Title:
Aerosol propellants comprising unsaturated fluorocarbons
Kind Code:
A1


Abstract:
Disclosed herein are propellants comprising fluorocarbons and/or hydrofluorocarbons. Also disclosed are sprayable compositions comprising the propellants.



Inventors:
Nappa, Mario Joseph (Newark, DE, US)
Creazzo, Joseph Anthony (Wilmington, DE, US)
Sievert, Allen Capron (Elkton, MD, US)
Swearingen, Ekaterina N. (Wilmington, DE, US)
Application Number:
11/590344
Publication Date:
05/03/2007
Filing Date:
10/30/2006
Primary Class:
International Classes:
A61K9/12
View Patent Images:



Primary Examiner:
BROOKS, CLINTON A
Attorney, Agent or Firm:
DUPONT SPECIALTY PRODUCTS USA, LLC (LEGAL PATENT RECORDS CENTER CHESTNUT RUN PLAZA 721/2340 974 CENTRE ROAD, P.O. BOX 2915, WILMINGTON, DE, 19805, US)
Claims:
We Claim:

1. A propellant comprising at least one fluorocarbon or hydrofluorocarbon selected from the group consisting of: (i) a hydrofluorocarbon having the formula E- or Z-R° CH═CHR2, wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups; and (iii) a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF3CF═CHF, CF3CH═CF2, CHF2CF═CF2, CHF2CH═CHF, CF3CF═CH2, CF3CH═CHF, CH2FCF═CF2, CHF2CH═CF2, CHF2CF═CHF, CHF2CF═CH2, CF3CH═CH2, CH3CF═CF2, CH2FCHCF2, CH2FCF═CHF, CHF2CH═CHF, CF3CF═CFCF3, CF3CF2CF═CF2, CF3CF═CHCF3, CF3CF2CF═CH2, CF3CH═CHCF3, CF3CF2CH═CH2, CF2═CHCF2CF3, CF2═CFCHFCF3, CF2═CFCF2CHF2, CHF2CH═CHCF3, (CF3)2C═CHCF3, CF3CF═CHCF2CF3, CF3CH═CFCF2CF3, (CF3)2CFCH═CH2, CF3CF2CF2CH═CH2, CF3(CF2)3CF═CF2, CF3CF2CF═CFCF2CF3, (C F3)2C═C(CF3)2, (CF3)2CFCF═CHCF3, CF2═CFCF2CH2F, CF2═CFCHFCHF2, CH2═C(CF3)2, CH2CF2CF═CF2, CH2FCF═CFCHF2, CH2FCF2CF═CF2, CF2═C(CF3)(CH3), CH2═C(CHF2)(CF3), CH2═CHCF2CHF2, CF2═C(CHF2)(CH3), CHF═C(CF3)(CH3), CH2═C(CHF2)2, CF3CF═CFCH3, CH3CF═CHCF3, CF2═CFCF2CF2CF3, CHF═CFCF2CF2CF3, CF2═CHCF2CF2CF3, CF2═CFCF2CF2CHF2, CHF2CF═CFCF2CF3, CF3CF═CFCF2CHF2, CF3CF═CFCHFCF3, CHF═CFCF(CF3)2, CF2═CFCH(CF3)2, CF3CH═C(CF3)2, CF2═CHCF(CF3)2, CH2═CFCF2CF2CF3, CHF═CFCF2CF2CHF2, CH2═C(CF3)CF2CF3, CF2═CHCH(CF3)2, CHF═CHCF(CF3)2, CF2═C(CF3)CH2CF3, CH2═CFCF2CF2CHF2, CF2═CHCF2CH2CF3, CF3CF═C(CF3)(CH3), CH2═CFCH(CF3)2, CHF═CHCH(CF3)2, CH2FCH═C(CF3)2, CH3CF═C(CF3)2, CH2═CHCF2CHFCF3, CH2C(CF3)CH2CF3, (CF3)2C═CHC2F5, (CF3)2CFCF═CHCF3, CH2═CHC(CF3)3, (CF3)2C═C(CH3)(CF3), CH2═CFCF2CH(CF3)2, CF3CF═C(CH3)CF2CF3, CF3CH═CHCH(CF3)2, CH2═CHCF2CF2CF2CHF2, (CF3)2C═CHCF2CH3, CH2═C(CF3)CH2C2F5, CH2═CHCH2CF2C2F5, CH2═CHCH2CF2C2F5, CF3CF2CF═CFC2H5, CH2═CHCH2CF(CF3)2, CF3CF═CHCH(CF3)(CH3), (CF3)2C═CFC2H5, cyclo-CF2CF2CF2CH═CH—, cyclo-CF2CF2CH═CH—, CF3CF2CF2C(CH3)=CH2, CF3CF2CF2CH═CHCH3, cyclo-CF2CF2CF═CF—, cyclo-CF2CF═CFCF2CF2—, cyclo-CF2CF═CFCF2CF2CF2, CF3CF2CF2CF2CH═CH2, CF3CH═CHCF2CF3, CF2CF2CH═CHCF2CF3, CF3CH═CHCF2CF2CF3, CF3CF═CFC2F5, CF3CF═CFCF2CF2C2F5, CF3CF2CF═CFCF2C2F5, CF3CH═CFCF2CF2C2F5, CF3CF═CHCF2CF2C2F5, CF3CF2CH═CFCF2C2F5, CF3CF2CF═CHCF2C2F5, C2F5CF2CF═CHCH3, C2F5CF═CHCH3, (CF3)2C═CHCH3, CF3C(CH3)=CHCF3, CHF═CFC2F5, CHF2CF═CFCF3, (CF3)2C═CHF, CH2FCF═CFCF3, CHF═CHCF2CF3, CHF2CH═CFCF3, CHF═CFCHFCF3, CF3CH═CFCHF2, CHF═CFCF2CHF2, CHF2CF═CFCHF2, CH2CF═CFCF3, CH2FCH═CFCF3, CH2═CFCHFCF3, CH2═CFCF2CHF2, CF3CH═CFCH2F, CHF═CFCH2CF3, CHF═CHCHFCF3, CHF═CHCF2CHF2, CHF2CF═CHCHF2, CHF═CFCHFCHF2, CF3CF═CHCH3, CF2═CHCF2Br, CHF═CBrCHF2, CHBr═CHCF3, CF3CBr═CFCF3, CH2═CBrCF2CF3, CHBr═CHCF2CF3, CH2═CHCF2CF2Br, CH2═CHCBrFCF3, CH3CBr═CHCF3, CF3CBr═CHCH3, (CF3)2C═CHBr, CF3CF═CBrCF2CF3, E-CHF2CBr═CFC2F5, Z-CHF2CBr═CFC2F5, CF2═CBrCHFC2F5, (CF3)2CFCBr═CH2, CHBr═CF(CF2)2CHF2, CH2═CBrCF2C2F5, CF2═C(CH2Br)CF3, CH2═C(CBrF2)CF3, (CF3)2CHCH═CHBr, (CF3)2C═CHCH2Br, CH2═CHCF(CF3)CBrF2, CF2═CHCF2CH2CBrF2, CFBr═CHCF3, CFBr═CFCF3, CF3CF2CF2CBr═CH2, and CF3(CF2)3CBr═CH2.

