Quantitative kinetic analysis of EDOT emulsion polymerization: linking oxidant controlled reaction rate to PEDOT structure and conductivity
Abstract
Poly(3,4-ethylenedioxythiophene) (PEDOT) is the most researched conducting polymer, yet the oxidative polymerization of its monomer EDOT in aqueous emulsion remains poorly understood. In particular, the influence of oxidant concentration on polymerization kinetics and the resulting structure–property relationship has not been quantitatively established. Here, a quantitative ¹H NMR (q-NMR) protocol was developed, that enables direct time-resolved measurement of EDOT conversion during emulsion polymerization with an anionic surfactant. By coupling q-NMR with kinetic modelling, the rate-determining step is identified as the oxidation of EDOT by iron chloride. It is demonstrated that the polymerization follows pseudo-first-order kinetics governed by the oxidant concentration. Structural and electronic characterization reveals that slower polymerization at lower oxidant ratios promotes increased chain planarity, less surfactant entrapment and enhanced electrical conductivity in PSS-free PEDOT. This work aims to establish a quantitative link between oxidant-controlled reaction rate, structural organization, and conductivity in PEDOT synthesized in emulsion, leading to an improved understanding and optimization for conductive PEDOT materials.
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BibTeX
@article{schmidt2026quantitative,
title = {{Quantitative kinetic analysis of EDOT emulsion polymerization: linking oxidant controlled reaction rate to PEDOT structure and conductivity}},
author = {Jan Niklas Schmidt and Adèle Karst and Erol-Dan Licsandru and Laure Biniek and Sébastien Boukhris and Jérôme Combet and Michel Bouquey and Cédric Samuel and Thibault Parpaite},
journal = {European Polymer Journal},
year = {2026},
month = sep,
doi = {10.1016/j.eurpolymj.2026.115060},
url = {https://hal.science/hal-05742159v1},
note = {CC BY},
}
RIS
TY - JOUR
TI - Quantitative kinetic analysis of EDOT emulsion polymerization: linking oxidant controlled reaction rate to PEDOT structure and conductivity
AU - Jan Niklas Schmidt
AU - Adèle Karst
AU - Erol-Dan Licsandru
AU - Laure Biniek
AU - Sébastien Boukhris
AU - Jérôme Combet
AU - Michel Bouquey
AU - Cédric Samuel
AU - Thibault Parpaite
PY - 2026
DA - 2026/09/08
JO - European Polymer Journal
DO - 10.1016/j.eurpolymj.2026.115060
UR - https://hal.science/hal-05742159v1
AB - Poly(3,4-ethylenedioxythiophene) (PEDOT) is the most researched conducting polymer, yet the oxidative polymerization of its monomer EDOT in aqueous emulsion remains poorly understood. In particular, the influence of oxidant concentration on polymerization kinetics and the resulting structure–property relationship has not been quantitatively established. Here, a quantitative ¹H NMR (q-NMR) protocol was developed, that enables direct time-resolved measurement of EDOT conversion during emulsion polymerization with an anionic surfactant. By coupling q-NMR with kinetic modelling, the rate-determining step is identified as the oxidation of EDOT by iron chloride. It is demonstrated that the polymerization follows pseudo-first-order kinetics governed by the oxidant concentration. Structural and electronic characterization reveals that slower polymerization at lower oxidant ratios promotes increased chain planarity, less surfactant entrapment and enhanced electrical conductivity in PSS-free PEDOT. This work aims to establish a quantitative link between oxidant-controlled reaction rate, structural organization, and conductivity in PEDOT synthesized in emulsion, leading to an improved understanding and optimization for conductive PEDOT materials.
SN - 0014-3057
SN - 1873-1945
ER -