1,1,1,3,3,3-Hexafluoroisopropylmethyl ether (HFE-356mmz) is an important substitute for chlorofluorocarbons and hydrochlorofluorocarbons due to its zero ozone depletion potential and low global warming potential. However, mass production of HFE-356mmz remains a long-standing challenge. Herein, we applied metal fluorides as catalysts in the methylation of 1,1,1,3,3,3-hexafluoroisopropanol to produce HFE-356mmz for the first time.

The catalyst not only improves the synthetic efficiency, but also makes the reaction solvent-free.

The pollution-free, recyclable, and continuous synthetic process enables industrial production of HFE-356mmz. To optimize the synthetic efficiency, a series of metal fluorides (AlF₃, MgF₂, CaF₂, SrF₂, and BaF₂) was used, among which MgF₂ exhibited the highest activity. Through careful examination of each metal fluoride, it was found that the activity of the catalyst was determined by co-operative action of the surface acid–base properties and the total amount of surface acid sites. Based on these results, a rational mechanism for the vapor-phase methylation was proposed.

1,1,1,3,3,3-六氟异丙基甲基醚（HFE-356mmz）由于其臭氧消耗潜能为零且全球变暖潜能较低，因此是氯氟烃和氢氯氟烃的重要替代品。但是，批量生产HFE-356mmz仍然是一项长期挑战。在本文中，我们首次将金属氟化物用作1,1,1,3,3,3-六氟异丙醇的甲基化催化剂，以生产HFE-356mmz。

该催化剂不仅提高了合成效率，而且使反应不含溶剂。

无污染，可回收和连续的合成工艺可实现HFE-356mmz的工业生产。为了优化合成效率，使用了一系列金属氟化物（AlF ₃，MgF ₂，CaF ₂，SrF ₂和BaF ₂），其中MgF ₂表现出最高的活性。通过仔细检查每种金属氟化物，发现催化剂的活性是由表面酸碱性质和表面酸位点总量的协同作用决定的。基于这些结果，提出了气相甲基化的合理机理。