AZEOTROPE-LIKE COMPOSITIONS OP DICHLOROPENTAFLUOROPROPANE, AN ALKANOL

HAVING 1-3 CARBON ATOMS AND 2-METHYL-2-PROPANOL

Field of the Invention

This invention relates to azeotrope-like mixtures of dichloropentafluoropropane, an alkanol having 1-3 carbon atoms and 2-methyl-2-propanol. These mixtures are useful in a variety of vapor degreasing, cold cleaning, and solvent cleaning applications including defluxing and dry cleaning.

BACKGROUND OF THE INVENTION

Fluorocarbon based solvents have been used extensively for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.

In its simplest form, vapor degreasing or solvent cleaning consists of exposing a room temperature object to be cleaned to the vapors of a boiling solvent. Vapors condensing on the object provide clean distilled solvent to wash away grease or other contamination. Final evaporation of solvent from the object leaves the object free of residue. This is contrasted with liquid solvents which leave deposits on the object after rinsing.

A vapor degreaser is used for difficult to remove soils where elevated temperature is necessary to improve the cleaning action of the solvent, or for large volume assembly line operations where the

cleaning of metal parts and assemblies must be done efficiently. The conventional operation of a vapor degreaser consists of immersing the part to be cleaned in a sump of boiling solvent which removes the bulk of the soil, thereafter immersing the part in a sump containing freshly distilled solvent near room temperature, and finally exposing the part to solvent vapors over the boiling sump which condense on the cleaned part. In addition, the part can also be sprayed with distilled solvent before final rinsing.

Vapor degreasers suitable in the above- described operations are well known in the art. For example, Sherliker et al. in U.S. Patent 3,085,918 disclose such suitable vapor degreasers comprising a boiling sump, a clean sump, a water separator, and other ancillary equipment. Cold cleaning is another application where a number of solvents are used. In most cold cleaning applications, the soiled part is either immersed in the fluid or wiped with cloths soaked in solvents and allowed to air dry.

Recently, nontoxic nonflammable fluorocarbon solvents like trichlorotrifluoroethane, have been used extensively in degreasing applications and other solvent cleaning applications. Trichlorotrifluoro¬ ethane has been found to have satisfactory solvent power for greases, oils, waxes and the like. It has therefore found widespread use for cleaning electric motors, compressors, heavy metal parts, delicate precision metal parts, printed circuit boards, gyroscopes, guidance systems, aerospace and missile hardware, aluminum parts, etc.

The art has looked towards azeotropic compositions having fluorocarbon components because the fluorocarbon components contribute additionally desired characteristics, like polar functionality, increased solvency power, and stabilizers. Azeotropic compositions are desired because they do not fractionate upon boiling. This behavior is desirable because in the previously described vapor degreasing equipment with which these solvents are employed, redistilled material is generated for final rinse-cleaning. Thus, the vapor degreasing system acts as a still. Therefore, unless the solvent composition is essentially constant boiling, fractionation will occur and undesirable solvent distribution may act to upset the cleaning and safety of processing. Preferential evaporation of the more volatile components of the solvent mixtures, which would be the case if they were not an azeotrope or azeotrope-like, would result in mixtures with changed compositions which may have less desirable properties, such as lower solvency towards soils, less inertness towards metal, plastic or elastomer components, and increased flammability and toxicity.

The art is continually seeking new fluoro¬ carbon based azeotropic mixtures or azeotrope-like mixtures which offer alternatives for new and special applications for vapor degreasing and other cleaning applications. Currently, fluorocarbon-based azeotrope-like mixtures are of particular interest because they are considered to be stratospherically safe substitutes for presently used fully halogenated chlorofluorocarbons. The latter have been implicated in causing environmental problems associated with the depletion of the earth's protective ozone layer. Mathematical models have substantiated that hydrochlorofluorocarbons, like dichloropentafluoro-

propane, have a much lower ozone depletion potential and global warming potential than the fully halo¬ genated species.

Accordingly, it is an object of the present invention to provide novel environmentally acceptable azeotrope-like compositions which are useful in a variety of industrial cleaning applications.

It is another object of this invention to provide azeotrope-like compositions which are liquid at room temperature and which will not fractionate under conditions of use.

Other objects and advantages of the invention will become apparent from the following description.

