Investigation of a Microchannel Reactor for the Synthesis of Low Molecular Weight K-Type Perfluoropolyether Methyl Esters

Wenjie Yu; Zhibin Chen; Bo Liu; Yue Zhang; Ming Zhang; Yanli Liang; Jianzhi Wang; Xiaoyan Ma

doi:10.6919/ICJE.202603_12(3).0025

Authors

Wenjie Yu
Zhibin Chen
Bo Liu
Yue Zhang
Ming Zhang
Yanli Liang
Jianzhi Wang
Xiaoyan Ma

DOI:

https://doi.org/10.6919/ICJE.202603_12(3).0025

Keywords:

Hexafluoropropylene Oxide; Microchannel Reactor; Polymerization; Esterification; K-type PFPE Methyl Ester.

Abstract

This study demonstrates the synthesis of perfluoropolyether (PFPE) acyl fluoride from hexafluoropropylene oxide (HFPO) using a microchannel reactor. The reaction was conducted under low-temperature conditions with diethylene glycol dimethyl ether as the solvent and tetramethylethylenediamine (TMEDA) as the catalyst. The resulting acyl fluoride was esterified with methanol at room temperature to obtain K-type PFPE methyl ester, and its molecular weight was determined. The polymerization degree of the product was precisely regulated by systematically varying the microchannel length, HFPO flow rate, and reaction temperature. Compared to traditional systems, the microchannel reactor offers enhanced control over reaction parameters and can be seamlessly integrated into continuous production lines, underscoring its strong potential for the scalable synthesis of low-molecular-weight K-type PFPEs.

Downloads

Download data is not yet available.

References

[1] S. Saxena, P. Malik, G. Seshadri, A.K. Tyagi, U.K. Mandal. One step synthesis of low molecular weight perfluoropolyethers (PFPEs) by photo-oxidation of hexafluoropropylene (HFP), Radiat. Phys. Chem, vol. 165 (2019), 108417-108417.

[2] K. Dušek, D. Bušek, M. Plaček, A. Géczy, O. Krammer, B. Illés. Influence of vapor phase soldering fluid Galden on wetting forces (tombstone effect), J. Mater. Process. Technol, vol. 251 (2017), 20-25.

[3] B. Illés. Modeling Galden layer formation on PCB surface during Vapour Phase Soldering, Proc. 2013 IEEE 19th Int. Symp. Design Technol. Electron. Packag., 2013, pp. 69-74.

[4] X. Hao, A. Yoshida, N. Hoshi. ChemInform Abstract: Recyclable Hafnium(IV) Bis(perfluorooctanesulfonyl)amide Complex for Catalytic Friedel-Crafts Acylation and Prins Reaction in Fluorous Biphase System, ChemInform, vol. 39 (2008), 0-0.

[5] P. Saravanan, S. Jayaraman, D.H. Minh, S.K. Sinha. The Role of Functional End Groups of Perfluoropolyether (Z-dol and Z-03) Lubricants in Augmenting the Tribology of SU-8 Composites, Tribol. Lett, vol. 56 (2014), 423-434.

[6] F. L. Xing. Studies on Hexafluoropropylene Oligomerization, Organo-Fluorine Ind., 2016, 22-25. (In Chinese)

[7] X. Y. He, X. Hu. Preparation of Perfluoropolyether Carboxylate Surfactant from Hexafluoropropylene Oxide (HFPO), Chem. Prod. Technol, 2005, 5-7+51. (In Chinese)

[8] S.H. Korzeniowski, R.C. Buck, R.M. Newkold, et al. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers, Integr. Environ. Assess. Manag, vol. 19 (2022), 326-354.

[9] W. J. Yang, C. Fang, J. C. Zhou, et al. Catalytic synthesis of perfluorolyethers, J. Cent. South Univ, vol. 20 (2013), 629-633.

[10] M.Y. Keating, J.L. Howell. Decomposition of perfluoropolyether lubricants: A study using TG–MS in the presence of alumina powder, J. Therm. Anal. Calorim., vol. 106 (2011), 213-220.

[11] Q. F. Liu, X.-Y. Wu. Study on Decomposition of Z-type Perfluoropolyether, Organo-Fluorine Ind, 2025, 1-5+10. (In Chinese)

[12] X. T. Chen, L. L. Zhang, L. Zhou, et al. Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene, AIChE J, vol. 70 (2024), 0-0.

[13] W. Zhang, B. Liu, M. Zhang, et al. Research Progress in Anionic Ring-opening Polymerization of Hexafluoropropylene Oxide, Organo-Fluorine Ind, 2024, 34-39. (In Chinese)

[14] M. Koyama, M. Akiyama, K. Kashiwagi, et al. Synthesis of Crystalline CF3-Rich Perfluoropolyethers from Hexafluoropropylene Oxide and (Trifluoromethyl)Trimethylsilane, Macromol. Rapid Commun, vol. 43 (2022), 0-0.

[15] M. Gleirscher, A. Wolfberger, S. Schlögl, et al. Accelerated Thermo-Catalytic Degradation of Perfluoropolyether (PFPE) Lubricants for Space Applications, Lubricants, vol. 11 (2023), 81-81.

[16] S. Jiang, Z. Yang, J. Zhang, et al. Development of a Mini-Channel Heat Exchanger Reactor with Arborescent Structures for Fast Exothermic Reactions, Ind. Eng. Chem. Res, vol. 61 (2022), 14121-14131.

[17] G. Dong, B. Chen, B. Liu, et al. Advanced oxidation processes in microreactors for water and wastewater treatment: Development, challenges, and opportunities, Water Res, vol. 211 (2022), 118047-118047.

[18] K. Subramaniam, K.Y. Wong, K.H. Wong, et al. Enhancing Biodiesel Production: A Review of Microchannel Reactor Technologies, Energies, vol. 17 (2024), 1652-1652.

[19] B. Kamenická. Critical review on enhanced production of methane in microchannel reactors as carbon dioxide utilization approach, Chem. Eng. Process. Process Intensif, vol. 217 (2025), 110532-110532.

[20] H. Liu, N. Yang, J. Jiang, et al. Seamless scale‐up of tube‐in‐tube millireactors by annular structure and feed method design: Micromixing, residence time distribution and heat transfer, AIChE J, vol. 71 (2024), 0-0.