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Hydrofluoroether
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Hydrofluoroethers (HFEs) are a class of organic solvents. As non-ozone-depleting chemicals, they were developed originally as a replacement for CFCs, HFCs, HCFCs, and PFCs.[1][unreliable source?] They are typically colorless, odorless, tasteless, low toxicity, low viscosity, and liquid at room temperature. The boiling point of HFEs vary from 50 °C (122 °F) to nearly 100 °C (212 °F). Although 3M first developed HFEs, other manufacturers have begun producing them.
Applications
[edit]Industrial uses are many and varied, including:
- Vapor de-greasing solvent
- Refrigerant and heat-transfer fluid
- Anhydrous fluid cleaner
They are sometimes applied as blends such as HFE 7100, which is a mixture of methyl nonafluorobutyl ether (methoxyperfluorobutane) and methyl nonafluoroisobutyl ether.[2]
3M produces hydrofluoroether compounds under the names Novec 7000, 7100, 7200, 7300, 7500, and 7700 as liquid coolants for many applications, including full immersion cooling of computer electronics.[3]
Environmental impact
[edit]Because of their high molecular weights, HFEs remain in the atmosphere for less than two weeks, being absorbed into the ground rather than remaining dissolved in the atmosphere. Although HFEs are greenhouse gases, the EPA does not regulate their use due to the short atmospheric lifetimes and zero ozone depletion potential compared to alternative chemicals.[4]
See also
[edit]External links
[edit]References
[edit]- ^ "earthscape.org". Archived from the original on 2002-11-30. Retrieved 2009-03-17.
- ^ "Novec HFE-7100 MSDS" (PDF). Pioneer Forensics. Retrieved 22 July 2020.
- ^ "Immersion cooling for data centers". 3M. Retrieved 7 April 2021.
- ^ "products3.3m.com". Archived from the original on 2009-04-04. Retrieved 2009-03-17.
Hydrofluoroether
View on GrokipediaIntroduction
Definition and Classification
Hydrofluoroethers (HFEs) are a class of organic compounds defined by the general formula , where is a perfluoroalkyl group and is a partially or non-fluorinated alkyl group.[6] This ether linkage connects a fluorinated segment to a hydrogen-containing one, setting HFEs apart from fully fluorinated ethers like perfluoroethers, which lack C-H bonds and exhibit different reactivity and environmental profiles.[7] HFEs are classified into segregated and non-segregated types based on the distribution of fluorine atoms. Segregated HFEs feature a distinct perfluoroalkyl chain () separated from the alkyl chain () by the oxygen atom, exemplified by structures like .[6] Non-segregated HFEs, in contrast, have fluorine atoms distributed across both sides of the ether linkage, such as in , leading to varied physical properties.[8] A representative commercial segregated HFE is HFE-7100, a mixture of approximately 40% methyl nonafluorobutyl ether () and 60% methyl nonafluoroisobutyl ether ().[9] These compounds are typically colorless, low-odor liquids at room temperature, exhibiting low toxicity, boiling points between 50°C and 100°C, and low viscosity, which facilitate their use in precision applications.[6] Developed as non-ozone-depleting alternatives to chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) in the wake of the 1987 Montreal Protocol, HFEs possess zero ozone depletion potential while offering compatible solvency and stability.Historical Development
The development of hydrofluoroethers (HFEs) emerged in the 1990s as a direct response to international environmental regulations aimed at phasing out ozone-depleting substances. The 1987 Montreal Protocol, which entered into force in 1989, mandated the global elimination of chlorofluorocarbons (CFCs) and later hydrochlorofluorocarbons (HCFCs) due to their role in stratospheric ozone depletion. This created an urgent need for alternative solvents and refrigerants that maintained performance without environmental harm, prompting research into fluorinated compounds with zero ozone depletion potential (ODP). Building on over four decades of fluorochemical expertise, 3M initiated the synthesis of HFEs using organo-fluorine chemistry, computational modeling, and toxicological assessments to engineer fluids that balanced efficacy, safety, and ecological compatibility.[10] In 1996, 3M introduced the first commercial HFEs under the Novec Engineered Fluids brand as non-ozone-depleting substitutes for CFCs and HCFCs, marking a pivotal milestone in the transition away from legacy solvents like CFC-113.[11] These early products, including Novec 7000, addressed the impending 1996 U.S. phaseout of Class I ozone-depleting substances under the Clean Air Act Amendments and Montreal Protocol requirements. The U.S. Environmental Protection Agency's Significant New Alternatives Policy (SNAP) program quickly approved HFEs for applications in electronics, metal, and precision cleaning, recognizing their low toxicity and compatibility with existing equipment. By the late 1990s, 3M expanded the lineup with fluids like Novec 7100 and 7200, which were evaluated for specialized uses such as latent fingerprint development, demonstrating comparable performance to banned CFCs.[10] The 1997 Kyoto Protocol further accelerated HFE innovation by targeting hydrofluorocarbons (HFCs) as potent greenhouse gases under its framework for reducing global emissions. This positioned HFEs as short-lived, low-global-warming-potential (GWP) options to replace not only ozone-depleters but also high-GWP HFCs, aligning with evolving climate commitments. By the early 2000s, production expanded beyond 3M to other manufacturers, including international firms like Daikin Industries and AGC Chemicals, fostering broader adoption and diversification of HFE formulations.[11][12] In December 2022, 3M announced its exit from per- and polyfluoroalkyl substances (PFAS) manufacturing, discontinuing production of all Novec engineered fluids, including HFEs, by the end of 2025. This shift has increased reliance on other manufacturers such as Daikin Industries and AGC Chemicals.[13]Chemistry