2. The propellant of claim 1, wherein R1 and R2 are, independently, CF3, C2F5, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3, CF(CF3)CF2CF3, CF2CF(CF3)2, C(CF3)3, CF2CF2CF2CF2CF3, CF2CF2CF(CF3)2, C(CF3)2C2F5, CF2CF2CF2CF2CF2CF3, CF(CF3) CF2CF2C2F5, or C(CF3)2CF2C2F5.

3. The propellant of claim 1, wherein the hydrofluorocarbon is CF3CH═CHCF3, CF3CH═CHC2F5, CF3CH═CHCF2C2F5, CF3CH═CHCF(CF3)2, C2F5CH═CHC2F5, CF3CH═CH(CF2)3CF3, CF3CH═CHCF2CF(CF3)2, CF3CH═CHCF(CF3)C2F5, CF3CH═CHC(CF3)3, C2F5CH═CHCF2C2F5, C2F5CH═CHCF(CF3)2, CF3CH═CH(CF2)4CF3, CF3CH═CHCF2CF2CF(CF3) 2, CF3CH═CHC(CF3)2C2F5, C2F5CH═CH(CF2)3CF3, C2F5CH═CHCF2CF(CF3)2, C2F5CH═CHCF(CF3)C2F5, C2F5CH═CHC(CF3)3, C2F5CF2CH═CHCF2C2F5, (CF3)2CFCH═CHCF(CF3)2, C2F5CH═CHCF(CF3)2, CF3CH═CH(CF2)5CF3, CF3CH═CHCF(CF3)(CF2)2C2F5, CF3CH═CHC(CF3)2CF2C2F5, C2F5CH═CH(CF2)4CF3, C2F5CH═CHCF2CF2CF(CF3)2, C2F5CH═CHC(CF3)2C2F5, C2F5CF2CH═CH(CF2)3CF3, C2F5CF2CH═CHCF2CF(CF3)2, C2F5CF2CH═CHCF(CF3)C2F5, C2F5CF2CH═CHC(CF3)3, (CF3)2CFCH═CH(CF2)3CF3, (CF3)2CFCH═CHCF2CF(CF3)2, (CF3)2CFCH═CHCF(CF3)C2F5, (CF3)2CFCH═CHC(CF3)3, C2F5CH═CH(CF2)5CF3, C2F5CH═CHCF(CF3)(CF2)2C2F5, C2F5CH═CHC(CF3)2CF2C2F5, C2F5CF2CH═CH(CF2) 4CF3, C2F5CF2CH═CHCF2CF2CF(CF3)2, C2F5CF2CH═CHC(CF3)2C2F5, (CF3)2CFCH═CH(CF2)44CF3, (CF3)2CFCH═CHCF2CF2CF(CF3)2, (CF3)2CFCH═CHC(CF3)2C2F5, CF3(CF2)3CH═CH(CF2)3CF3, CF3(CF2)3CH═CHCF2CF(CF3)2, CF3(CF2)3CH═CHCF(CF3)C2F5, CF3 (CF2)3CH═CHC(CF3)3, (CF3)2CFCF2CH═CHCF2CF(CF3)2, (CF3)2CFCF2CH═CHCF(CF3)C2F5, (CF3)2CFCF2CH═CHC(CF3)3, C2F5CF(CF3)CH═CHCF(CF3)C2F5, C2F5CF(CF3)CH═CHC(CF3)3, or (CF3)3CCH═CHC(CF3)3.

4. The propellant of claim 1, wherein the propellant consists essentially of the fluorocarbon or hydrofluorocarbon.

5. The propellant of claim 4, wherein the propellant consists of the fluorocarbon or hydrofluorocarbon.

6. A sprayable composition comprising the propellant of claim 1.

7. The sprayable composition of claim 6, wherein the sprayable composition is an aerosol.

8. The sprayable composition of claim 7, wherein the aerosol has a vapor pressure in a range of from about 138 to 621 kPa at 21° C.

9. The sprayable composition of claim 6, wherein the sprayable composition is a cleaner, duster, personal care product, household product, automotive product, or medicament.

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

11. The sprayable composition of claim 9, wherein the household product is a wax, polish, pan spray, room freshener, or household insecticide.

12. The sprayable composition of claim 9, wherein medicament is a metered dose inhaler.

13. The sprayable composition of claim 9, wherein the medicament further comprises a beta-agonist or a corticosteroid.

14. The sprayable composition of claim 9, wherein the automotive product is a cleaner or polisher.

15. An aerosol dispensing system comprising the propellant of claim 1.

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

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

18. A pro cess for producing aerosol products comprising the step of adding a composition of claim 1 to active ingredients in an aerosol container, wherein said composition functions as a propellant.

19. A pro cess for producing aerosol products comprising the step of adding a composition of claim 3 to active ingredients in an aerosol container, wherein said composition functions as a propellant.

Description:

CROSS REFERENCE TO RELATED APPLICATION(S)

This application claims the benefit of priority to U.S. Provisional Application Ser. No. 60/732,292, the complete disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

Disclosed herein are aerosol propellant compositions comprising unsaturated fluorocarbons or unsaturated hydrofluorocarbons. Also disclosed is the use of these compositions in preparing aerosol products.

BACKGROUND OF THE INVENTION

In the early 1970s, concern began to be expressed that the stratospheric ozone layer (which provides protection against penetration of the Earth's atmosphere by ultraviolet radiation) was being depleted by chlorine atoms introduced to the atmosphere from the release of chlorofluorocarbons. These chlorofluorocarbons were used as propellants in aerosols, as blowing agents for foams, as refrigerants and as cleaning/drying solvent systems. Because of the great chemical stability of fully halogenated chlorofluorocarbons, according to the ozone depletion theory, these compounds do not decompose in the Earth's troposphere but reach the stratosphere where they slowly degrade liberating chlorine atoms which in turn react with the ozone.

Concern reached such a level that in 1978 the U.S. Environmental Protection Agency (EPA) placed a ban on nonessential uses of fully halogenated chlorofluorocarbons (CFC) as aerosol propellants, and in 1995 banned nonessential uses of hydrochlorofluorocarbon (HCFC) propellants.

There is also a demand for aerosol propellants which have significantly less photochemical reactivity than hydrocarbons that contribute to the formation of ambient ozone and ground level smog. These compounds are typically referred to as low-VOC (volatile organic compound) or non-VOC.

The disclosure herein relates to the discovery of compositions, which include unsaturated fluorocarbons and hydrofluorocarbons. These compositions have zero ozone depletion potential (ODP), low global warming potential (GWP) and are lower VOC than hydrocarbons. These compositions are useful as pure components or in mixtures. These compositions are used as aerosol propellants.

