Azeotropic and non-azeotropic hydrofluoro olefin formulations and uses

Abstract

The present disclosure relates generally to azeotropic and non-azeotropic hydrofluoro olefin formulations, particularly formulations including cis-1-Chloro-3,3,3-trifluoropropene, also known as HFO-1233zd(Z), for applications including vapor degreasing, non-flammable aerosol cleaning, swelling solvents, liquid oxygen service line cleaning, carrier and deposition solvents, and metal working fluids.

Description

Attorney Docket No. 68573WO01 (71899-WO)Electronically Filed on: [December 11 , 20251AZEOTROPIC AND NON-AZEOTROPIC HYDROFLUORO OLEFIN FORMULATIONS AND USESCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. provisional patent application no. 63 / 734,525, entitled “Azeotropic and Non-Azeotropic Hydrofluoro Olefin Formulations and Uses”, filed December 16, 2024, and U.S. non-provisional application number 19 / 413,178, also entitled, “Azeotropic and Non-Azeotropic Hydrofluoro Olefin Formulations and Uses,” filed December 9, 2025, the contents of each of which are herein incorporated by reference in their entirety.FIELD

[0002] The present disclosure relates generally to azeotropic and non-azeotropic hydrofluoro olefin formulations and uses, particularly formulations including cis-1 - Chloro-3,3,3-trifluoropropene, also known as HFO-1233zd(Z).BACKGROUND

[0003] 1 -Chloro-3,3,3-trifluoropropene (HFO-1233zd) is an unsaturated chlorofluorocarbon that has the chemical formula HCIC=C(H)CF3. HFO-1233zd exists as Z- (cis-) and E- (trans-) isomers. The trans-isomer, HFO-1233zd(E), has become of some interest as a more environmentally friendly refrigerant, since it has a lower global warming potential or GWP than certain existing refrigerants. Both HFO-1233zd isomers may be prepared by fluorination and dehydrohalogenation reactions starting with 1 , 1 ,1 ,3,3-pentachloropropane.

[0004] While there has been some interest in HFO-1233zd(E) as a more environmentally friendly refrigerant, formulations containing HFO-1233zd(Z) may also have potential, and are explored in the present disclosure. As such, there exists a need for formulations containing HFO-1233zd(Z) and uses for these formulations.Attorney Docket No. 68573WO01 (71899-WO)SUMMARY

[0005] According to an aspect of the present disclosure, a vapor degreasing solution may comprise trans-1 ,2-dichloroethylene and cis-1 -Chloro-3, 3, 3- trifluoropropene. The vapor degreasing solution may further comprise methanol.

[0006] According to another aspect of the present disclosure, a non-flammable aerosol cleaning solution may comprise trans-1 ,2-dichloroethylene, cis-1 -Chloro- 3,3,3-trifluoropropene, and trans-1 ,3,3,3-tetrafluoropropene. The non-flammable aerosol cleaning solution may further comprise ethanol, or carbon dioxide, or both.

[0007] According to another aspect of the present disclosure, a swelling solvent may comprise cis-1-Chloro-3,3,3-trifluoropropene. The swelling solvent may further comprise heptane, or trans-1 -Chloro-3, 3, 3-trifluoropropene, or both.

[0008] According to another aspect of the present disclosure, a liquid oxygen service line cleaning fluid may comprise cis-1 -Chloro-3, 3, 3-trifluoropropene.

[0009] According to another aspect of the present disclosure, a carrier and deposition solvent for fluoropolymer (fluorinated acrylate) coatings may comprise cis- 1 -Chloro-3, 3, 3-trifluoropropene.

[0010] According to another aspect of the present disclosure, a carrier and deposition solvent for solid pesticides may comprise cis-1 -Chloro-3, 3,3- trifluoropropene. The carrier and deposition solvent for solid pesticides may be applied to inert particles. The inert particles may be made of gypsum.

[0011] According to another aspect of the present disclosure, a metal working fluid for cooling cutting and drilling operations may comprise cis-1 -Chloro-3, 3,3- trifluoropropene. The metal working fluid may further comprise dodecanoate.

[0012] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate the various embodiments describedAttorney Docket No. 68573WO01 (71899-WO) herein, and together with the description serve to explain the principles and operations of the claimed subject matter.BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The following is a description of the examples depicted in the accompanying drawings. The figures are not necessarily to scale, and certain features and certain views of the figures may be exaggerated in scale or in schematic for clarity or conciseness.

[0014] FIG. 1 illustrates a skeletal structural formula of cis-1 -Chloro-3,3,3- trifluoropropene, also known as HFO-1233zd(Z).

