Propellant compositions containing 1,1-difluoropropene

Abstract

Compositions and methods relating to propellants, sprayable compositions, and aerosol dispensing systems comprising HFO-1252zc.

Description

TS0098-W001TITLE OF THE INVENTION PROPELLANT COMPOSITIONS CONTAINING 1 ,1-DIFLUOROPROPENE CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 745,409 filed January 15, 2025, the disclosure of which is incorporated herein by reference in its entirety.BACKGROUND OF THE INVENTION

[0002] Fluorinated compounds commonly employed as propellants include hydrofluorocarbons (HFCs) such as HFC-134a (CF3CH2F) and HFC-227ea (CF3CHFCF3), and hydrofluoroolefins (HFOs) such as HFO-1234zeE (E- CF3CH=CHF). These HFCs and HFOs do not contribute to ozone depletion, but due to their large contributions to global warming, HFCs such as HFC-134a and HFC- 227ea are currently limited to use in special applications, such as their use as propellants in metered dose inhalers (MDIs). HFOs such as HFO-1234zeE, which contain a CF3 group, have a low impact on global warming but degrade in the atmosphere to produce trifluoroacetic acid (TFA). In addition they are classified as perfluoroalkyl and perfluoroalkyl substances (PFASs) and are hence subject to PFAS-related regulations. There clearly exists a need then for propellants which do not contribute to ozone depletion, have a minimal impact on global warming, are not classified as PFAS, and have minimal or no degradation in the atmosphere to TFA.SUMMARY OF THE INVENTION

[0003] According to some aspects of the present invention, a propellant may include HFO-1252zc. In some aspects, a propellant may further include HFO-1123 (CF2=CHF), HFC-32 (CH2F2), HFC-152a (CH3CF2H), HFO-1243zf (CF3CH=CH2), HFO-1234zeE (E-CF3CH=CHCF), HFO-1243yc (CF2=CFCH3), HFO-1234zc (CF2HCH=CF2), HFO1243zc (CH2FCH=CF2), propane, dimethyl ether, isobutane, n- butane, methanol, ethanol, isopropyl alcohol, and / or water.

[0004] In some aspects, the propellant is azeotropic. In some aspects, the propellant is azeotrope-like. In some aspects, the propellant is zeotropic.TS0098-W001

[0005] In some aspects, a sprayable composition includes a propellant as described herein. In some aspects, a sprayable composition includes a propellant as described herein and an active ingredient. In some aspects the sprayable composition is an aerosol. The sprayable composition may be a cleaner, duster, personal care product, household product, automotive product, or medicament.

[0006] Examples of personal care products include a deodorant, perfume, or hair spray. Examples of household products include a wax, polish, pan spray, room freshener, or household insecticide. An example of a medicament includes a metered dose inhaler. A medicament may further include a beta-agonist ora corticosteroid. An example of an automotive product may include a cleaner or polisher.

[0007] In some aspects, an aerosol dispensing system may include a propellant as described herein. In some aspects, a sealed container includes an aerosol dispensing system. The sealed container may also include an aerosol dispensing valve.

[0008] In some aspects, a process for producing aerosol products includes the step of adding a propellant as described herein to active ingredients in an aerosol container, wherein said propellant functions as a propellant.DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure relates to compositions containing 1,1- difluoropropene (HFO-1252zc), described in further detail below. The compositions may be useful as propellants in sprayable compositions, such as liquified gas aerosol compositions. It has been found that the compositions as described herein exhibit environmental responsibility while retaining desirable properties associated with aerosol dispensing systems.Propellant

[0010] Compositions of the present invention may be useful as propellants in sprayable compositions, such as liquified gas aerosol compositions.

[0011] In some aspects, a sprayable composition includes a propellant comprising HFO-1252zc, either alone or in combination with additional components. In someTS0098-W001aspects, a propellant may include HFO-1252zc in combination with one or more component such as HFO-1123 (CF2=CHF), HFC-32 (CH2F2), HFC-152a (CH3CF2H), HFO-1243zf (CF3CH=CH2), HFO-1234zeE (E-CF3CH=CHCF), HFO-1243yc (CF2=CFCH3), HFO-1234zc (CF2HCH=CF2), HFO1243zc (CH2FCH=CF2), HFO- 1132E (CHF=CHF), HFC-134 (HCF2CF2H), propane, dimethyl ether, isobutane, n- butane, methanol, ethanol, isopropyl alcohol, and / or water. The propellant composition may comprise, consist essentially of, or consist of component(s) and / or composition(s) disclosed herein.