SUMMARY OF THE INVENTION

The invention relates to novel azeotrope-like compositions of dichloropentafluoropropane, an alkanol having 1-3 carbon atoms and 2-methyl- 2-propanol which are useful in a variety of industrial cleaning applications including cold cleaning and defluxing of printed circuit boards.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the invention, novel azeotrope-like compositions have been discovered comprising from about 81.2 to about 99.99 weight percent dichloropentafluoropropane, from about 0.01 to about 17.8 weight percent of an alkanol having 1-3 carbon atoms and from about 0.01 to about 1 weight percent 2-methyl-2-proρanol which boil at about 50.3°C ± about 5.9°C at 760 mm Hg.

Dichloropentafluoropropane exists in nine isomeric forms: (1) 2,2-dichloro-l,l,1,3,3-penta- fluoro-propane (HCFC-225a); (2) l,2-dichloro-l,2,3,- ₅ 3,3-ρentafluoropropane (HCFC-225ba) ; (3) 1,2- dichloro-1,1,2,3,3-pentafluoropropane (HCFC-225bb) ; (4) 1,l-dichloro-2,2,3,3,3-pentafluoropropane (HCFC-225ca); (5) 1,3-dichloro-l,1,2,2,3-pentafluoro¬ propane (HCFC-225cb); (6) 1,l-dichloro-1,2,2,3,3-

_1Q pentafluoro-propane (HCFC-225cc); (7) 1,2-dichloro- 1,1,3,3,3-pentafluoropropane (HCFC-225d); (8) 1,3- dichloro-1,1,2,3,3-pentafluoropropane (HCFC-225ea); and (9) 1,1-dichloro-l,2,3,3,3-pentafluoropropane (HCFC-225eb) . For purposes of this invention,

, m dichloropentafluoropropane will refer to any of the iso ers or an admixture of the isomers in any proportion. The l,l-dichloro-2,2,3,3,3-pentafluoro¬ propane and 1,3-dichloro-l,1,2,2,3-pentafluoropropane isomers, however, are the preferred isomers.

20

The dichloropentafluoropropane component of the invention has good solvent properties. The alkanol components also have good solvent capabilities dissolving polar organic materials and amine hydrochlorides. In addition, the 2-methyl-

25 2-propanol component functions as a stabilizer, retarding the decomposition of the solvent. Thus, when these components are combined in effective amounts, a stable and efficient azeotropic solvent

30 results.

When the alkanol is methanol, the azeotrope- like compositions of the invention consist essentially of from about 81.2 to about 97 weight 35 percent dichloropentafluoropropane, from about 3 to about 17.8 weight percent methanol and from

-6- about 0.01 to about 1 weight percent 2-methyl-2- propanol and boil at about 47.2°C ± about 1.9°C at 760 mm Hg.

When the alkanol is ethanol, the azeotrope- like compositions of the invention consist essentially of from about 85.1 to about 99 weight percent dichloropentafluoropropane, from about 1 to ^ _Q about 13.9 weight percent ethanol and from about 0.01 to about 1 weight percent 2-methyl-2-ρroρanol and boil at about 52.1°C ± about 2.2°C at 760 mm Hg.

When the alkanol is 1-propanol, the azeotrope- _j c like compositions of the invention consist essentially of from about 95 to about 99.99 weight percent dichloropentafluoropropane, from about 0.01 to about 4 weight percent 1-ρroρanol and from about

0.01 to about 1 weight percent 2-methyl-2-ρropanol aanndd bbooiill aat about 53.6°C ± about 2.5°C at

20 760 mm Hg.

When the alkanol is 2-prσpanol, the azeotrope- like compositions of the invention consist essentially of from about 93.1 to about 99.99 weight

25 percent dichloropentafluoropropane, from about 0.01 to about 5.9 weight percent 2-propanol and from about 0.01 to about 1 weight percent 2-methyl-2-propanol and boil at about 53.6°C ± about 2.3°C at ₃₀ 760 mm Hg.

When the dichloropentafluoropropane component is HCFC-225ca and the alkanol is methanol, the azeotrope-like compositions of the invention consist 5 essentially of from about 81.6 to about 97 weight percent HCFC-225ca, from about 3 to about 17.9 weight

percent methanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol and boil at about 45.7°C ± about 0.5°C at 760 mm Hg.

5

In a preferred embodiment utilizing is

HCFC-225ca and methanol, the azeotrope-like compositions of the invention consist essentially of from about 85.6 to about 96 weight percent HCFC-225ca

^Q from about 4 to about 13.9 weight percent methanol and from about 0.01 to about 0.5 weight percent

2-methyl-2-propanol.

