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Synthesis of polypyrrole and its derivative nanoparticles via a surfactant-free coupling polymerization protocol

Polymer Journal volume 57, pages 723–735 (2025)Cite this article

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Abstract

Surfactant-free coupling polymerization of pyrrole (Py) and its derivatives, namely, N-methylpyrrole (MPy) and N-ethylpyrrole (EPy), was conducted using solid Fe(NO3)3 in the presence of an aqueous medium, resulting in aqueous dispersions of polymer particles. Dynamic light scattering studies revealed the production of colloidally stable polymer nanoparticles with diameters of 153–206 nm, 262–294 nm and 273–278 nm in aqueous media for the Py, MPy and EPy systems, respectively. The particle sizes of poly(N-methylpyrrole) (PMPy) and poly(N-ethylpyrrole) (PEPy) were larger than those of polypyrrole (PPy), which could be due to the greater hydrophobicity of MPy and EPy than Py. The particles could achieve colloidal stability through an electrostatic stabilization mechanism, as the polymerization process introduces cationic charges to the polymers via doping. Larger amounts of hydroxy and carbonyl groups were introduced into PMPy and PEPy because of the easier overoxidation of MPy and EPy due to their lower redox potentials than that of Py. Furthermore, the resulting particles could adsorb on oil‒water interfaces and work as effective Pickering-type emulsifiers. Suspension polymerization of vinyl monomer-in-water Pickering emulsions stabilized with PPy and PMPy nanoparticles resulted in the production of nanoparticle-coated polymer microparticles with diameters of 25 μm and 154 μm, respectively.

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Acknowledgements

The authors are grateful to Ms. Nano Shioda and Ms. Wakana Hamada (Keio Univ.) for conducting SEM and TEM studies.

Funding

This work was supported by Grants-in-Aid for Scientific Research (B) (JSPS KAKENHI Grant Numbers JP20H02803 and JP24K01562), a JSPS-DAAD Bilateral Joint Research Project (Grant Numbers JPJSBP120203509 and JPJSBP120223510), Challenging Research (Pioneering) (JSPS KAKENHI Grant Number JP22K19071), Scientific Research on Innovative Areas “New Polymeric Materials Based on Element-Blocks (JSPS KAKENHI Grant Number JP15H00767)” and “Aquatic Functional Materials: Creation of New Materials Science for Environment-Friendly and Active Functions (JSPS KAKENHI Grant Number JP22H04559)”, and a Private University Research Branding Project (Type A: Osaka Industrial Technology Platform).

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Authors and Affiliations

  1. Division of Applied Chemistry, Environmental and Biomedical Engineering, Graduate School of Engineering, Osaka Institute of Technology, 5-16-1 Omiya, Asahi-ku, Osaka, 535-8585, Japan

    Yuya Atsuta & Kazusa Takeuchi

  2. Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, 223–8522, Japan

    Tomoki Sakuma & Yuya Oaki

  3. Osaka Research Institute of Industrial Science and Technology, 1-6-50 Morinomiya, Joto-ku, Osaka, 536-8553, Japan

    Koji Mitamura & Seiji Watase

  4. Department of Applied Chemistry, Faculty of Engineering, Osaka Institute of Technology, 5-16-1 Omiya, Asahi-ku, Osaka, 535-8585, Japan

    Yuan Song, Tomoyasu Hirai, Yoshinobu Nakamura & Syuji Fujii

  5. Nanomaterials Microdevices Research Center, Osaka Institute of Technology, 5-16-1 Omiya, Asahi-ku, Osaka, 535-8585, Japan

    Tomoyasu Hirai, Yoshinobu Nakamura & Syuji Fujii

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Contributions

Yuya Atsuta: Methodology, Investigation. Kazusa Takeuchi: Methodology, Investigation. Tomoki Sakuma: Methodology. Koji Mitamura: Methodology. Seiji Watase: Methodology. Yuan Song: Methodology. Tomoyasu Hirai: Methodology, Investigation. Yoshinobu Nakamura: Methodology, Investigation. Yuya Oaki: Conceptualization, Methodology, Investigation, Writing - Review & Editing, Supervision, Project administration, Funding acquisition. Syuji Fujii: Conceptualization, Methodology, Investigation, Writing - Original Draft, Writing - Review & Editing, Supervision, Project administration, Funding acquisition.

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Correspondence to Yuya Oaki or Syuji Fujii.

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Atsuta, Y., Takeuchi, K., Sakuma, T. et al. Synthesis of polypyrrole and its derivative nanoparticles via a surfactant-free coupling polymerization protocol. Polym J 57, 723–735 (2025). https://doi.org/10.1038/s41428-025-01026-8

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