[0012] In some aspects, the HFO-1252zc is present in the propellant in an amount from about 1 wt% to about 100 wt%, about 1 wt% to about 99 wt%, such as about 30 wt% to about 99 wt%; about 50 wt% to about 99 wt%; about 75 wt% to about 99 wt%; about 85 wt% to about 99 wt%; about 20 wt% to about 80 wt%; about 90 wt% to about 99 wt%; about 95 wt% to about 99 wt%; about 1 wt% to about 20 wt%; about 1 wt% to about 40 wt%; about 1 wt% to about 50 wt%; about 5 wt% to about 20 wt%; about 5 wt% to about 40 wt%; about 5 wt% to about 60 wt%; about 10 wt% to about 80 wt%; about 10 wt% to about 90 wt%; about 20 wt% to about 80 wt%; or about 20 wt% to about 90 wt% of the propellant.

[0013] In some aspects, the propellants disclosed herein have a Global Warming Potential (GWP) of not greater than 150, not greater than 100, or not greater than 75. As used herein, “GWP” is measured relative to that of carbon dioxide and over a 100-year time horizon, as defined in “The Scientific Assessment of Ozone Depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project,” which is incorporated herein by reference.

[0014] In some aspects, the propellants discloses herein have an Ozone Depletion Potential (ODP) of not greater than 0.05, not greater than 0.02 or about zero. As used herein, “ODP” is as defined in “The Scientific Assessment of Ozone Depletion, 2002, A report of the World Meteorological Association's Global Ozone Research and Monitoring Project,” which is incorporated herein by reference.Sprayable Composition

[0015] A sprayable composition may include a propellant and one or more additional components such as an active ingredient. In some embodiments, the sprayable composition is a blend.TS0098-W001

[0016] Suitable active ingredients to be sprayed may include, without limitation, lubricants, insecticides, cleaners, cosmetic materials such as deodorants, perfumes and hairsprays, polishing agents, as well as medicinal materials such as skin cooling agents (sunburn treatment), topical anesthetics and anti-asthma medications, and any other medication or the like, including any other medicament or agent intended to be inhaled. In some aspects, the medicament or other therapeutic agent is present in the composition in a therapeutic amount, with a substantial portion of the balance of the sprayable composition comprising or consisting essentially of HFO-1252zc.

[0017] In some aspects, the HFO-1252zc is present in the sprayable composition in an amount from about 1 wt% to about 99 wt%, such as about 30 wt% to about 99 wt%; about 50 wt% to about 99 wt%; about 75 wt% to about 99 wt%; about 85 wt% to about 99 wt%; about 20 wt% to about 80 wt%; about 90 wt% to about 99 wt%; about 95 wt% to about 99 wt%; about 1 wt% to about 20 wt%; about 1 wt% to about 40 wt%; about 1 wt% to about 50 wt%; about 5 wt% to about 20 wt%; about 5 wt% to about 40 wt%; about 5 wt% to about 60 wt%; about 10 wt% to about 80 wt%; about 10 wt% to about 90 wt%; about 20 wt% to about 80 wt%; or about 20 wt% to about 90 wt% of the sprayable composition.

[0018] In some aspects, the sprayable composition may include an active ingredient to be sprayed as well as inert ingredients, solvents, and / or other components. In some aspects, the sprayable composition is an aerosol.