In a more preferred embodiment utilizing , m HCFC-225ca and methanol, the azeotrope-like compositions of the invention consist essentially of from about 88.6 to about 95 weight percent HCFC-225ca, from about 5 to about 10.9 weight percent methanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol.

When the dichloropentafluoropropane component is HCFC-225ca and the alkanol is ethanol, the azeotrope-like compositions of the invention consist essentially of from about 91.5 to about 99 weight percent HCFC-225ca, from about 1 to about 8 weight percent ethanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol and boil at about 50.3°C ± about 0.5°C at 760 mm Hg.

30

In a preferred embodiment utilizing HCFC-225ca and ethanol, the azeotrope-like compositions of the invention consist essentially of from about 93.5 to about 99 weight percent HCFC-225ca, from about 1 to

25 about 6 weight percent ethanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol.

In a more preferred embodiment utilizing HCFC-225ca and ethanol, the azeotrope-like

compositions of the invention consist essentially of from about 95 to about 98.5 weight percent HCFC-225ca, from about 1.5 to about 4.5 weight percent ethanol and from about 0.01 to about 0.5 weight percent 2-rnethyl-2-propanol,

When the dichloropentafluoropropane component is HCFC-225ca and the alkanol is 2-propanol, the azeotrope-like compositions of the invention consist essentially of from about 95.5 to about 99.99 weight percent HCFC-225ca, from about 0.01 to about 4 weight percent 2-propanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol and boil at about 51.3°C ± about 0.3°C at 760 mm Hg.

In a preferred embodiment utilizing HCFC-225ca and 2-propanol, the azeotrope-like compositions of the invention consist essentially of from about 97.5 to about 99.99 weight percent HCFC-225ca, from about 0.01 to about 2 weight percent 2-propanol and from about 0.01 to about 0.5 weight percent 2-methyl-2- propanol.

When the dichloropentafluoropropane component is HCFC-225cb and the alkanol is methanol, the azeotrope-like compositions of the invention consist essentially of from about 83.2 to about 97 weight percent HCFC-225cb, from about 3 to about 15.8 weight percent methanol and from about 0.01 to about 1 weight percent 2-methyl-2-propanol and boil at about 48.6°C ± about 0.6°C at 760 mm Hg.

In a preferred embodiment utilizing HCFC-225cb and methanol, the azeotrope-like compositions of the invention consist essentially of from about 83.7 to about 97 weight percent HCFC-225cb from about 3 to

about 15.8 weight percent methanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol.

5 In a more preferred embodiment utilizing

HCFC-225cb and methanol, the azeotrope-like compositions of the invention consist essentially of from about 87.1 to about 95 weight percent HCFC-225cb, from about 5 to about 11.9 weight percent 10 methanol and from about 0.01 to about 1 weight percent 2-methyl-2-propanol.

In a still more preferred embodiment utilizing HCFC-225cb and methanol, the azeotrope-like , -■ compositions of the invention consist essentially of from about 87.6 to about 95 weight percent HCFC-225cb, from about 5 to about 11.9 weight percent methanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol.

20

When the dichloropentafluoropropane component is HCFC-225cb and the alkanol is ethanol, the azeotrope-like compositions of the invention consist essentially of from about 85.1 to about 97 weight

25 percent HCFC-225cb, from about 3 to about 13.9 weight percent ethanol and from about 0.01 to about 1 weight percent 2-methyl-2-propanol and boil at about 53.9°C ± about 0,5°C at 760 mm Hg.

30 In a preferred embodiment utilizing HCFC-225cb and ethanol, the azeotrope-like compositions of the invention consist essentially of from about 85.6 to about 97 weight percent HCFC-225cb, from about 3 to about 13.9 weight percent ethanol and from about 0.01 35 to about 0.5 weight percent 2-methyl-2-ρroρanol.

In a more preferred embodiment utilizing HCFC-225cb and ethanol, the azeotrope-like

compositions of the invention consist essentially of from about 88.1 to about 97 weight percent HCFC-225cb, from about 3 to about lo.9 weight percent ethanol and from about 0.01 to about 1 weight percent 2-methyl-2-propanol.

In a still more preferred embodiment utilizing HCFC-225cb and ethanol, the azeotrope-like compositions of the invention consist essentially of from about 88.6 to about 97 weight percent HCFC-225cb, from about 3 to about 10.9 weight percent ethanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol.

