Investigation of reaction pathways and kinetics in the gas-phase noncatalytic oxidation of hexafluoropropylene

doi:10.1016/j.cjche.2025.02.023

Chinese Journal of Chemical Engineering ›› 2025, Vol. 83 ›› Issue (7): 286-297.DOI: 10.1016/j.cjche.2025.02.023

Previous Articles Next Articles

Investigation of reaction pathways and kinetics in the gas-phase noncatalytic oxidation of hexafluoropropylene

Xintuo Chen^1,2, Wencong Chen³, Yu Zhou³, Liangliang Zhang^1,2, Jianfeng Chen^1,2

1 Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029, China;
2 State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China;
3 Zhejiang Jinhua New Material Co., Ltd., Quzhou 324004, China

Received:2024-11-06 Revised:2025-02-08 Accepted:2025-02-17 Online:2025-07-28 Published:2025-07-28
Contact: Liangliang Zhang,E-mail:zhll@mail.buct.edu.cn
Supported by:
This work was supported by the National Key Research & Development Program of China (2021YFB3803200) and the National Natural Science Foundation of China (22288102).

Investigation of reaction pathways and kinetics in the gas-phase noncatalytic oxidation of hexafluoropropylene

Xintuo Chen^1,2, Wencong Chen³, Yu Zhou³, Liangliang Zhang^1,2, Jianfeng Chen^1,2

1 Research Center of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029, China;
2 State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China;
3 Zhejiang Jinhua New Material Co., Ltd., Quzhou 324004, China

通讯作者: Liangliang Zhang,E-mail:zhll@mail.buct.edu.cn
基金资助:
This work was supported by the National Key Research & Development Program of China (2021YFB3803200) and the National Natural Science Foundation of China (22288102).

Abstract

Abstract: Hexafluoropropylene oxide (HFPO) is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene (HFP) through the oxidation of oxygen. However, the reaction network and kinetic characteristics are not fully understood yet, resulting in a lack of theoretical basis for synthesis process improvement. Here, the free radical reaction mechanism and complete reaction network involved in the noncatalytic oxidation of HFP to synthesize HFPO was explored by density functional theory. Transition state theory was employed to calculate the intrinsic reaction rate constants for elementary reactions. Based on theoretical reaction rate ratios, reaction pathways were selected, and a simplified reaction network was derived. It was found that byproducts were formed owing to the decomposition of HFPO and subsequent reactions with excessive oxygen while oxygen tended to participate more in the main reaction under oxygen-deficient conditions. The variations in reaction pathways occurring at different HFP/oxygen molar ratios was well elucidated by comparing with experimental data. This research establishes a robust theoretical foundation for optimizing and regulating the synthesis of HFPO.

Key words: Kinetics, Oxidation, Reaction pathway, Hexafluoropropylene oxide

摘要： Hexafluoropropylene oxide (HFPO) is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene (HFP) through the oxidation of oxygen. However, the reaction network and kinetic characteristics are not fully understood yet, resulting in a lack of theoretical basis for synthesis process improvement. Here, the free radical reaction mechanism and complete reaction network involved in the noncatalytic oxidation of HFP to synthesize HFPO was explored by density functional theory. Transition state theory was employed to calculate the intrinsic reaction rate constants for elementary reactions. Based on theoretical reaction rate ratios, reaction pathways were selected, and a simplified reaction network was derived. It was found that byproducts were formed owing to the decomposition of HFPO and subsequent reactions with excessive oxygen while oxygen tended to participate more in the main reaction under oxygen-deficient conditions. The variations in reaction pathways occurring at different HFP/oxygen molar ratios was well elucidated by comparing with experimental data. This research establishes a robust theoretical foundation for optimizing and regulating the synthesis of HFPO.

关键词: Kinetics, Oxidation, Reaction pathway, Hexafluoropropylene oxide

Xintuo Chen, Wencong Chen, Yu Zhou, Liangliang Zhang, Jianfeng Chen. Investigation of reaction pathways and kinetics in the gas-phase noncatalytic oxidation of hexafluoropropylene[J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 286-297.

