Hexafluoropropene trimer

Description

Hexafluoropropylene Trimer (HFPT), also known as HFP Trimer, exists in three structural isomers: T-1, T-2, and T-3, with a boiling point of approximately 110–120°C. This high-performance fluorinated material combines chemical inertness, good thermal stability, and excellent dielectric properties, finding broad applications in thermal management and surface treatment.

Chemical Properties

Characteristics

Hexafluoropropylene trimer is a high-end perfluoroalkene compound produced through the catalytic isomerisation of hexafluoropropylene monomers, followed by precision distillation and purification. The industrial product primarily contains the highly reactive T3 isomer and is available in two main grades: industrial grade and electronic grade.
Hexafluoropropylene trimer offers a range of comprehensive advantages, including zero ozone depletion, low GWP environmental properties, absolute non-flammability, high insulation, exceptional stability and low surface tension, making it the ideal replacement for traditional, highly polluting, high-risk, high-global-warming-potential fluorinated solvents and cooling media.

Uses

Hexafluoropropene, trimer may be used in the preparation of photochromic spiroindolinonaphthoxazine derivative. It may be used in the preparation of 2-trifluoromethyl-3-heptadifluoroisopropyl-2-perfluoropentene-4-(N′,N′-dimethylamino propyl) imino(I).

Uses

Hexafluoropropene trimer (HFPT) is a mixture comprising perfluoro-2,4-dimethyl-3-heptene (C9F18, T1, including the E and Z isomers), perfluoro-4-methyl-3-isopropyl-2-penten (C9F18, T2) and perfluoro-2,4-dimethyl-3-ethyl-2-penten (C9F18, T3) (Figure 1). This product exhibits excellent stability, an extremely low dielectric constant, a negligible global warming potential, good fluidity and low toxicity. It can be used in the synthesis of pharmaceuticals and fluorinated surfactants, as well as in cleaning and cooling applications for electronic equipment [3-4].

General Description

Spectra of three isomeric trimers of hexafluoropropene have been investigated. It reacts with primary amines, via indirect substitution of fluorine atoms, to form the corresponding enamines and enimines.

Synthesis

Hexafluoropropene (HFP) can undergo oligomerisation to form hexafluoropropene dimers (HFPD) and trimers (HFPT). The liquid-phase method is the most widely used approach for the oligomerisation (trimerisation) of HFP. In a polar, non-protonic solvent, a nucleophilic catalyst is used to initiate the trimerisation of HFP to form hexafluoropropene trimer (HFPT). The optimal reaction conditions are 50 °C, 1.5 h, 0.4 mmol of the [C₈DABCO][SCN] catalyst, a pressure of 0.5 MPa, and 10 mL of DMF as the solvent. The HFP conversion was close to 100 per cent. The resulting HFPT primarily comprised perfluoro-2,4-dimethyl-3-heptene (C9F18, T1, including the E and Z isomers), perfluoro-4-methyl-3-isopropyl-2-penten (C9F18, T2) and perfluoro-2,4-dimethyl-3-ethyl-2-penten (C9F18, T3), as well as a small amount of dimers [3].

References

[1] Makarov, K. N., et al. "Hexafluoropropene trimer. Synthesis and properties of functional derivatives." Journal of Fluorine Chemistry 10.4 (1977): 323-327.
[2] Hayakawa, Yoshio, Masakazu Nishida, and Taizo Ono. "Novel polystyrene bearing highly branched hexafluoropropene trimer pendants." Polymer bulletin 67.5 (2011): 805-814.
[3] Yang, H., Song, B., Zhang, P., Zhu, Q., Ding, F., Wang, Y., Liu, G., Diao, Y., Wang, H. (2025). Catalytic selectivity in hexafluoropropylene trimerization using tailored nucleophilic ionic liquids. New Journal of Chemistry, 49(26), 11548–11555. https://doi.org/10.1039/d5nj00490j
[4] Makarov, K., Gervits, L., Cheburkov, Y., Knunyants, I., Sass, V. (1977). Hexafluoropropene trimer. Synthesis and properties of functional derivatives. Journal of Fluorine Chemistry, 10(4), 323–327. https://doi.org/10.1016/s0022-1139(00)83107-3