[0019] The compositions may be prepared by any convenient method to combine the desired amounts of the individual components. One method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.Aerosol Product

[0020] Another aspect of the present disclosure relates to a process for producing aerosol products comprising the step of adding a propellant composition as disclosed herein to active ingredients in an aerosol container, wherein the propellant composition functions as a propellant. Such products may utilize the pressure of a propellant gas or a mixture of propellant gases (i.e., a propellant gas system) to expel active ingredients from the container. For this purpose, most aerosols employTS0098-W001liquefied gases which vaporize and provide the pressure to propel the active ingredients when the valve on the aerosol container is pressed open. The medicinal aerosol and / or propellant and / or sprayable compositions in many applications include, in addition to a compound disclosed herein, a medicament such as a betaagonist, a corticosteroid or other medicament, and, optionally, other ingredients, such as surfactants, solvents, other propellants, flavorants, and other excipients. The compositions disclosed herein, unlike many compositions previously used in these applications, have good environmental properties and are not considered to be potential contributors to global warming. The present compositions therefore provide in certain aspects substantially nonflammable, liquefied gas propellants having very low GWPs.

[0021] As used herein, the term "nonflammable" refers to compounds and compositions of the present invention which do not exhibit a flashpoint as measured by one of the standard flash point methods, for example, ASTM-1310- 86 "Flash point of liquids by tag Open-cup apparatus."

[0022] In some aspects, the compositions comprising HFO-1252zc are used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, and the like and consumer aerosols such as personal care products, household products and automotive products. In some embodiments, the aerosol or sprayable composition is a medicinal aerosol, such as a metered dose inhaler. In some embodiments, the medicinal aerosol and / or propellant and / or sprayable compositions includes, in addition to HFO-1252zc, a medicament such as a beta-agonist, a corticosteroid or other medicament, and, optionally, other ingredients, such as surfactants, solvents, other propellants, flavorants and other excipients.Azeotropes

[0023] In some embodiments, the propellant component comprises a mixture of hydrofluoroolefms in an amount sufficient to form an azeotropic mixture or an azeotrope-like mixture. Azeotrope and azeotrope-like propellants offer certain advantageous properties (see e.g., P.A. Sanders, Handbook of Aerosol Technology, Second Edition, Robert A. Krieger Publishing Company (Malabar FL), 1987, 41). The composition of the vapor phase is the same as that in the liquid phase in suchTS0098-W001mixtures. Therefore, when azeotrope or azeotrope-like mixtures are used, the composition of the liquid phase remains constant during aerosol product discharge. This is a considerable advantage for products such as dry -type antiperspirants, since the properties of the spray do not change with time.

[0024] In some aspects, a propellant as described herein is azeotropic. In some aspects, a propellant as described herein is azeotrope-like. In some aspects, a propellant as described herein is zeotropic.

[0025] In some aspects, a propellant comprises HFO-1252zc and one or more solvent components selected from «- pentane, iso-pentane, cyclopentane, «-butane, iso-butane, and / or HFO-I1438ezy-E, wherein the HFO-1252zc propellant component and one or more solvent components are present in the composition in an amount sufficient to form an azeotrope or an azeotrope-like composition.

[0026] In some aspects, a propellant comprises HFO-1252zc and one or more components selected from HFO-1123 (CF2=CHF), HFC-32 (CH2F2), HFC-152a (CH3CF2H), HFO-1243zf (CF3CH=CH2), HFO-1234zeE (E-CF3CH=CHCF), HFO- 1243yc (CF2=CFCH3), HFO-1234ZC (CF2HCH=CF2), HFO1243ZC (CH2FCH=CF2), propane, dimethyl ether, isobutane, n-butane, methanol, ethanol, isopropyl alcohol, and / or water wherein the HFO-1252zc and one or more other components are present in the composition in an amount sufficient to form an azeotrope or an azeotrope-like composition.

[0027] As used herein, an azeotropic composition (i.e. , an azeotrope or azeotrope composition) refers to an admixture of two or more different components which, when in liquid form and (la) under a given constant pressure, will boil at a substantially constant temperature, which temperature may be higher or lower than the boiling temperatures of the individual components, or (lb) at a given constant temperature, will boil at a substantially constant pressure, which pressure may be higher or lower than the boiling pressure of the individual components, and (2) will boil at substantially constant composition, which phase compositions, while constant, are not necessarily equal (see, e.g., M. F. Doherty and M.F. Malone, Conceptual Design of Distillation Systems, McGraw-Hill (New York), 2001, 185).