References

[1] W. Wang, H.P. Shao, C. Sun, X.Z. Jiang, S.X. Zhou, G. Yu, S.B. Deng, Preparation of magnetic covalent triazine frameworks by ball milling for efficient removal of PFOS and PFOA substitutes from water, Environ. Sci. Nano 9(4) (2022) 1466-1475.
[2] M. Ortel, N. Kalinovich, G.V. Roschenthaler, V. Wagner, Long-term stabilization äof sprayed zinc oxide thin film transistors by hexafluoropropylene oxide self assembled monolayers, J. Appl. Phys. 114(9) (2013) 094512.
[3] A. Pysanenko, D. Kollarov a, J. Fedor, J. Ko ci sek, M. Farník, Positive ionization and electron attachment of hexafluoropropylene oxide in different cluster environments, Int. J. Mass Spectrom. 435(2019) 145-150.
[4] A.I. Safonov, V.S. Sulyaeva, E.Y. Gatapova, S.V. Starinskiy, N.I. Timoshenko, O.A. Kabov, Deposition features and wettability behavior of fluoropolymer coatings from hexafluoropropylene oxide activated by NiCr wire, Thin Solid Films 653(2018) 165-172.
[5] H. Olvera-Vargas, Z.X. Wang, J.X. Xu, O. Lefebvre, Synergistic degradation of GenX (hexafluoropropylene oxide dimer acid) by pairing graphene-coated Ni-foam and boron doped diamond electrodes, Chem. Eng. J. 430(2022) 132686.
[6] J.F. Bian, W.R. Lujan, D. Harper-Nixon, H.S. Jeon, D.H. Weinkauf, Effect of hexafluoropropylene oxide plasma polymer particle coatings on the rheological properties of boron nitride/poly(dimethylsiloxane) composites, J. Colloid Interface Sci. 290(2) (2005) 582-591.
[7] M. Koyama, M. Akiyama, K. Kashiwagi, K. Nozaki, T. Okazoe, Synthesis of crystalline CF3-rich perfluoropolyethers from hexafluoropropylene oxide and (trifluoromethyl)trimethylsilane, Macromol. Rapid Commun. 43(9) (2022) e2200038.
[8] A.F. Lowell, Polymerization of Hexafluoropropylene Oxide, US Pat. 3412148A (1968).
[9] D. Lokhat, A. Singh, M. Starzak, D. Ramjugernath, Design of a continuous gasphase process for the production of hexafluoropropene oxide, Chem. Eng. Res. Des. 119(2017) 93-100.
[10] N.T. Tran, S. Cheong, M.D. Ramadhan, J. Kim, K. Kim, H. Kim, H. Lee, Synthesis of hexafluoropropylene oxide from hexafluoropropylene and hypochlorite using hydrofluoroether solvent, Kor. J. Chem. Eng. 41(6) (2024) 1833-1840.
[11] A. Wroblewska, E. Milchert, E. Meissner, Oxidation of hexa fluoropropylene with oxygen to hexafluoropropylene oxide, Org. Process Res. Dev. 14(1) (2010) 272-277.
[12] M. Ła?giewczyk, Z. Czech, Oxidation of hexafluoropropylene to hexafluoropropylene oxide using oxygen, Pol. J. Chem. Technol. 12(2) (2010) 1-3.
[13] D. Lokhat, D. Ramjugernath, M. Starzak, Kinetics of the gas-phase noncatalytic oxidation of hexafluoropropene, Ind. Eng. Chem. Res. 51(43) (2012) 13961-13972.
[14] S. Grimme, Density functional theory with London dispersion corrections, Wiley Interdiscip. Rev. Comput. Mol. Sci. 1(2) (2011) 211-228.
[15] F. Weigend, R. Ahlrichs, Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy, Phys. Chem. Chem. Phys. 7(18) (2005) 3297-3305.