SUMMARY OF THE INVENTION

One aspect is for a propellant comprising at least one fluorocarbon or hydrofluorocarbon selected from the group consisting of:

    • (i) a hydrofluorocarbon having the formula E— or Z—R1CH═CHR2, wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups; or
    • (ii) a fluorocarbon or hydrofluorocarbon selected from the group consisting of CF3CF═CHF, CF3CH═CF2, CHF2CF═CF2, CHF2CH═CHF, CF3CF═CH2, CF3CH═CHF, CH2FCF═CF2, CHF2CH═CF2, CHF2CF═CHF, CHF2CF═CH2, CF3CH═CH2, CH3CF═CF2, CH2FCHCF2, CH2FCF═CHF, CHF2CH═CHF, CF3CF═CFCF3, CF3CF2CF═CF2, CF3CF═CHCF3, CF3CF2CF═CH2, CF3CH═CHCF3, CF3CF2CH═CH2, CF2═CHCF2CF3, CF2═CFCHFCF3, CF2═CFCF2CHF2, CHF2CH═CHCF3, (CF3)2C=CHCF3, CF3CF═CHCF2CF3, CF3CH═CFCF2CF3, (CF3)2CFCH═CH2, CF3CF2CF2CH═CH2, CF3(CF2)3CF═CF2, CF3CF2CF═CFCF2CF3, (CF3)2C═C(CF3)2, (CF3)2CFCF═CHCF3, CF2═CFCF2CH2F, CF2═CFCHFCHF2, CH2═C(CF3)2, CH2CF2CF═CF2, CH2FCF═CFCHF2, CH2FCF2CF═CF2, CF2═C(CF3)(CH3), CH2═C(CHF2)(CF3), CH2═CHCF2CHF2, CF2═C(CHF2)(CH3), CHF═C(CF3)(CH3), CH2═C(CHF2)2, CF3CF═CFCH3, CH3CF═CHCF3, CF2═CFCF2CF2CF3, CHF═CFCF2CF2CF3, CF2═CHCF2CF2CF3, CF2═CFCF2CF2CHF2, CHF2CF═CFCF2CF3, CF3CF═CFCF2CHF2, CF3CF═CFCHFCF3, CHF═CFCF(CF3)2, CF2═CFCH(CF3)2, CF3CH═C(CF3)2, CF2═CHCF(CF3)2, CH2═CFCF2CF2CF3, CHF═CFCF2CF2CHF2, CH2═C(CF3)CF2CF3, CF2═CHCH(CF3)2, CHF═CHCF(CF3)2, CF2═C(CF3)CH2CF3, CH2═CFCF2CF2CHF2, CF2═CHCF2CH2CF3, CF3CF═C(CF3)(CH3), CH2═CFCH(CF3)2, CHF═CHCH(CF3)2, CH2FCH═C(CF3)2, CH3CF═C(CF3)2, CH2═CHCF2CHFCF3, CH2C(CF3)CH2CF3, (CF3)2C═CHC2F5, (CF3)2CFCF═CHCF3, CH2═CHC(CF3)3, (CF3)2C═C(CH3)(CF3), CH2═CFCF2CH(CF3)2, CF3CF═C(CH3)CF2CF3, CF3CH═CHCH(CF3)2, CH2═CHCF2CF2CF2CHF2, (CF3)2C═CHCF2CH3, CH2═C(CF3)CH2C2F5, CH2═CHCH2CF2C2F5, CH2═CHCH2CF2C2F5, CF3CF2CF═CFC2H5, CH2═CHCH2CF(CF3)2, CF3CF═CHCH(CF3)(CH3), (CF3)2C═CFC2H5, cyclo-CF2CF2CF2CH═CH—, cyclo-CF2CF2CH═CH—, CF3CF2CF2C(CH3)═CH2, CF3CF2CF2CH═CHCH3, cyclo-CF2CF2CF═CF—, cyclo-CF2CF═CFCF2CF2—, cyclo-CF2CF═CFCF2CF2CF2, CF3CF2CF2CF2CH═CH2, CF3CH═CHCF2CF3, CF2CF2CH═CHCF2CF3, CF3CH═CHCF2CF2CF3, CF3CF═CFC2F5, CF3CF═CFCF2CF2C2F5, CF3CF2CF═CFCF2C2F5, CF3CH═CFCF2CF2C2F5, CF3CF═CHCF2CF2C2F5, CF3CF2CH═CFCF2C2F5, CF3CF2CF═CHCF2C2F5, C2F5CF2CF═CHCH3, C2F5CF═CHCH3, (CF3)2C═CHCH3, CF3C(CH3)=CHCF3, CHF═CFC2F5, CHF2CF═CFCF3, (CF3)2C═CHF, CH2FCF═CFCF3, CHF═CHCF2CF3, CHF2CH═CFCF3, CHF═CFCHFCF3, CF3CH═CFCHF2, CHF═CFCF2CHF2, CHF2CF═CFCHF2, CH2CF═CFCF3, CH2FCH═CFCF3, CH2═CFCHFCF3, CH2═CFCF2CHF2, CF3CH═CFCH2F, CHF═CFCH2CF3, CHF═CHCHFCF3, CHF═CHCF2CHF2, CHF2CF═CHCHF2, CHF═CFCHFCHF2, CF3CF═CHCH3, CF2═CHCF2Br, CHF═CBrCHF2, CHBr═CHCF3, CF3CBr═CFCF3, CH2═CBrCF2CF3, CHBr═CHCF2CF3, CH2═CHCF2CF2Br, CH2═CHCBrFCF3, CH3CBr═CHCF3, CF3CBr═CHCH3, (CF3)2C═CHBr, CF3CF═CBrCF2CF3, E-CHF2CBr═CFC2F5, Z—CHF2CBr═CFC2F5, CF2═CBrCHFC2F5, (CF3)2CFCBr═CH2, CHBr═CF(CF2)2CHF2, CH2═CBrCF2C2F5, CF2═C(CH2Br)CF3, CH2═C(CBrF2)CF3, (CF3)2CHCH═CHBr, (CF3)2C═CHCH2Br, CH2═CHCF(CF3)CBrF2, CF2═CHCF2CH2CBrF2, CFBr═CHCF3, CFBr═CFCF3, CF3CF2CF2CBr═CH2, and CF3(CF2)3CBr═CH2.

A further aspect is for a sprayable composition comprising the above-described propellant. Preferably, the sprayable composition is an aerosol.

Other objects and advantages will become apparent to those skilled in the art upon reference to the detailed description that hereinafter follows.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate the entire content of all cited references in this disclosure. Applicants also incorporate by reference the co-owned and concurrently filed applications entitled “Fire Extinguishing and Fire Suppression Compositions Comprising Unsaturated Fluorocarbons” (Attorney Docket # FL 1165 US PRV), “Solvent Compositions Comprising Unsaturated Fluorocarbons” (Attorney Docket # FL 1181 US PRV), “Blowing Agents for Forming Foam Comprising Unsaturated Fluorocarbons” (Attorney Docket # FL 1184 US PRV), and “Compositions Comprising Fluoroolefins and Uses Thereof” (Attorney docket # FL 1159). `

Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

One aspect relates to compositions useful in aerosol; i.e., pressurized, dispensing systems. The disclosure herein relates in particular to the field of aerosol compositions which exhibit environmental responsibility while retaining desirable properties associated with aerosol dispensing systems.

There are numerous difficulties associated with formulating an environmentally responsible propellant for use with an aerosol dispensing system, including but not limited to achieving a single phase, soluble composition which will retain desirable spray characteristics and product performance characteristics of aerosols currently marketed. Flammability is also a consideration. Also problematic in the formulation of personal care products is obtaining a composition useful in dispensing active ingredient from an aerosol dispensing system absent toxic side effects.

Aerosol products are generally preferred over products dispensed by pumps or other systems. Many advantages of aerosols stem from the fact that air is not drawn into the aerosol container to replace ingredients dispensed. Thus the product is not exposed to deteriorating or oxidizing effects of air and/or transient moisture, the product maintains its sterility, and preservatives need not be included in the product composition. Consumers prefer aerosols for their convenience, ease of use and cleanliness. Broadly speaking, the characteristics of the spray dispensed from aerosol systems are superior to those of other systems. The product composition is generally applied with a finer, more even spray than when applied with pump sprays. Pump-type dispensers tend to over-concentrate the product in one spot because of inability to maintain uniformity of product dispersal throughout the target area. This is important, for example, in a hairspray product where it is desirable that the spray retain manageability and hold of the hair style yet not weigh the hair down, give an unnatural hold, or feel sticky to touch.