[0015] FIG. 2 illustrates a skeletal structural formula of trans-1 -Chloro-3,3,3- trifluoropropene, also known as HFO-1233zd(E).

[0016] The foregoing summary, as well as the following detailed description, will be better understood when read in conjunction with the figures. It should be understood that the claims are not limited to the arrangements and instrumentality shown in the figures. Furthermore, the appearance shown in the figures is one of many ornamental appearances that can be employed to achieve the stated functions of the apparatus.DETAILED DESCRIPTION

[0017] In the following detailed description, specific details may be set forth to provide a thorough understanding of the embodiments of the present disclosure. However, it will be clear to one skilled in the art when disclosed examples may be practiced without some or all of these specific details. For the sake of brevity, well- known features or processes may not be described in detail. In addition, like or identical reference numerals may be used to identify common or similar elements.

[0018] One or more specific embodiments of the present disclosure will be described below. In an effort to provide a concise description of these embodiments, all features with an actual implementation may not be described in the specification. It should be appreciated that in the development of any such actual implementation,Attorney Docket No. 68573WO01 (71899-WO) as in any engineering or design project, numerous implementation-specific decisions must be made to achieve the developers' specific goals, such as compliance with system-related and business-related constraints, which may vary from one implementation to another. Moreover, it should be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking of design, fabrication, and manufacture for those of ordinary skill having the benefit of this disclosure.

[0019] When introducing elements of various embodiments of the present disclosure, the articles “a,” “an,” “the,” and “said” are intended to mean that there are one or more of the elements. The terms “comprising,” “including,” and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0020] Cis-1 -Chloro-3,3,3-trifluoropropene, also known as HFO-1233zd(Z) is a nonflammable organic solvent. Its ultra low global warming potential (GWP) of less than 1 makes it an environmental friendly solvent candidate in various industry applications, including electronic cleaning. Due to its boiling point of 39 °C and Kb value, HFO-1233zd(Z) can be used in vapor degreasing and aerosol cleaning applications.

[0021] Vapor degreasing.

[0022] According to certain aspects of the present disclosure, a vapor degreasing solution may comprise cis-1 -Chloro-3,3,3-trifluoropropene and methanol. In certain embodiments, such a vapor degreasing solution may comprise 90-99, or 95-98, or 96- 97 wt. % cis-1 -Chloro-3,3,3-trifluoropropene and 1 -10, or 2-5, or 3-4 wt. % methanol. The boiling point of this solution may be approximately 38 °C. Combining HFO1233zd(Z) with methanol may add polarity and hydrogen bonding characteristics that improve the ability of the composition to remove polar contaminants such as soldering fluxes, some hydraulic fluids, and machining fluids. The azeotropic composition remains nonflammable.Attorney Docket No. 68573WO01 (71899-WO)

[0023] According to certain aspects of the present disclosure, a vapor degreasing solution may comprise trans-1 ,2-dichloroethylene and cis-1 -Chloro-3,3,3- trifluoropropene. In certain embodiments, such a vapor degreasing solution may comprise 65-90, or 70-85, or 75-80 wt. % trans-1 ,2-dichloroethylene and 10-35, or 15- 30, or 20-25 wt. % cis-1-Chloro-3,3,3-trifluoropropene. An example vapor degreasing solution and its effectiveness in removing certain soils is shown in Table 1. In certain embodiments, the vapor degreasing solution may further comprise methanol.

[0024] Table 1. Example vapor degreasing solution comprising trans-1 ,2- dichloroethylene and cis-1-Chloro-3,3,3-trifluoropropene (HFO1233zd(Z)).

[0025] According to certain aspects of the present disclosure, a vapor degreasing solution may comprise cis-1-Chloro-3,3,3-trifluoropropene, trans-1 ,2- dichloroethylene, and methanol. Such a solution may be considered a binary azeotrope (two azeotropes blended). In certain embodiments, a vapor degreasing solution may comprise 0-5, or 1-4, or 3 wt. % methanol, and 20-30, or 21-25, or 22 wt. % trans-1 ,2-dichloroethylene and 70-80, or 72-78, or 75 wt. % cis-1 -Chloro-3,3,3- trifluoropropene. An example vapor degreasing solution and its effectiveness in removing certain soils is shown in Table 2.