[16] J.J. Zheng, X.F. Xu, D.G. Truhlar, Minimally augmented Karlsruhe basis sets, Theor. Chem. Acc. 128(3) (2011) 295-305.
[17] D. Cremer, A.N. Wu, A. Larsson, E. Kraka, Some thoughts about bond energies, bond lengths, and force constants, Mol. Model. Annu. 6(4) (2000) 396-412.
[18] Z. Konkoli, D. Cremer, A new way of analyzing vibrational spectra. I. Derivation of adiabatic internal modes, Int. J. Quant. Chem. 67(1) (1998) 1-9.
[19] Z. Konkoli, D. Cremer, A new way of analyzing vibrational spectra. III. Characterization of normal vibrational modes in terms of internal vibrational modes, Int. J. Quant. Chem. 67(1) (1998) 29-40.
[20] Y.W. Tao, W.L. Zou, D. Sethio, N. Verma, Y. Qiu, C. Tian, D. Cremer, E. Kraka, In situ measure of intrinsic bond strength in crystalline structures: local vibrational mode theory for periodic systems, J. Chem. Theor. Comput. 15(3) (2019) 1761-1776.
[21] R. Kalescky, W. Zou, E. Kraka, D. Cremer, Local vibrational modes of the water dimereComparison of theory and experiment, Chem. Phys. Lett. 554(2012) 243-247.
[22] Y.W. Tao, C. Tian, N. Verma, W.L. Zou, C. Wang, D. Cremer, E. Kraka, Recovering intrinsic fragmental vibrations using the generalized subsystem vibrational analysis, J. Chem. Theor. Comput. 14(5) (2018) 2558-2569.
[23] K. Yamaguchi, The electronic structures of biradicals in the unrestricted Hartree-Fock approximation, Chem. Phys. Lett. 33(2) (1975) 330-335.
[24] T. Lu, F.W. Chen, Multiwfn: a multifunctional wavefunction analyzer, J. Comput. Chem. 33(5) (2012) 580-592.
[25] S. Canneaux, F. Bohr, E. Henon, KiSThelP: a program to predict thermodynamic properties and rate constants from quantum chemistry results, J. Comput. Chem. 35(1) (2014) 82-93.
[26] T. Lu, Q.X. Chen, Shermo: a general code for calculating molecular thermochemistry properties, Comput. Theor. Chem. 1200(2021) 113249.
[27] Y. Zhu, C. Chen, J.W. Shi, W.F. Shangguan, A novel simulation method for predicting ozone generation in corona discharge region, Chem. Eng. Sci. 227(2020) 115910.
[28] A. Yehia, Calculation of ozone generation by positive DC corona discharge in coaxial wire-cylinder reactors, J. Appl. Phys. 101(2) (2007) 023306.
[29] K. Yanallah, F. Pontiga, Y. Meslem, A. Castellanos, An analytical approach to wire-to-cylinder corona discharge, J. Electrost. 70(4) (2012) 374-383.
[30] X.T. Chen, L.L. Zhang, L.Y. Zhou, S.H. Wang, J.F. Chen, Mechanism and kinetics study of the chemically initiated oxidative polymerization of hexafluoropropylene, AIChE J. 70(11) (2024) e18534.
[31] D. Sianesi, A. Pasetti, R. Fontanelli, G.C. Bernardi, G. Caporiccio, Perfluoropolyethers by photooxidation of fluoroolefins, La Chimica e l’Industria. 55(2) (1973) 208-221.
[32] S.V. Kartsov, P.I. Valov, L.F. Sokolov, S.V. Sokolov, The role of the reactor surface in the liquid-phase oxidation of hexafluoropropylene, Bull. Acad. Sci. USSR Div. Chem. Sci. 27(10) (1978) 2006-2010.