Molecular Structure
Hydrofluoroethers (HFEs) possess a general molecular structure represented as , where is a fluorinated alkyl group (such as or ) and is a non-fluorinated or partially fluorinated alkyl group (such as or ). This ether linkage via the oxygen atom connects the segregated fluorinated and hydrogenated chains, distinguishing HFEs from fully fluorinated or hydrocarbon ethers.[14] The core bonding in HFEs features a central C-O-C ether moiety, which imparts polarity and solubility characteristics, flanked by multiple C-F bonds. These C-F bonds exhibit high strength, with bond dissociation energies typically around 485-544 kJ/mol, contributing to the overall chemical inertness and thermal stability of the molecules.[15][16] Unlike chlorofluorocarbons, HFEs lack chlorine atoms in their structure, eliminating potential reactivity with stratospheric ozone.[17] Representative examples illustrate this structure. HFE-7000, also known as methyl heptafluoropropyl ether, has the formula (C4H3F7O). HFE-7100 is a commercial mixture primarily of two isomers: the linear methyl nonafluorobutyl ether and the branched methyl nonafluoroisobutyl ether (both C5H3F9O). Similarly, Novec 7200, or ethyl nonafluorobutyl ether, follows the pattern (C6H5F9O), with analogous linear and branched variants.[18][17][19] In the context of low-GWP alternatives to perfluorocarbons for semiconductor plasma etching, desirable structural features include 3–6 carbons, ether (-O-) or alcohol groups to facilitate atmospheric degradation, unsaturation for very low GWP, and moderate F/C ratios (~1.5–2.0) to balance fluorine radical supply for etching and minimize polymerization. HFEs exemplify these traits through their ether linkages and typical F/C ratios in this range.[20][21] Structural variations in HFEs include linear versus branched configurations in the chain, which influence molecular packing and intermolecular forces, thereby affecting boiling points and solvency behavior. For instance, branched structures like those in the iso-isomers of HFE-7100 tend to lower boiling points relative to linear counterparts due to reduced symmetry.[22]Physical and Chemical Properties
Hydrofluoroethers (HFEs) exhibit a range of physical properties that make them suitable for various technical applications, characterized by their liquid state at room temperature and low intermolecular forces due to the presence of fluorine atoms. Typical densities for HFEs fall in the range of 1.4 to 1.6 g/cm³ at 25°C, as exemplified by HFE-7100 with a density of 1.51 g/cm³.[23] They possess low viscosity, typically 0.4 to 0.6 cP at 25°C, with HFE-7100 showing a dynamic viscosity of approximately 0.57 cP calculated from its kinematic viscosity of 0.38 cSt.[23] Surface tension is notably low, ranging from 13 to 18 dyn/cm, such as 13.6 dyn/cm for HFE-7100, which facilitates wetting and penetration in diverse substrates.[24] The refractive index is around 1.3, with HFE-7100 measured at 1.301 at 20°C.[25] HFEs are generally non-flammable, with most exhibiting no flash point under standard testing conditions, as confirmed for HFE-7100 by ASTM methods.[26] Vapor pressure at 25°C typically spans 20 to 50 kPa, for instance, 26.9 kPa for HFE-7100, contributing to their volatility.[26] Boiling points vary from 50 to 100°C across the class, with HFE-7100 boiling at 61°C, reflecting their tunable chain lengths.[27] This dual hydrophilic and hydrophobic nature, stemming from the ether oxygen and fluorinated segments, imparts high solvency for both polar and non-polar substances.[28] Chemically, HFEs demonstrate high thermal and chemical stability, with decomposition temperatures exceeding 200°C; for example, HFE-7100 remains stable up to 300°C before thermal decomposition occurs.[29] They are inert toward most metals, plastics, and elastomers, showing no significant reactivity under ambient conditions.[30] Hydrolysis proceeds slowly in acidic or basic environments, with HFE-7100 displaying minimal reactivity in stability assessments.[31] The dielectric constant ranges from 2 to 7, as seen in HFE-7300 at 7.16 at 1 kHz, which supports non-conductive behavior in electronic contexts.[32]| Property | Typical Range for HFEs | Example (HFE-7100 at 25°C) | Source |
|---|---|---|---|
| Density | 1.4–1.6 g/cm³ | 1.51 g/cm³ | [23] |
| Viscosity | 0.4–0.6 cP | 0.57 cP | [23] |
| Surface Tension | 13–18 dyn/cm | 13.6 dyn/cm | [24] |
| Refractive Index | ~1.3 | 1.301 (at 20°C) | [25] |
| Boiling Point | 50–100°C | 61°C | [27] |
| Vapor Pressure | 20–50 kPa | 26.9 kPa | [26] |
| Dielectric Constant | 2–7 | 7.4 (at 1 kHz for similar HFE) | [33] |