[0026] Table 2. Example solution comprising methanol, trans-1 ,2- dichloroethylene, and cis-1-Chloro-3,3,3-trifluoropropene.Attorney Docket No. 68573WO01 (71899-WO)

[0027] According to certain aspects of the present disclosure, a vapor degreasing solution may comprise 75-99, or 80-95, or 85-90 wt. % trans-1 ,2-dichloroethylene and 1 -25, or 4-20, or 9-15 wt. % cis-1-Chloro-3,3,3-trifluoropropene. In certain other embodiments, a vapor degreasing solution may comprise 80-90 or 90-95 wt. % trans- 1 ,2-dichloroethylene and 4-10 or 10-20 wt. % cis-1-Chloro-3,3,3-trifluoropropene. In certain embodiments, such a solution may be considered a near- non- or pseudoazeotrope. The boiling point of this solution may be approximately 38 °C. Combining HFO1233zd(Z) with trans-1 ,2-dichloroethylene may increase solvency which improves the ability of the composition to remove a wide variety of contaminants such as soldering fluxes, some hydraulic fluids, oils and greases, some coatings, and excess adhesives. The azeotropic composition remains nonflammable.

[0028] According to certain aspects of the present disclosure, a vapor degreasing solution may comprise cis-1 -Chloro-3,3,3-trifluoropropene and one or more of the following solvents, all designed to keep the boiling point of the vapor degreasing solution between 25 °C and 65 °C: acetone, cyclopentane, isopentane, ethyl formate, methyl formate, and methyl acetate.

[0029] Aerosol Cleaning.

[0030] According to certain aspects of the present disclosure, a non-flammable aerosol cleaning solution may comprise trans-1 ,2-dichloroethylene, cis-1 -Chloro- 3,3,3-trifluoropropene, and trans-1 ,3,3,3-tetrafluoropropene. The non-flammable aerosol cleaning solution may further comprising ethanol, or carbon dioxide, or both. For example, the non-flammable aerosol cleaning solution may comprise 35-40 wt. % trans-1 , 2-dichloroethylene, 30-35 wt. % cis-1 -Chloro-3,3,3-trifluoropropene, and 20- 25 wt. % trans-1 ,3,3,3-tetrafluoropropene.Attorney Docket No. 68573WO01 (71899-WO)

[0031] According to certain aspects of the present disclosure, a non-flammable aerosol cleaning solution may comprise trans-1 ,2-dichloroethylene, cis-1 -Chloro- 3,3,3-trifluoropropene, and trans-1 ,3,3,3-tetrafluoropropene. The non-flammable aerosol cleaning solution may further comprising ethanol, or carbon dioxide, or both. For example, the non-flammable aerosol cleaning solution may comprise 35-40 wt. % trans-1 , 2-dichloroethylene, 30-35 wt. % cis-1 -Chloro-3,3,3-trifluoropropene, and 20- 25 wt. % trans-1 ,3,3, 3-tetrafluoropropene. One advantage of this aerosol cleaning solution is that it has a lower global warming potential (GWP) compared to existing aerosol cleaning solutions.

[0032] HFO1233zd(E) is the trans isomer of 1 -Chloro-3,3,3-trifluoropropene and could operate as an aerosol cleaning solution. However, HFO1233zd(E) is highly volatile and its boiling point is 19°C (66°F), which makes it difficult to handle at typical ambient temperatures. In fact, it may diminish the cleaning strength of other solvents with which it might otherwise be combined by removing heat through latent heat of vaporization. Table 3 shows a comparison of GWP for an aerosol cleaning solution where HFO1233zd(Z) has been substituted for a high GWP HFC245fa (nonflammable solvent) and HFO1234ze has been substituted for HFC134a (nonflammable propellant). These two substitutions reduced greenhouse gas (GHG) content and global warming potential (GWP) significantly.

[0033] Table 3. Comparison of global warming potentials of different solvents and propellants.Attorney Docket No. 68573WO01 (71899-WO)

[0034] Table 4. Comparison of global warming potentials of different solvents and propellants.

[0035] According to certain aspects of the present disclosure, other formulas with varying ratios of flammable contents (e.g., ethanol and trans-1 ,2-dichloroethylene) to non-flammable contents (e.g., HFO-1233zd(Z), HFO-1234ze, and CO2) may be formulated to achieve specific cleaning strengths and characteristics.

[0036] Swelling solvent.

[0037] In swelling applications, parts including silicone and urethane tubes can be assembled by temporarily enlarging (swelling) the tubes with a volatile solvent so that the tubes fit easily over male connectors. A tight gripping bond is formed when the solvent volatilizes and returns to its original shape. Flammable silicone solvents (e.g., hexamethyldisiloxane (HMDS)) and hydrocarbons (e.g., n-heptane) are typically used. However, because the solvent is released to the environment, non-PFAS (non- polyfluoroalkyl substances) solvents are desirable to environmentally conscious users. Further, because this technique is often used to assemble medical devices (critical applications) a non-flammable solvent like HFO1233zd(Z) is desirable to eliminate chances of fire in a factory making mission critical devices.