When the dichloropentafluoropropane component is HCFC-225cb and the alkanol is 1-propanol, the azeotrope-like compositions of the invention consist essentially of from about 95 to about 99.99 weight percent HCFC-225cb, from about 0.01 to about 4 weight percent 1-propanol and from about 0.01 to about 1 weight percent 2-methyl-2-propanol and boil at about 56.0°C ± about 0.2°C at 760 mm Hg.

In a preferred embodiment utilizing HCFC-225cb and 1-propanol, the azeotrope-like compositions of the invention consist essentially of from about 95.9 to about 99.99 weight percent HCFC-225cb, from about 0.01 to about 4 weight percent 1-propanol and from about 0.01 to about 0.5 weight percent 2-methyl-2- propanol.

In a more preferred embodiment utilizing HCFC-225cb and 1-propanol, the azeotrope-like compositions of the invention consist essentially of from about 97 to about 99.99 weight percent

HCFC-225cb, from about 0.01 to about 2 weight percent 1-propanol and from about 0.01 to about 1 weight percent 2-methyl-2-propanol.

5

In a still more preferred embodiment utilizing

HCFC-225cb and 1-propanol, the azeotrope-like compositions of the invention consist essentially of from about 97.5 to about 99.99 weight percent

_ _Q HCFC-225cb, from about 0.01 to about 2 weight percent

1-propanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-ρropanol.

When the dichloropentafluoropropane component ,j- is HCFC-225cb and the alkanol is 2-propanol, the azeotrope-like compositions of the invention consist essentially of from about 93.1 to about 99 weight percent HCFC-225cb, from about 1 to about 6 weight percent 2-ρropanol and from about 0.01 to about 1

20 weight percent 2-methyl-2-proρanol and boil at about

55.6°C ± about 0.4°C at 760 mm Hg.

In a preferred embodiment utilizing HCFC-225cb and 2-proρanol, the azeotrope-like compositions of the invention consist essentially of from about 93.6

25 to about 99 weight percent HCFC-225cb, from about 1 to about 6 weight percent 2-propanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol.

30 In a more preferred embodiment utilizing HCFC-225cb and 2-propanol, the azeotrope-like compositions of the invention consist essentially of from about 94.5 to about 98.5 weight percent HCFC-225cb, from about 1.5 to about 4.5 weight 35 percent 2-propanol and from about 0.01 to about 1 weight percent 2-methyl-2-propanol.

In a still more preferred embodiment utilizing HCFC-225cb and 2-propanol, the azeotrope-like compositions of the invention consist essentially of from about 95 to about 98.5 weight percent

HCFC-225cb, from about 1.5 to about 4.5 weight percent 2-proρanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-proρanol.

,« When the dichloropentafluoropropane component is a mixture of HCFC-225ca and HCFC-HCFC-225cb and the alkanol is methanol, the azeotrope-like compositions of the invention consist essentially of from about 81.7 to about 97 weight percent of a 5 mixture of HCFC-225ca and HCFC-225cb, wherein the amount of HCFC-225ca and HCFC-225cb in said mixture may vary from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99 weight percent HCFC-225cb, from about 3 to about 17.8 weight percent methanol and from about 0.01 to about 0.5 0 weight percent 2-methyl-2-ρropanol and boil at about 47.2°C ± about 1.8°C at 760 mm Hg.

In a preferred embodiment utilizing a mixture of HCFC-225ca and HCFC-225cb and methanol, the 5 azeotrope-like compositions of the invention consist essentially of from about 87.6 to about 95 weight percent of a mixture of HCFC-225ca and HCFC-225cb, wherein the amount of HCFC-225ca and HCFC-225cb in 0 said mixture may vary from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99 weight percent HCFC-225cb, from about 5 to about 11.9 weight percent methanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-ρropanol. 5

When the dichloropentafluoropropane component is a mixture of HCFC-225ca and HCFC-225cb and the

alkanol is ethanol, the azeotrope-like compositions of the invention consist essentially of from about 85.6 to about 99 weight percent of a mixture of 5 HCFC-225ca and HCFC-225cb, wherein the amount of

HCFC-225ca and HCFC-225cb in said mixture may vary from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99 weight percent HCFC-225cb, from about 1 to about 13.9 weight ^0 percent ethanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-ρropanol and boil at about 52.1°C ± about 2.2°C at 760 mm Hg.