It is, therefore, desirable to develop a homogeneous, soluble and nontoxic composition with limited flammability, useful in an aerosol dispensing system for personal care as well as other products, which retains advantageous spray characteristics and other properties of an aerosol, while achieving environmental responsibility.

Accordingly, one aspect to provide a composition useful in an aerosol dispensing system which achieves the advantageous properties of an aerosol.

A further object to provide a sealed container with an aerosol dispensing system and a composition which attains the objectives described herein.

The foregoing objectives are achieved with the unsaturated fluorocarbon and hydrofluorocarbon propellant compositions disclosed herein. The compositions may be formulated with active ingredient from about 1-15% by weight, or more. Total propellant may vary from 15-95%.

Also contemplated is an aerosol dispensing system comprising a sealed container equipped with an aerosol dispensing valve and containing therein the composition and active ingredient as above.

An important physical property associated with the dispensing of aerosol products is the vapor pressure of the propellant. By “vapor pressure” is meant the pressure exerted when a liquefied propellant gas is in equilibrium with its vapor in a closed container, such as an aerosol can. Vapor pressure can be measured by connecting a pressure gauge to the valve on an aerosol can or gas cylinder containing the vapor/liquid mixture. A standard of measurement of vapor pressure in the U.S. aerosol industry is pounds per square inch gauge (psig) with the gas/liquefied mixture at constant temperature, most commonly at 70° F. (21° C). The vapor pressure of liquefied gases most widely employed as aerosol propellants will vary over the range of about 20 to 90 psig (138 to 621 kPa) at 70° F. (21° C). The propellant systems disclosed herein have vapor pressures in this range.

One aspect encompasses non-toxic compositions useful in an aerosol dispensing system. The compositions comprise unsaturated fluorocarbons (FCs) and/or hydrofluorocarbons (HFCs) alone or in mixture with each other or other suitable propellants, including saturated HFCs, hydrocarbons (HCs), dimethylether, carbon dioxide, nitrous oxide, and nitrogen. Optional active ingredients and additives may be included in the formulation in order to prepare different forms of end products by numerous methods known to those skilled in the art.

One embodiment provides blowing agents having the formula E— or Z—R1CH═CHR2 (Formula I), wherein R1 and R2 are, independently, C1 to C6 perfluoroalkyl groups. Examples of R1 and R2 groups include, but are not limited to, CF3, C2F5, CF2CF2CF3, CF(CF3)2, CF2CF2CF2CF3, CF(CF3)CF2CF3, CF2CF(CF3)2, C(CF3)3, CF2CF2CF2CF2CF3, CF2CF2CF(CF3)2, C(CF3)2C2F5, CF2CF2CF2CF2CF2CF3, CF(CF3) CF2CF2C2F5, and C(CF3)2CF2C2F5. Exemplary, non-limiting Formula I compounds are presented in Table 1.

TABLE 1
CodeStructureChemical Name
F11ECF3CH═CHCF31,1,1,4,4,4-hexafluorobut-2-ene
F12ECF3CH═CHC2F51,1,1,4,4,5,5,5-octafluoropent-2-ene
F13ECF3CH═CHCF2C2F51,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene
F13iECF3CH═CHCF(CF3)21,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene
F22EC2F5CH═CHC2F51,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene
F14ECF3CH═CH(CF2)3CF31,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene
F14iECF3CH═CHCF2CF—(CF3)21,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene
F14sECF3CH═CHCF(CF3)—C2F51,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene
F14tECF3CH═CHC(CF3)31,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene
F23EC2F5CH═CHCF2C2F51,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene
F23iEC2F5CH═CHCF(CF3)21,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene
F15ECF3CH═CH(CF2)4CF31,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-ene
F15iECF3CH═CH—CF2CF2CF(CF3)21,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene
F15tECF3CH═CH—C(CF3)2C2F51,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2-ene
F24EC2F5CH═CH(CF2)3CF31,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-ene
F24iEC2F5CH═CHCF2CF—(CF3)21,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene
F24sEC2F5CH═CHCF(CF3)—C2F51,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept-3-ene
F24tEC2F5CH═CHC(CF3)31,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene
F33EC2F5CF2CH═CH—CF2C2F51,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene
F3i3iE(CF3)2CFCH═CH—CF(CF3)21,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene
F33iEC2F5CF2CH═CH—1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene
F16ECF3CH═CH(CF2)5CF31,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene
F16sECF3CH═CHCF(CF3)—(CF2)2C2F51,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-
ene
F16tECF3CH═CHC(CF3)2—CF2C2F51,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene
F25EC2F5CH═CH(CF2)4CF31,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene
F25iEC2F5CH═CH—CF2CF2CF(CF3)21,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-
ene
F25tEC2F5CH═CH—C(CF3)2C2F51,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3-
ene
F34EC2F5CF2CH═CH—(CF2)3CF31,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene
F34iEC2F5CF2CH═CH—CF2CF(CF3)21,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-
ene
F34sEC2F5CF2CH═CH—CF(CF3)C2F51,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)oct-4-
ene
F34tEC2F5CF2CH═CH—C(CF3)31,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-
ene
F3i4E(CF3)2CFCH═CH—(CF2)3CF31,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3-
ene
F3i4iE(CF3)2CFCH═CH—CF2CF(CF3)21,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-
ene
F3i4sE(CF3)2CFCH═CH—CF(CF3)C2F51,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3-
ene
F3i4tE(CF3)2CFCH═CH—C(CF3)31,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-ene
F26EC2F5CH═CH(CF2)5CF31,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene
F26sEC2F5CH═CHCF(CF3)—(CF2)2C2F51,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-
(trifluoromethyl)non-3-ene
F26tEC2F5CH═CHC(CF3)2—CF2C2F51,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)oct-
3-ene
F35EC2F5CF2CH═CH—(CF2)4CF31,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene
F35iEC2F5CF2CH═CH—CF2CF2CF(CF3)21,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-
(trifluoromethyl)non-4-ene
F35tEC2F5CF2CH═CH—C(CF3)2C2F51,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)oct-
4-ene
F3i5E(CF3)2CFCH═CH—(CF2)4CF31,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-
(trifluoromethyl)non-3-ene
F3i5iE(CF3)2CFCH═CH—CF2CF2CF(CF3)21,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-
3-ene
F3i5tE(CF3)2CFCH═CH—C(CF3)2C2F51,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-
ene
F44ECF3(CF2)3CH═CH—(CF2)3CF31,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec-5-ene
F44iECF3(CF2)3CH═CH—CF2CF(CF3)21,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-
(trifluoromethyl)non-4-ene
F44sECF3(CF2)3CH═CH—CF(CF3)C2F51,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-
(trifluoromethyl)non-4-ene
F44tECF3(CF2)3CH═CH—C(CF3)31,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-bis(trifluoromethyl)oct-
3-ene
F4i4iE(CF3)2CFCF2CH═CH—CF2CF(CF3)21,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-
4-ene
F4i4sE(CF3)2CFCF2CH═CH—CF(CF3)C2F51,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)oct-
4-ene
F4i4tE(CF3)2CFCF2CH═CH—C(CF3)31,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-
ene
F4s4sEC2F5CF(CF3)CH═CH—CF(CF3)C2F51,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct-
4-ene
F4s4tEC2F5CF(CF3)CH═CH—C(CF3)31,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-
ene
F4t4tE(CF3)3CCH═CH—C(CF3)31,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3-
ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyl iodide of the formula R1I with a perfluoroalkyltrihydroolefin of the formula R2CH═CH2 to form a trihydroiodoperfluoroalkane of the formula R1CH2CHIR2. This trihydroiodoperfluoroalkane can then be dehydroiodinated to form R1CH═CHR2. Alternatively, the olefin R1CH═CHR2 may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane of the formula R1CHICH2R2 formed in turn by reacting a perfluoroalkyl iodide of the formula R2I with a perfluoroalkyltrihydroolefin of the formula R1CH═CH2.