Investigation of reaction pathways and kinetics in the gas-phase noncatalytic oxidation of hexafluoropropylene

Investigation of reaction pathways and kinetics in the gas-phase noncatalytic oxidation of hexafluoropropylene

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Zhe Wang, Zhengpeng Zhu, Kai Xue, Xingmei Guo, Yuanjun Liu, Xiangjun Zheng, Qianqian Fan, Zhongyao Duan, Qinghong Kong, Junhao Zhang. Fabrication of Sb-based alloys/carbon nanofibers with uniform dispersion as anode material for high efficiency sodium storage [J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 208-216.
[2]	Yilun Dong, Kang Xue, Zexing He, Chongjun Li, Ruijie Gao, Zhenfeng Huang, Chengxiang Shi, Xiangwen Zhang, Lun Pan, Jijun Zou. Efficient hydrogen evolution from Amberlyst-15 mediated hydrolysis of ammonia borane under mild conditions [J]. Chinese Journal of Chemical Engineering, 2025, 83(7): 217-228.
[3]	Mingqiang Chen, Tingting Zhu, Yishuang Wang, Defang Liang, Chang Li, Haosheng Xin, Jun Wang. Catalytic oxidation of methane for methanol production over copper sepiolite: Effect of noble metals [J]. Chinese Journal of Chemical Engineering, 2025, 82(6): 1-14.
[4]	Zhuolin Yang, Zhenyu Yang, Yanbin Li, Guangwen Chu, Jianfeng Chen. Enhanced degradation of chloramphenicol wastewater in a submerged rotating packed bed reactor: O₃/PDS synergistic oxidation [J]. Chinese Journal of Chemical Engineering, 2025, 82(6): 176-184.
[5]	Shuang Wei, Yingwei Li, Longlong Wang, Kexin Li, Bin He, Ruirui Zhang, Ruixia Liu. Sulfuric acid etching CeO₂ nanoparticles to promote high KA-Oil selectivity in cyclohexane selective oxidation [J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 151-160.
[6]	Siwen Huang, Kui Wang, Haibo Wang, Li Lv, Tao Zhang, Wenxiang Tang, Zongpeng Zou, Shengwei Tang. Comprehensive utilization of titanium-bearing blast furnace slag by H₂SO₄ roasting and stepwise precipitation [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 24-37.
[7]	Zhengyang Liu, Xianlong Liu, Shuang Ma, Xiaolei Guo, Minhua Ai, Chengxiang Shi, Zhenfeng Huang, Xiangwen Zhang, Jijun Zou, Lun Pan. One-step synthesis of caged hydrocarbon fuel via photoinduced intramolecular cycloaddition of 5-vinyl-2-norbornene [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 61-69.
[8]	Xiao Wei, Xuan Fang, Shuming Ma, Huaqiang He, Zhixin Wu, Silin Li, Shihao Zhang, Pei Nian, Wenlan Ji, Yibin Wei. CC/CoNi-LDH anode doped with Ce³⁺ achieving enhanced electrocatalytic oxidation of ciprofloxacin [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 79-88.
[9]	Yaqi Qu, Hualiang An, Xinqiang Zhao, Yanji Wang. Heterogeneously catalyzed self-condensation of n-butanal [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 89-99.
[10]	Wei Zhang, Yuming Zhang, Haixin Wu, Xinyu Yang, Pei Qiao, Jiazhou Li, Zhewen Chen, Yan Wang. Investigation on the pyrolysis behaviors and kinetics of walnut shell lignocellulosic biomass with additives [J]. Chinese Journal of Chemical Engineering, 2025, 80(4): 303-314.
[11]	Aleksey K. Sagidullin, Sergey S. Skiba, Tatyana P. Adamova, Andrey Y. Manakov. Investigation of the formation processes of CO₂ hydrate films on the interface of liquid carbon dioxide with humic acids solutions [J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 53-61.
[12]	Yiyang Qiu, Chong Liu, Xueting Meng, Yuesen Liu, Jiangtao Fan, Guojun Lan, Ying Li. Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination [J]. Chinese Journal of Chemical Engineering, 2025, 79(3): 145-154.
[13]	Jianfang Liu, Hongwei Huang, Jie Yang, Laishuan Liu, Yu Li. Gold nanoparticles on Fe-doped Co₃O₄ for enhanced low-temperature CO oxidation [J]. Chinese Journal of Chemical Engineering, 2025, 78(2): 175-186.
[14]	Zhuo Wang, Zetao Jin, Hanqi Ning, Baishun Jiang, Kaiyuan Xie, Shufeng Zuo, Qiuyan Wang. Study on sulfur resistance of MnO₂/Beta zeolite in toluene catalytic combustion: The effect of increased acidity on catalytic performance [J]. Chinese Journal of Chemical Engineering, 2025, 78(2): 187-195.
[15]	Feng Gao, Sixiao Zhu, Liping Chang, Weiren Bao, Jinghong Ma, Junjie Liao. Kinetics of hydrogen sulfide removal from coke oven gas over faujasite zeolite: Experimental and modeling studies [J]. Chinese Journal of Chemical Engineering, 2025, 78(2): 232-244.