In a preferred embodiment utilizing a mixture _jc of HCFC-225ca and HCFC-225cb and ethanol, the azeotrope-like compositions of the invention consist essentially of from about 89.5 to about 98.5 weight percent of a mixture of HCFC-225ca and HCFC-225cb, wherein the amount of HCFC-225ca and HCFC-225cb in said mixture may vary from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99 weight percent HCFC-225cb, from about 1.5 to about 10 weight percent ethanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol.

25

When the dichloropentafluoropropane component is a mixture of HCFC-225ca and HCFC-225cb and the alkanol is 2-proρanol, the azeotrope-like compositions of the invention consist essentially of

3 _Q from about 93.5 to about 99.99 weight percent of a mixture of HCFC-225ca and HCFC-225cb, wherein the amount of HCFC-225ca and HCFC-225cb in said mixture may vary from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99

35 weight percent HCFC-225cb, from about 0.01 to about 6 weight percent 2-propanol and from about 0.01 to aobut 0.5 weight percent 2-methyl-2-ρropanol and boil at about 53.6°C ± about 2.6°C at 760 mm Hg.

In a preferred embodiment utilizing a mixtiure of HCFC-225ca and HCFC-225cb and 2-propanol, the azeotrope-like compositions of the invention consist essentially of from about 95 to about 98.5 weight percent of a mixture of HCFC-225ca and HCFC-225cb, wherein the amount of HCFC-225ca and HCFC-225cb in said mixture may vary from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99 weight percent HCFC-225cb, from about 1.5 to about 4.5 weight percent 2-ρroρanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol.

When the dichloropentafluoropropane component is HCFC-225d and the alkanol is methanol, the azeotrope-like compositions of the invention consist essentially of from about 87.5 to about 99 weight percent 225d, from about 1 to about 12 weight percent methanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-ρropanol and boil at about 45.2°C ± about 0.7°C and preferably boil at about 45.2°C ± about 0.4°C at 760 mm Hg.

In a preferred embodiment utilizing 225d and methanol, the azeotrope-like compositions of the invention consist essentially of from about 91.5 to about 98 weight percent 225d, from about 2 to about 8 weight percent methanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol and boil at about 45.2°C ± about 0.7°C and preferably boil at about 45.2°C ± about 0.4°C at 760 mm Hg.

When the dichloropentafluoropropane component is HCFC-225d and the alkanol is ethanol, the azeotrope-like compositions of the invention consist essentially of from about 91.5 to about 99 weight percent 225d, from about 1 to about 8 weight percent

ethanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol and boil at about 49.8°C ± about 0.7°C and preferably boil at about 49.8°C ± about 0.4°C at 760 mm Hg.

In a preferred embodiment utilizing 225d and ethanol, the azeotrope-like compositions of the invention consist essentially of from about 94.5 to about 99 weight percent 225d, from about 1 to about 5 weight percent ethanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol and boil at about 49.8°C ±. about 0.7°C and preferably boil at about 49.8°C ± about 0.4°C at 760 mm Hg.

When the dichloropentafluoropropane component is HCFC-225d and the alkanol is 2-propanol, the azeotrope-like compositions of the invention consist essentially of from about 95.5 to about 99.99 weight percent 225d, from about 0.01 to about 4 weight percent 2-propanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-proρanol and boil at about 50.5°C ± about 0.5°C and preferably boil at about 50.5°C ± about 0.3°C at 760 mm Hg.

In a preferred embodiment utilizing 225d and 2-propanol, the azeotrope-like compositions of the invention consist essentially of from about 97.5 to about 99.99 weight percent 225d, from about 0.01 to about 2 weight percent ethanol and from about 0.01 to about 0.5 weight percent 2-methyl-2-propanol and boil at about 50.5°C ± about 0.5°C and preferably boil at about 50.5°C ± about 0.3°C at 760 mm Hg.

The precise or true azeotrope compositions have not been determined but have been ascertained to be within the indicated ranges. Regardless of where the true azeotropes lie, all compositions within the

indicated ranges, as well as certain compositions outside the indicated ranges, are azeotrope-like, as defined more particularly below.

From fundamental principles, the thermodynamic state of a fluid is defined by four variables: pressure, temperature, liquid composition and vapor composition, or P-T-X-Y, respectively. An azeotrope is a unique characteristic of a system of two or more components where X and Y are equal at a stated P and

T. In practice, this means that the components of a mixture cannot be separated during distillation, and therefore are useful in vapor phase solvent cleaning as described above.