Said contacting of a perfluoroalkyl iodide with a perfluoroalkyltrihydroolefin may take place in batch mode by combining the reactants in a suitable reaction vessel capable of operating under the autogenous pressure of the reactants and products at reaction temperature. Suitable reaction vessels include fabricated from stainless steels, in particular of the austenitic type, and the well-known high nickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickel based alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may take be conducted in semi-batch mode in which the perfluoroalkyltrihydroolefin reactant is added to the perfluoroalkyl iodide reactant by means of a suitable addition apparatus such as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefin should be between about 1:1 to about 4:1, preferably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1 adduct as reported by Jeanneaux, et al. in Journal of Fluorine Chemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide with said perfluoroalkyltrihydroolefin are preferably within the range of about 150° C. to 300° C., preferably from about 170° C to about 250° C., and most preferably from about 180° C. to about 230° C.

Suitable contact times for the reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18 hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of the perfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be used directly in the dehydroiodination step or may preferably be recovered and purified by distilled prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting the trihydroiodoperfluoroalkane with a basic substance. Suitable basic substances include alkali metal hydroxides (e.g., sodium hydroxide or potassium hydroxide), alkali metal oxide (for example, sodium oxide), alkaline earth metal hydroxides (e.g., calcium hydroxide), alkaline earth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, or mixtures of basic substances such as soda lime. Preferred basic substances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basic substance may take place in the liquid phase preferably in the presence of a solvent capable of dissolving at least a portion of both reactants. Solvents suitable for the dehydroiodination step include one or more polar organic solvents such as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., acetonitrile, propionitrile, butyronitrile, benzonitrile, or adiponitrile), dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choice of solvent may depend on the boiling point product and the ease of separation of traces of the solvent from the product during purification. Typically, ethanol or isopropanol are good solvents for the reaction.

Typically, the dehydroiodination reaction may be carried out by addition of one of the reactants (either the basic substance or the trihydroiodoperfluoroalkane) to the other reactant in a suitable reaction vessel. Said reaction may be fabricated from glass, ceramic, or metal and is preferably agitated with an impellor or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about 10° C. to about 100° C., preferably from about 20° C. to about 70° C. The dehydroiodination reaction may be carried out at ambient pressure or at reduced or elevated pressure. Of note are dehydroiodination reactions in which the compound of Formula I is distilled out of the reaction vessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted by contacting an aqueous solution of said basic substance with a solution of the trihydroiodoperfluoroalkane in one or more organic solvents of lower polarity such as an alkane (e.g., hexane, heptane, or octane), aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g., methylene chloride, ethylene dichloride, chloroform, carbon tetrachloride, or perchloroethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, dimethoxyethane, diglyme, or tetraglyme) by in the presence of a phase transfer catalyst. Suitable phase transfer catalysts include quaternary ammonium halides (e.g., tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride, dodecyltrimethylammonium chloride, and tricaprylylmethylammonium chloride), quaternary phosphonium halides (e.g., triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride), cyclic ether compounds known in the art as crown ethers (e.g., 18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in the absence of solvent by adding the trihydroiodoperfluoroalkane to a solid or liquid basic substances.

Suitable reaction times for the dehydroiodination reactions are from about 15 minutes to about six hours or more depending on the solubility of the reactants. Typically the dehydroiodination reaction is rapid and requires about 30 minutes to about three hours for completion.

The compound of formula I may be recovered from the dehydroiodination reaction mixture by phase separation after addition of water, by distillation, or by a combination thereof.

The compositions disclosed herein may comprise a single compound of Formula I, for example, one of the compounds in Table 1, or may comprise a combination of compounds of Formula I.

In addition to the inventive compounds described above, compounds presented in Table 2 can be used as aerosol propellants.