[0028] A homogeneous azeotrope, in which a single vapor phase is in equilibrium with a single liquid phase, has, in addition to properties (1a), (1b), and (2) above, theTS0098-W001property that the composition of each component is the same in each of the coexisting equilibrium phases. The general term “azeotrope” is a commonly used alternative name for a homogeneous azeotrope.

[0029] A heterogeneous azeotrope, in which a single vapor phase is in equilibrium with two liquid phases, has properties (1a), (1b), and (2) as described above where, while constant, the three coexisting equilibrium phases each have different compositions (See e.g., M. F. Doherty and M.F. Malone, Conceptual Design of Distillation Systems, McGraw-Hill (New York), 2001, 352). At the heterogeneous azeotrope, the composition of the overall liquid phase, (i.e., the liquid phase composition obtained by combining the two equilibrium liquid phases), is identical to the composition of the equilibrium vapor phase.

[0030] As used herein, an “azeotrope-like” composition refers to a composition that behaves like an azeotropic composition (i.e., has constant boiling characteristics or a tendency not to fractionate upon boiling or evaporation). Hence, during boiling or evaporation, the vapor and liquid compositions, if they change at all, change only to a minimal or negligible extent. In contrast, the vapor and liquid compositions of non azeotrope-like compositions change to a substantial degree during boiling or evaporation.

[0031] As used herein, the terms “azeotrope-like” or “azeotrope-like behavior” refer to compositions that exhibit dew point pressure and bubble point pressure with virtually no pressure differential. In some embodiments, the difference in the dew point pressure and bubble point pressure at a given temperature is 3% or less. In some aspects, the difference in the bubble point and dew point pressures is 5% or less.

[0032] Global warming potential (GWP) is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide. GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas. The GWP for the 100-year time horizon is commonly the valuereferenced.TS0098-W001

[0033] The term "a liquefied gas" is intended to mean a chemical compound or a mixture of chemical compounds that is in a liquid state under pressure. Such chemical compound or such mixture of chemical compounds is in a gaseous state at about 25°C and atmospheric pressure.

Claims

TS0098-W001CLAIMSWhat is claimed is:

1. A propellant comprising HFO-1252zc.

2. The propellant of claim 1 , further comprising HFO-1123 (CF2=CHF), HFC-32 (CH2F2), HFC-152a (CH3CF2H), HFO-1243zf (CF3CH=CH2), HFO-1234zeE (E-CF3CH=CHCF), HFO-1243yc (CF2=CFCH3), HFO-1234zc (CF2HCH=CF2), HFO-1243zc (CH2FCH=CF2), HFO-1132E (CHF=CHF), HFC-134 (HCF2CF2H), propane, dimethyl ether, isobutane, n-butane, methanol, ethanol, isopropyl alcohol, and / or water.

3. The propellant of any of the preceding claims, wherein the propellant is azeotropic.

4. The propellant of claims 1 or 2, wherein the propellant is azeotrope-like.

5. A sprayable composition comprising the propellant of any of the preceding claims.

6. The sprayable composition of claim 5, further comprising an active ingredient.

7. The sprayable composition of claim 5, wherein the sprayable composition is an aerosol.

8. The sprayable composition of claim 5, wherein the sprayable composition is a cleaner, duster, personal care product, household product, automotive product, or medicament.

9. The sprayable composition of claim 5, wherein the personal care product is a deodorant, perfume, or hair spray.

10. The sprayable composition of claim 8, wherein the household product is a wax, polish, pan spray, room freshener, or household insecticide.

11. The sprayable composition of claim 8, wherein medicament is a metered dose inhaler.

12. The sprayable composition of claim 8, wherein the medicament further comprises a beta-agonist or a corticosteroid.TS0098-W00113. The sprayable composition of claim 8, wherein the automotive product is a cleaner or polisher.

14. An aerosol dispensing system comprising the propellant of any of claims 1-4.

15. A sealed container comprising the aerosol dispensing system of claim 14.

16. The sealed container of claim 15, further comprising an aerosol dispensing valve.

17. A process for producing aerosol products comprising the step of adding a propellant of any of claims 1-4 to active ingredients in an aerosol container, wherein said propellant functions as a propellant.