions (S 2 O 8 2− ) into sulfate radicals (SO 4 ˙ − ) that oxidize polymers together with Fe 3+ ions. 40 Typically, every third or fourth thiophene unit carries a positive charge 41 that results in Coulomb interactions between PEDOT cations and negatively charged AQS and forms a stable AQS–PEDOT complex. Compared with the bare PEDOT, the AQS–PEDOT (1 : 5) complex exhibits high dispersion properties in aqueous solutions (Fig.…”

Hydroxymethyl-Functionalized PEDOT-MeOH:PSS for Perovskite Solar Cells

“…Materials for monomer synthesis and polymerization were used the same as in ref . Lead (II) iodide (PbI 2 , 99.9%), γ-butyrolactone (GBL, ≥99.5%), and bathocuproine (BCP) powder (99.99%) were purchased from Sigma-Aldrich (St. Louis, MO).…”

“…EDOT-MeOH monomers were synthesized, and the purity was verified by 1 H NMR. 60 The molar ratios of PSSH, Na 2 S 2 O 8 , Fe 2 (SO 4 ) 3 , and NaOH to monomer EDOT-MeOH used in the synthesis are listed in Table S1. The amount of PSSH and Fe 2 (SO 4 ) 3 were varied in the polymerization.…”