TABLE 2
NameStructureChemical name
HFC-1225sC3HF5
HFC-1225yeCF3CF═CHF1,2,3,3,3-pentafluoro-1-propene
HFC-1225zcCF3CH═CF21,1,3,3,3-pentafluoro-1-propene
HFC-1225ycCHF2CF═CF21,1,2,3,3-pentafluoro-1-propene
HFC-1234sC3H2F4
HFC-1234yeCHF2CF═CHF1,2,3,3-tetrafluoro-1-propene
HFC-1234yfCF3CF═CH22,3,3,3-tetrafluoro-1-propene
HFC-1234zeCF3CH═CHF1,3,3,3-tetrafluoro-1-propene
HFC-1234ycCH2FCF═CF21,1,2,3-tetrafluoro-1-propene
HFC-1234zcCHF2CH═CF21,1,3,3-tetrafluoro-1-propene
HFC-1234yeCHF2CF═CHF1,2,3,3-tetrafluoro-1-propene
HFC-1243sC3H3F3
HFC-1243yfCHF2CF═CH22,3,3-trifluoro-1-propene
HFC-1243zfCF3CH═CH23,3,3-trifluoro-1-propene
HFC-1243ycCH3CF═CF21,1,2-trifluoro-1-propene
HFC-1243zcCH2FCH═CF21,1,3-trifluoro-1-propene
HFC-1243yeCHF2CF═CHF1,2,3-trifluoro-1-propene
HFC-1243zeCHF2CH═CHF1,3,3-trifluoro-1-propene
FC-1318sC4F8
FC-1318myCF3CF═CFCF31,1,1,2,3,4,4,4-octafluoro-2-butene
FC-1318cyCF3CF2CF═CF21,1,2,3,3,4,4,4-octafluoro-1-butene
HFC-1327sC4HF7
HFC-1327myCF3CF═CHCF31,1,1,2,4,4,4-heptafluoro-2-butene
HFC-1327yeCHF═CFCF2CF31,2,3,3,4,4,4-heptafluoro-1-butene
HFC-1327pyCHF2CF═CFCF31,1,1,2,3,4,4-heptafluoro-2-butene
HFC-1327et(CF3)2C═CHF1,3,3,3-tetrafluoro-2-(trifluoromethyl)-
1-propene
HFC-1327czCF2═CHCF2CF31,1,3,3,4,4,4-heptafluoro-1-butene
HFC-1327cyeCF2═CFCHFCF31,1,2,3,4,4,4-heptafluoro-1-butene
HFC-1327cycCF2═CFCF2CHF21,1,2,3,3,4,4-heptafluoro-1-butene
HFC-1336sC4H2F6
HFC-1336yfCF3CF2CF═CH22,3,3,4,4,4-hexafluoro-1-butene
HFC-1336zeCHF═CHCF2CF31,3,3,4,4,4-hexafluoro-1-butene
HFC-1336eyeCHF═CFCHFCF31,2,3,4,4,4-hexafluoro-1-butene
HFC-1336eycCHF═CFCF2CHF21,2,3,3,4,4-hexafluoro-1-butene
HFC-1336pyyCHF2CF═CFCHF21,1,2,3,4,4-hexafluoro-2-butene
HFC-1336qyCH2FCF═CFCF31,1,1,2,3,4-hexafluoro-2-butene
HFC-1336pzCHF2CH═CFCF31,1,1,2,4,4-hexafluoro-2-butene
HFC-1336mzyCF3CH═CFCHF21,1,1,3,4,4-hexafluoro-2-butene
HFC-1336qcCF2═CFCF2CH2F1,1,2,3,3,4-hexafluoro-1-butene
HFC-1336peCF2═CFCHFCHF21,1,2,3,4,4-hexafluoro-1-butene
HFC-1336ftCH2═C(CF3)23,3,3-trifluoro-2-(trifluoromethyl)-1-
propene
HFC-1345sC4H3F5
HFC-1345qzCH2FCH═CFCF31,1,1,2,4-pentafluoro-2-butene
HFC-1345mzyCF3CH═CFCH2F1,1,1,3,4-pentafluoro-2-butene
HFC-1345fzCF3CF2CH═CH23,3,4,4,4-pentafluoro-1-butene
HFC-1345mzzCHF2CH═CHCF31,1,1,4,4-pentafluoro-2-butene
HFC-1345syCH3CF═CFCF31,1,1,2,3-pentafluoro-2-butene
HFC-1345fycCH2═CFCF2CHF22,3,3,4,4-pentafluoro-1-butene
HFC-13455yzCHF2CF═CHCHF21,1,2,4,4-pentafluoro-2-butene
HFC-1345cycCH3CF2CF═CF21,1,2,3,3-pentafluoro-1-butene
HFC-1345pyyCH2FCF═CFCHF21,1,2,3,4-pentafluoro-2-butene
HFC-1345eycCH2FCF2CF═CF21,2,3,3,4-pentafluoro-1-butene
HFC-1345ctmCF2═C(CF3)(CH3)1,1,3,3,3-pentafluoro-2-methyl-1-
propene
HFC-1345ftpCH2═C(CHF2)(CF3)2-(difluoromethyl)-3,3,3-trifluoro-1-
propene
HFC-1354sC4H4F4
HFC-1354fzcCH2═CHCF2CHF23,3,4,4-tetrafluoro-1-butene
HFC-1354ctpCF2═C(CHF2)(CH3)1,1,3,3-tetrafluoro-2-methyl-1-
propene
HFC-1354etmCHF═C(CF3)(CH3)1,3,3,3-tetrafluoro-2-methyl-1-
propene
HFC-1354tfpCH2═C(CHF2)22-(difluoromethyl)-3,3-difluoro-1-
propene
HFC-1354myCF3CF═CFCH31,1,1,2-tetrafluoro-2-butene
HFC-1354mzyCH3CF═CHCF31,1,1,3-tetrafluoro-2-butene
FC-141-10sC5F10
FC-141-10myyCF3CF═CFCF2CF31,1,1,2,3,4,4,5,5,5-decafluoro-2-
pentene
FC-141-10cyCF2═CFCF2CF2CF31,1,2,3,3,4,4,5,5,5-decafluoro-1-
pentene
HFC-1429sC5HF9
HFC-1429mzt(CF3)2C═CHCF31,1,1,4,4,4-hexafluoro-2-
(trifluoromethyl)-2-butene
HFC-1429myzCF3CF═CHCF2CF31,1,1,2,4,4,5,5,5-nonafluoro-2-
pentene
HFC-1429mzyCF3CH═CFCF2CF31,1,1,3,4,4,5,5,5-nonafluoro-2-
pentene
HFC-1429eycCHF═CFCF2CF2CF31,2,3,3,4,4,5,5,5-nonafluoro-1-
pentene
HFC-1429czcCF2═CHCF2CF2CF31,1,3,3,4,4,5,5,5-nonafluoro-1-
pentene
HFC-1429cyccCF2═CFCF2CF2CHF21,1,2,3,3,4,4,5,5-nonafluoro-1-
pentene
HFC-1429pyyCHF2CF═CFCF2CF31,1,2,3,4,4,5,5,5-nonafluoro-2-
pentene
HFC-1429myycCF3CF═CFCF2CHF21,1,1,2,3,4,4,5,5-nonafluoro-2-
pentene
HFC-1429myyeCF3CF═CFCHFCF31,1,1,2,3,4,5,5,5-nonafluoro-2-
pentene
HFC-1429eyymCHF═CFCF(CF3)21,2,3,4,4,4-hexafluoro-3-
(trifluoromethyl)-1-butene
HFC-1429cyzmCF2═CFCH(CF3)21,1,2,4,4,4-hexafluoro-3-
(trifluoromethyl)-1-butene
HFC-1429mztCF3CH═C(CF3)21,1,1,4,4,4-hexafluoro-3-
(trifluoromethyl)-2-butene
HFC-1429czymCF2═CHCF(CF3)21,1,3,4,4,4-hexafluoro-3-
(trifluoromethyl)-1-butene
HFC-1438sC5H2F8
HFC-1438fyCH2═CFCF2CF2CF32,3,3,4,4,5,5,5-octafluoro-1-pentene