[0038] According to certain aspects of the present disclosure, a swelling solvent may comprise cis-1 -Chloro-3,3,3-trifluoropropene. In some embodiments, the swellingAttorney Docket No. 68573WO01 (71899-WO) solvent may further comprise heptane. For example, the swelling solvent may comprise 90-95 wt. % cis-1 -Chloro-3,3,3-trifluoropropene and 5-10 wt. % heptane. In some embodiments, the swelling solvent may further comprise trans-1 -Chloro-3,3,3- trifluoropropene. For example, the swelling solvent may further comprise 50-80 wt. % cis-1 -Chloro-3,3,3-trifluoropropene and 20-50 wt. % trans-1 -Chloro-3,3,3- trifluoropropene. In other embodiments, the swelling solvent may comprise hexamethyldisiloxane (HMDS).

[0039] Table 5. Comparison of swelling solvents.

[0040] Liquid oxygen service line cleaning fluid.

[0041] A strong non-flammable solvent is typically required for cleaning lines and vessels containing liquid oxygen (LOx). Any organic or remotely flammable material, traces of residue and particles could react with the LOx, which could result in a catastrophic explosion and failure. HFO1233zd(Z) is a strong solvent capable of removing such traces and it is completely non-flammable so poses no danger if tracesAttorney Docket No. 68573WO01 (71899-WO) are left behind. While HF01233zd(E) can be used for this process, its low boiling point (as discussed above with respect to aerosol cleaning) makes it difficult to use.

[0042] Another potential use is for cleaning validation. Manufacturing operations may use less expensive organic or water-based cleaning chemistries to do most of the manufacturing, processing, machining, and drawing oil removal. However, regardless of how the parts are cleaned, the cleaning must be validated. A liquid oxygen service line cleaning fluid may comprising or consisting of HFO1233zd(Z) may be ideal for cleaning validation. The properties that make HFO1233zd(Z) a good solvent for cleaning also make it a good solvent for cleaning validation. Its strong solvency essentially or practically removes all traces of contaminants and previous cleaning chemistry, when a cleaning validation fluid containing HFO1233zd(Z) is flushed through the system of cleaned lines. The cleaning validation fluid that is flushed through is then evaporated, either leaving behind (or, more ideally, not leaving behind) any remaining non-volatile residue (NVR) or particles.

[0043] According to certain aspects of the present disclosure, a liquid oxygen service line cleaning fluid may comprise or consist of cis-1 -Chloro-3,3,3- trifluoropropene.

[0044] Carrier and deposition solvent.

[0045] According to certain aspects of the present disclosure, a carrier and deposition solvent may be used to apply solid pesticides application to inert (e.g., gypsum) particles to disperse the pesticide as a heavier-than-air powder. The solid nature of the pesticide provides a timed-release feature and some pesticides are available only as solids. For example, a nematodicide called Aldicarb is applied to gypsum substrate by dissolving it in methylene chloride, then mixing the solution with the gypsum to make a slurry. Methylene chloride is then vacuum evaporated from the slurry. Methylene chloride may not be desired due to certain of its properties, so there is potential interest in alternative solvents that may be more environmentally friendly.

[0046] According to certain aspects of the present disclosure, a carrier and deposition solvent may comprise cis-1-Chloro-3,3,3-trifluoropropene. The carrier andAttorney Docket No. 68573WO01 (71899-WO) deposition solvent may be used to carry and deposit fluoropolymer (fluorinated acrylate) coatings.

[0047] According to certain aspects of the present disclosure, a carrier and deposition solvent may comprise cis-1 -Chloro-3,3,3-trifluoropropene. In certain embodiments, the carrier and deposition solvent may comprise 1 -Chloro-2,3,3- trifluoropropene (HFO1233yd). In certain embodiments, the carrier and deposition solvent may comprise both cis-1 -Chloro-3,3,3-trifluoropropene and 1 -Chloro-2,3,3- trifluoropropene. The carrier and deposition solvent may be used to carry and deposit solid pesticides onto inert particles. In some embodiments, the inert particles may be made of gypsum. The carrier and deposition solvent may be used to carry and deposit solid pesticides onto powders. The carrier and deposition solvent may be used to carry and deposit protective coatings onto seeds.

[0048] According to certain aspects of the present disclosure, a carrier solvent may comprise cis-1 -chloro-3,3,3-trifluoropropene. The carrier solvent may be used to carry silicone.

