Reactions of Methyl Perfluoroalkyl Ethers with Isopropyl Alcohol: Experimental and Theoretical Studies

The reaction of an isomeric mixture of the methyl perfluoroalkyl ether, C4F9OCH3 (Novec-7100), in the presence of isopropyl alcohol (IPA) and/or water has been studied by measuring the rate of product formation using an ion-selective electrode (ISE) for fluoride ion, Karl Fisher coulometric titrations for water, and 1H and 19F NMR spectroscopy for product identification and rate studies. The results showed the methyl perfluoroalkyl ether to be very stable with products forming at the rate of ∼1 ppm per year at a laboratory temperature of 20 °C. Measurements over the temperature range of 6° to 100 °C were made on samples aged for periods up to 1.8 years. Density functional theory calculations (DFT, B3LYP/6-31+G(d)) were employed to investigate different reaction pathways and formulate the probable reaction mechanism. The experimental enthalpy (ΔH⧧) and entropy (ΔS⧧) of activation were determined based on several different kinetic measurements. The ΔH⧧ values are in the range of 20–25 kcal/mol and the corresponding ΔS⧧ values range from −32 to −15 cal/(mol K). These are in good agreement with the theoretical values. While the range of ΔH⧧ values does not change appreciatively, the ΔS⧧ values are dependent on the proportion of vapor to liquid involved in the reaction of C4F9OCH3 with IPA so that the more vapor the more negative the ΔS⧧ value

Characterization by NMR of Reactants and Products of Hydrofluoroether Isomers, CF3(CF2)3OCH3 and (CF3)2C(F)CF2OCH3, Reacting with Isopropyl Alcohol

The 3M Company product Novec™ 71IPA DL, a mixture of methoxyperfluorobutane, methoxyperfluoroisobutane and 4.5 wt.% isopropyl alcohol, has been found to be very stable at ambient temperature, producing fluoride at the rate of ~1 ppm/year. Our earlier kinetic and theoretical studies have identified the reaction mechanism. This paper identifies the 1H and 19F NMR chemical shifts, multiplicities, and coupling constants of reactants and the major products that result from aging the mixture in sealed Pyrex NMR tubes for periods up to 1.8 years at temperatures from 26 °C to 102 °C. Chemical shifts and coupling constants of fluorine and hydrogen atoms on the hydrofluoroethers and isopropyl alcohol are traced through the reactions to their values in the products – esters, isopropylmethyl ether, and HF. These spectral positions, multiplicities, and coupling constants are presented in table format and as figures to clarify the transformations observed as the samples age

Electrochemical Evaluation of the Compatibility of Fresh and Aged NovecTM 71IPA with Beryllium, Stainless Uranium, 304L Stainless Steel, and 2024-T3 Aluminum Alloy

This study was a material compatibility assessment of four metals (beryllium, stainless uranium, 304L stainless steel, and 2024-T3 aluminum) with an environmentally benign, non-aqueous, near-azeotropic mixture of hydrofluoroether (Novec™ 7100) with 4.5 wt% isopropanol designated Novec™ 71IPA. The intent is to use the Novec™ 71IPA to clean materials in sensitive, long-term assemblies. There is concern when an aged solvent is used to clean a metal surface, it may cause corrosion due to fluoride formation as the solvent ages. Two solvent conditions, one having no detectable fluoride (fresh) and the other with ≥17 ppm fluoride (aged) were evaluated. Electrochemical evaluations using impedance spectroscopy were performed to monitor the metal surfaces for signs of reaction. Microscopic and spectroscopic techniques, including X-ray photoelectron spectroscopy, were used to characterize the metal surfaces before and after electrochemical tests. Increased impedance was observed when beryllium substrates were exposed to fresh or aged Novec™ 71IPA and was attributed to formation of organic and/or inorganic films on native beryllium oxide. Other metals exhibited insignificant changes in impedance but did show some passive film formation. Results confirmed Novec™ 71IPA, containing up to 17 ppm fluoride, had no corrosive effect on the four tested metals and may be used to safely clean them

Reactions of Methyl Perfluoroalkyl Ethers with Isopropyl Alcohol: Experimental and Theoretical Studies

The reaction of an isomeric mixture of the methyl perfluoroalkyl ether, C₄F₉OCH₃ (Novec-7100), in the presence of isopropyl alcohol (IPA) and/or water has been studied by measuring the rate of product formation using an ion-selective electrode (ISE) for fluoride ion, Karl Fisher coulometric titrations for water, and ¹H and ¹⁹F NMR spectroscopy for product identification and rate studies. The results showed the methyl perfluoroalkyl ether to be very stable with products forming at the rate of ∼1 ppm per year at a laboratory temperature of 20 °C. Measurements over the temperature range of 6° to 100 °C were made on samples aged for periods up to 1.8 years. Density functional theory calculations (DFT, <i>B3LYP/6-31+G­(d)</i>) were employed to investigate different reaction pathways and formulate the probable reaction mechanism. The experimental enthalpy (Δ<i>H</i>^⧧) and entropy (Δ<i>S</i>^⧧) of activation were determined based on several different kinetic measurements. The Δ<i>H</i>^⧧ values are in the range of 20–25 kcal/mol and the corresponding Δ<i>S</i>^⧧ values range from −32 to −15 cal/(mol K). These are in good agreement with the theoretical values. While the range of Δ<i>H</i>^⧧ values does not change appreciatively, the Δ<i>S</i>^⧧ values are dependent on the proportion of vapor to liquid involved in the reaction of C₄F₉OCH₃ with IPA so that the more vapor the more negative the Δ<i>S</i>^⧧ value