HFC-1438eyccCHF═CFCF2CF2CHF21,2,3,3,4,4,5,5-octafluoro-1-pentene
HFC-1438ftmcCH2═C(CF3)CF2CF33,3,4,4,4-pentafluoro-2-
(trifluoromethyl)-1-butene
HFC-1438czzmCF2═CHCH(CF3)21,1,4,4,4-pentafluoro-3-
(trifluoromethyl)-1-butene
HFC-1438ezymCHF═CHCF(CF3)21,3,4,4,4-pentafluoro-3-
(trifluoromethyl)-1-butene
HFC-1438ctmfCF2═C(CF3)CH2CF31,1,4,4,4-pentafluoro-2-
(trifluoromethyl)-1-butene
HFC-1447sC5H3F7
HFC-1447fzy(CF3)2CFCH═CH23,4,4,4-tetrafluoro-3-(trifluoromethyl)-
1-butene
HFC-1447fzCF3CF2CF2CH═CH23,3,4,4,5,5,5-heptafluoro-1-pentene
HFC-1447fyccCH2═CFCF2CF2CHF22,3,3,4,4,5,5-heptafluoro-1-pentene
HFC-1447czcfCF2═CHCF2CH2CF31,1,3,3,5,5,5-heptafluoro-1-pentene
HFC-1447mytmCF3CF═C(CF3)(CH3)1,1,1,2,4,4,4-heptafluoro-3-methyl-2-
butene
HFC-1447fyzCH2═CFCH(CF3)22,4,4,4-tetrafluoro-3-(trifluoromethyl)-
1-butene
HFC-1447ezzCHF═CHCH(CF3)21,4,4,4-tetrafluoro-3-(trifluoromethyl)-
1-butene
HFC-1447qztCH2FCH═C(CF3)21,4,4,4-tetrafluoro-3-(trifluoromethyl)-
2-butene
HFC-1447sytCH3CF═C(CF3)22,4,4,4-tetrafluoro-3-(trifluoromethyl)-
2-butene
HFC-1456sC5H4F6
HFC-1456szt(CF3)2C═CHCH33-(trifluoromethyl)-4,4,4-trifluoro-2-
butene
HFC-1456szyCF3CF2CF═CHCH33,4,4,5,5,5-hexafluoro-2-pentene
HFC-1456mstzCF3C(CH3)═CHCF31,1,1,4,4,4-hexafluoro-2-methyl-2-
butene
HFC-1456fzceCH2═CHCF2CHFCF33,3,4,5,5,5-hexafluoro-1-pentene
HFC-1456ftmfCH2═C(CF3)CH2CF34,4,4-trifluoro-2-(trifluoromethyl)-1-
butene
FC-151-12sC6F12
FC-151-12cCF3(CF2)3CF═CF21,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-
1-hexene (or perfluoro-1-hexene)
FC-151-12mcyCF3CF2CF═CFCF2CF31,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-
3-hexene (or perfluoro-3-hexene)
FC-151-12mmtt(CF3)2C═C(CF3)21,1,1,4,4,4-hexafluoro-2,3-
bis(trifluoromethyl)-2-butene
FC-151-12mmzz(CF3)2CFCF═CFCF31,1,1,2,3,4,5,5,5-nonafluoro-4-
(trifluoromethyl)-2-pentene
HFC-152-11sC6HF11
HFC-152-11mmtz(CF3)2C═CHC2F51,1,1,4,4,5,5,5-octafluoro-2-
(trifluoromethyl)-2-pentene
HFC-152-11mmyyz(CF3)2CFCF═CHCF31,1,1,3,4,5,5,5-octafluoro-4-
(trifluoromethyl)-2-pentene
HFC-1549sC6H3F9
PFBECF3CF2CF2CF2CH═CH23,3,4,4,5,5,6,6,6-nonafluoro-1-
(or HFC-1549fz)hexene (or perfluorobutylethylene)
HFC-1549fztmmCH2═CHC(CF3)34,4,4-trifluoro-3,3-bis(trifluoromethyl)-
1-butene
HFC-1549mmtts(CF3)2C═C(CH3)(CF3)1,1,1,4,4,4-hexafluoro-3-methyl-2-
(trifluoromethyl)-2-butene
HFC-1549fyczCH2═CFCF2CH(CF3)22,3,3,5,5,5-hexafluoro-4-
(trifluoromethyl)-1-pentene
HFC-1549mytsCF3CF═C(CH3)CF2CF31,1,1,2,4,4,5,5,5-nonafluoro-3-
methyl-2-pentene
HFC-1549mzzzCF3CH═CHCH(CF3)21,1,1,5,5,5-hexafluoro-4-
(trifluoromethyl)-2-pentene
HFC-1558sC6H4F8
HFC-1558szyCF3CF2CF2CF═CHCH33,4,4,5,5,6,6,6-octafluoro-2-hexene
HFC-1558fzcccCH2═CHCF2CF2CF2CHF23,3,4,4,5,5,6,6-octafluoro-2-hexene
HFC-1558mmtzc(CF3)2C═CHCF2CH31,1,1,4,4-pentafluoro-2-
(trifluoromethyl)-2-pentene
HFC-1558ftmfCH2═C(CF3)CH2C2F54,4,5,5,5-pentafluoro-2-
(trifluoromethyl)-1-pentene
HFC-1567sC6H5F7
HFC-1567ftsCF3CF2CF2C(CH3)═CH23,3,4,4,5,5,5-heptafluoro-2-methyl-1-
pentene
HFC-1567szzCF3CF2CF2CH═CHCH34,4,5,5,6,6,6-heptafluoro-2-hexene
HFC-1567fzfcCH2═CHCH2CF2C2F54,4,5,5,6,6,6-heptafluoro-1-hexene
HFC-1567sfyyCF3CF2CF═CFC2H51,1,1,2,2,3,4-heptafluoro-3-hexene
HFC-1567fzfyCH2═CHCH2CF(CF3)24,5,5,5-tetrafluoro-4-(trifluoromethyl)-
1-pentene
HFC-1567myzzmCF3CF═CHCH(CF3)(CH3)1,1,1,2,5,5,5-heptafluoro-4-methyl-2-
pentene
HFC-1567mmtyf(CF3)2C═CFC2H51,1,1,3-tetrafluoro-2-(trifluoromethyl)-
2-pentene
FC-161-14sC7F14
FC-161-14myyCF3CF═CFCF2CF2C2F51,1,1,2,3,4,4,5,5,6,6,7,7,7-
tetradecafluoro-2-heptene
FC-161-14mcyyCF3CF2CF═CFCF2C2F51,1,1,2,2,3,4,5,5,6,6,7,7,7-
tetradecafluoro-2-heptene
HFCs-162-13sC7HF13
HFC-162-13mzyCF3CH═CFCF2CF2C2F51,1,1,3,4,4,5,5,6,6,7,7,7-
tridecafluoro-2-heptene
HFC-162-13myzCF3CF═CHCF2CF2C2F51,1,1,2,4,4,5,5,6,6,7,7,7-
tridecafluoro-2-heptene
HFC-162-13mczyCF3CF2CH═CFCF2C2F51,1,1,2,2,4,5,5,6,6,7,7,7-
tridecafluoro-3-heptene
HFC-162-13mcyzCF3CF2CF═CHCF2C2F51,1,1,2,2,3,5,5,6,6,7,7,7-
tridecafluoro-3-heptene
CyclicCyclo[−CX═CY(CXY)n−]
fluoroolefins
HFC-C1316cccyclo-CF2CF2CF═CF—1,2,3,3,4,4-hexafluorocyclobutene
HFC-C1334cccyclo-CF2CF2CH═CH—3,3,4,4-tetrafluorocyclobutene
HFC-C1436cyclo-CF2CF2CF2CH═CH—3,3,4,4,5,5,-hexafluorocyclopentene
HFC-C1418ycyclo-CF2CF═CFCF2CF21,2,3,3,4,4,5,5-
octafluorocyclopentene
FC-C151-10ycyclo-CF2CF═CFCF2CF2CF21,2,3,3,4,4,5,5,6,6-
decafluorocyclohexene