[0049] Metal working fluid.

[0050] Metal working fluids comprising volatile HFE7100 may be useful for high precision metal working because such metal working fluids can cool the process site without contaminating it with the oils, surfactants, lubricants, and anticorrosive additives found in typical metal processing. Metal working fluids made by substituting HFO1233zd(Z) are an effective low GWP, non-PFAS, non-flammable alternative to HFE7100 based metal working fluids.

[0051] According to certain aspects of the present disclosure, a metal working fluid may comprise cis-1-Chloro-3,3,3-trifluoropropene. The metal working fluid may be used for cooling cutting and drilling operations. The metal working fluid may further comprise dodecanoate. For example, the metal working fluid may comprise 95 to 99.9 wt. % cis-1 -Chloro-3,3,3-trifluoropropen and 0.1 to 5 % dodecanoate.

[0052] The various aspects and embodiments disclosed herein are not intended to be limiting. Other embodiments may be utilized, and other changes may be made,Attorney Docket No. 68573WO01 (71899-WO) without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein and illustrated in the figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are contemplated herein.

Claims

Attorney Docket No. 68573WO01 (71899-WO)CLAIMS1 . A vapor degreasing solution comprising trans-1 ,2-dichloroethylene and cis-1-Chloro- 3,3,3-trifluoropropene.

2. The vapor degreasing solution of claim 1 , comprising 75-80 wt. % trans-1 ,2- dichloroethylene and 20-25 wt. % cis-1 -Chloro-3,3,3-trifluoropropene.

3. The vapor degreasing solution of claim 1 , comprising 80-95 wt. % trans-1 ,2- dichloroethylene and 4-20 wt. % cis-1 -Chloro-3,3,3-trifluoropropene.

4. The vapor degreasing solution of claim 1 , further comprising methanol.

5. A non-flammable aerosol cleaning solution comprising trans-1 ,2-dichloroethylene, cis- 1 -Chloro-3,3,3-trifluoropropene, and trans-1 ,3,3,3-tetrafluoropropene.

6. The non-flammable aerosol cleaning solution of claim 5, further comprising ethanol.

7. The non-flammable aerosol cleaning solution of claim 6, further comprising carbon dioxide.

8. The non-flammable aerosol cleaning solution of claim 5, comprising 35-40 wt. % trans- 1 ,2-dichloroethylene, 30-35 wt. % cis-1 -Chloro-3,3,3-trifluoropropene, and 20-25 wt. % trans-1 ,3,3,3-tetrafluoropropene.Attorney Docket No. 68573WO01 (71899-WO)9. A swelling solvent comprising cis-1-Chloro-3,3,3-trifluoropropene.

10. The swelling solvent of claim 9 further comprising heptane.11 . The swelling solvent of claim 9 further comprising hexamethylsiloxane.

12. The swelling solvent of claim 10 comprising 90-95 wt. % cis-1 -Chloro-3,3,3- trifluoropropene and 5-10 wt. % heptane.

13. The swelling solvent of claim 9 further comprising trans-1 -Chloro-3,3,3- trifluoropropene.

14. The swelling solvent of claim 12 comprising 50-80 wt. % cis-1 -Chloro-3,3,3- trifluoropropene and 20-50 wt. % trans-1 -Chloro-3,3,3-trifluoropropene.

15. A liquid oxygen service line cleaning fluid comprising cis-1 -Chloro-3,3,3- trifluoropropene.

16. A carrier and deposition solvent for fluoropolymer (fluorinated acrylate) coatings, wherein the carrier and deposition solvent comprises cis-1 -Chloro-3,3,3- trifluoropropene.

17. A carrier and deposition solvent for solid pesticides being applied to inert particles, wherein the carrier and deposition solvent comprises cis-1 -Chloro-3,3,3- trifluoropropene.Attorney Docket No. 68573WO01 (71899-WO)18. The carrier and deposition solvent of claim 16, wherein the inert particles are made of gypsum.

19. A carrier solvent for silicone, wherein the carrier solvent comprises comprising cis-1 - Chloro-3,3,3-trifluoropropene.

20. A metal working fluid for cooling cutting and drilling operations, wherein the metal working fluid comprises cis-1 -Chloro-3,3,3-trifluoropropene.

21. The metal working fluid of claim 20 further comprising dodecanoate.

22. The metal working fluid of claim 21 comprising 95 to 99.9 wt. % cis-1 -Chloro-3, 3,3- trifluoropropen and 0.1 to 5 % dodecanoate.

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