The compounds listed in Table 2 are available commercially or may be prepared by processes known in the art.

In addition to the inventive compounds described above, the 5 bromine-containing fluorocarbons or hydrofluorocarbons presented in Table 3 can be used as aerosol propellants.

TABLE 3
StructureChemical Names
CF2═CHCF2Br3-bromo-1,1,3,3-tetrafluoropropene
CF2═CFCBrH23-bromo-1,1,2-trifluoropropene
CHF═CBrCF32-bromo-1,3,3,3-tetrafluoropropene
CHF═CHCBrF23-bromo-1,3,3-trifluoropropene
CHF═CBrCHF22-bromo-1,3,3-trifluoropropene
CHBr═CFCF31-bromo-2,3,3,3-tetrafluoropropene
CHBr═CHCF31-bromo-3,3,3-trifluoropropene
CH2═CBrCF32-bromo-3,3,3-trifluoropropene
CH2═CFCBrF23-bromo-2,3,3-trifluoropropene
CFBr═CHCF31-bromo-1,3,3,3-tetrafluoropropene
CFBr═CFCF31-bromopentafluoropropene
CH2═CBrCF2CF32-bromo-3,3,4,4,4-pentafluoro-1-butene
CHBr═CHCF2CF31-bromo-3,3,4,4,4-pentafluoro-1-butene
CH2═CHCF2CF2Br4-bromo-3,3,4,4-tetrafluoro-1-butene
CH2═CHCBrFCF33-bromo-3,4,4,4-tetrafluoro-1-butene
CF3CBr═CFCF32-bromo-1,1,1,3,4,4,4-heptafluoro-2-butene
CH3CBr═CHCF32-bromo-4,4,4-trifluoro-2-butene
CF3CBr═CHCH32-bromo-1,1,1-trifluoro-2-butene
(CF3)2C═CHBr1-bromo-3,3,3-trifluoro-2-(trifluoromethyl)-propene
CF3CF═CBrCF2CF33-bromo-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene
E-CHF2CBr═CFC2F5E-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene
Z-CHF2CBr═CFC2F5Z-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene
CF2═CBrCHFC2F52-bromo-1,1,3,4,4,5,5,5-octafluoro-1-pentene
CHBr═CF(CF2)2CHF21-bromo-2,3,3,4,4,5,5-heptafluoro-1-pentene
CH2═CBrCF2C2F52-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene
CF2═CHCF2CH2CBrF25-bromo-1,1,3,3,5,5-hexafluoro-1-pentene
(CF3)2CFCBr═CH22-bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene
CF2═C(CH2Br)CF32-(bromomethyl)-1,1,3,3,3-pentafluoropropene
CH2═C(CBrF2)CF32-(bromodifluoromethyl)-3,3,3-trifluoropropene
(CF3)2CHCH═CHBr1-bromo-4,4,4-trifluoro-3-(trifluoromethyl)-1-butene
(CF3)2C═CHCH2Br4-bromo-1,1,1-trifluoro-2-(trifluoromethyl)-2-butene
CH2═CHCF(CF3)CBrF23-(bromodifluoromethyl)-3,4,4,4-tetrafluoro-1-butene
CF3CF2CF2CBr═CH22-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene
CF3(CF2)3CBr═CH22-bromo-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene

The compounds listed in Table 3 are available commercially or may be prepared by processes known in the art.

1 -Bromo-3,3,4,4,4-pentafluoro-1 -butene may be prepared by a three step sequence beginning with reaction of phosphorous tribromide with 3,3,4,4,4-pentafluoro-1-butanol to give 4-bromo-1,1,1,2,2-pentafluorobutane. Thermal bromination of 4-bromo-1,1,1,2,2-pentafluorobutane at 350-400° C. gives 4,4-dibromo-1,1,1,2,2-pentafluorobutane which may in turn be heated with powdered potassium hydroxide to give the desired bromobutene.

2-Bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene may be prepared by addition of bromine to 3,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene followed by treatment of the resulting dibromide with ethanolic potassium hydroxide.

Many of the compounds of Formulas I, Table 1, Table 2 and Table 3 exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the disclosure herein is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, CF3CH═CHCF3 is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. Another example is C2F5CF2CH═CH-CF2C2F5, by which is represented the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.

Aerosol propellants may comprise a single compound as listed, for example, in Table 2, or may comprise a combination of compounds from Table 2 or, alternatively, a combination of compounds from Table 1, Table 2, Table 3, and/or Formula I.

The amount of the fluorocarbons (FCs) or HFCs contained in the present compositions (from, e.g., Formula I, Table 1, or Table 2, or Table 3) can vary widely, depending the particular application, and compositions containing more than trace amounts and less than 100% of the compound are within broad the scope of the present disclosure. Preferably, the compositions have a Global Warming Potential (GWP) of not greater than 150, more preferably not greater than 100, and even more preferably 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.

The present compositions also preferably have an Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not greater than 0.02 and even more preferably 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.

The compositions may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.

The propellants may comprise a single compound as listed, for example, in Table 1, or may comprise a combination of compounds of Formula I, Table 1, Table 2, and/or Table 3. Additionally, many of the compounds described herein may exist as different configurational isomers or stereoisomers. The disclosure herein is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, Fl 1 E is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio. Another example is F33E, by which is represented the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.

Preferably, the propellants disclosed herein have a Global Warming Potential (GWP) of not greater than 150, more preferably not greater than 100, and even more preferably 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.

The present compositions also preferably have an Ozone Depletion Potential (ODP) of not greater than 0.05, more preferably not greater than 0.02 and even more preferably 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.

The compositions may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.

The propellant composition comprises, more preferably consists essentially of, and, even more preferably, consists of compositions disclosed herein. The active ingredient to be sprayed together with inert ingredients, solvents, and other materials may also be present in the sprayable mixture. Preferably, the sprayable composition is an aerosol.

Another embodiment of the present disclosure provides a process for producing aerosol products comprising the step of adding a composition as disclosed herein to active ingredients in an aerosol container, wherein said composition functions as a propellant.

The compositions are capable of providing nonflammable, liquefied gas propellant and aerosols that do not contribute substantially to global warming. The present compositions can be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, mold release sprays, and the like, and consumer aerosols such as personal care products (such as, e.g., hair sprays, deodorants, and perfumes), household products (such as, e.g., waxes, polishes, pan sprays, room fresheners, and household insecticides), and automotive products (such as, e.g., cleaners and polishers), as well as medicinal materials such as anti-asthma and anti-halitosis medications. Examples of this includes metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of medicaments to accessible mucous membranes or intranasally.

All such products 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 employ liquefied 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 beta-agonist, 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 preferred embodiments substantially nonflammable, liquefied gas propellants having very low GWPs.

All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods disclosed herein have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit, and scope of the present disclosure. More specifically, it will be apparent that certain agents which are chemically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the present disclosure as defined by the appended claims.

EXAMPLES

The present disclosure is further defined in the following Examples. It should be understood that these Examples, while indicating preferred embodiments, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the preferred features, and without departing from the spirit and scope thereof, can make various changes and modifications to adapt it to various uses and conditions.

Example 1

55% VOC Hair Spray

A 55% VOC (volatile organic compound) hairspray was formulated as follows:

Wt %
Octylacrylamide/acrylates/butylaminoethyl5.0
methylacrylate copolymer (National Starch
Amphomer LV-71)
AMP (2-amino-2-methyl-1-propanol)1.0
Water3.5
Ethanol55.0
Propellant35.0
Vapor Pressure @ 70□F.40 psig

The formulation was one phase indicating complete miscibility and showed good spray patterns and delivery.

Example 2

Air Freshener

An air freshener was formulated as follows:

Wt %
Fragrance (Dragoco 0/716873 mixed flowers scent)1.0
Water4.0
Ethanol30.0
Propellant65.0
Vapor Pressure @ 70□F.48 psig

The formulation was one phase indicating complete miscibility and showed good spray patterns and delivery.

Example 3

Fragrance

A fragrance was formulated as follows:

Wt %
Perfume (Dragoco 0/716873 mixed flowers scent)3.0
Water15.0
Ethanol70.0
Propellant12.0
Vapor Pressure @ 70□F.17 psig

The formulation was one phase indicating complete miscibility and showed good spray patterns and delivery.

Example 4

Aerosol Antiperspirant

An aerosol antiperspirant was formulated as follows:

Wt %
Aluminum chlorohydrate (Reheis Activated ACH10.0
Modified R277-265A)
Isopropyl myristate6.0
Silicone fluid DC-3446.0
Quaternium-18 hectorite (Rheox Bentone 38)0.5
Ethanol2.0
Propellant75.0
Propellant12.0
Vapor Pressure @ 70□F.48 psig
    • The formulation provided good suspendability for the antiperspirant active, showed good spray patterns and delivery, and did not plug the valve.

Similar formulations can also be developed for household disinfectants, insect foggers, and spray paints using the compositions of the present disclosure.