For purposes of this discussion, by azeotrope- like composition is intended to mean that the composition behaves like a true azeotrope in terms of its constant-boiling characteristics or tendency not to fractionate upon boiling or evaporation. Such compositions may or may not be a true azeotrope. Thus, in such compositions, the composition of the vapor formed during boiling or evaporation is identical or substantially identical to the original liquid composition. Hence, during boiling or evaporation, the liquid composition, if it changes at all, changes only minimally. This is contrasted with non-azeotrope-like compositions in which the liquid composition changes substantially during boiling or evaporation.

Thus, one way to determine whether a candidate mixture is "azeotrope-like" within the meaning of this invention, is to distill a sample thereof under conditions (i.e. resolution - number of plates) which would be expected to separate the mixture into its separate components. If the mixture is non-azeo-

tropic or non-azeotrope-like, the mixture will fractionate, i.e., separate into its various components with the lowest boiling component distilling off first, and so on. If the mixture is azeotrope-like, some finite amount of a first distillation cut will be obtained which contains all of the mixture components and which is constant boiling or behaves as a single substance. This phenomenon cannot occur if the mixture is not azeotrope-like, i.e., it is not part of an azeotropic system. If the degree of fractionation of the candidate mixture is unduly great, then a composition closer to the true azeotrope must be selected to minimize fractionation. Of course, upon distillation of an azeotrope-like composition such as in a vapor degreaser, the true azeotrope will form and tend to concentrate.

It follows from the above that another characteristic of azeotrope-like compositions is that there is a range of compositions containing the same components in varying proportions which are azeotrope- like. All such compositions are intended to be covered by the term azeotrope-like as used herein. As an example, it is well known that at different pressures, the composition of a given azeotrope will vary at least slightly as does the boiling point of the composition. Thus, an azeotrope of A and B represents a unique type of relationship but with a variable composition depending on temperature and/or pressure. Accordingly, another way of defining azeotrope-like within the meaning of the invention is to state that such mixtures boil within about ± 5.9°C (at 760 mm Hg) of the 50.3°C boiling point disclosed herein. As is readily understood by persons skilled in the art, the boiling point of the azeotrope will vary with the pressure.

In the process embodiment of the invention, the azeotrope-like compositions of the invention may be used to clean solid surfaces by treating said surfaces with said compositions in any manner well known in the art such as by dipping or spraying or use of conventional degreasing apparatus.

As stated above, the azeotrope-like compositions dicussed herein are useful as solvents for various cleaning applications including vapor degreasing, defluxing, cold cleaning, dry cleaning, dewatering, decontamination, spot cleaning, aerosol propelled rework, extraction, particle removal, and surfactant cleaning applications. These azeotrope- like compositions are also useful as blowing agents, Rankine cycle and absorption refrigerants, and power fluids.

The alkanol components of the invention are known materials. Preferably, they should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the solvent or constant boiling properties of the system.

Commercially available alkanols may be used in the present invention. Most dichloropentafluoro¬ propane isomers, like the preferred HCFC-225ca isomer, are not available in commercial quantities, therefore until such time as they become commercially available, they may be prepared by following the organic syntheses disclosed herein. For example, 1,l-dichloro-2,2,3,3,3-pentafluoropropane may be prepared by reacting 2,2,3,3,3-pentafluoro-1-propanol and p-toluenesulfonate chloride together to form 2,2,3,3,3-pentafluoropropyl-p-toluenesulfonate. Next, N-methylpyrrolidone, lithium chloride, and the

2,2,3,3,3,-pentafluoropropyl-p-toluenesulfonate are reacted together to form l-chloro-2,2,3,3,3-ρenta- fluoropropane. Finally, chlorine and 1-chloro- 2,2,3,3,3-pentafluoropropane are reacted together to form 1,l-dichloro-2,2,3,3,3-pentafluoropropane. A detailed synthesis is set forth in Example 1.

Synthesis of 2.2-dichloro-l.1.1.3.3-penta- fluoropropane ( 225B ) . This compound may be prepared by reacting a dimethylformamide solution of 1,1,1- trichloro-2,2,2-trifluoromethane with chlorotrimethyl- silane in the presence of zinc, forming l-(trimethyl- siloxy)-2,2-dichloro-3,3,3-trifluoro-N,N-dimethylpropyl amine. The l-(trimethylsiloxy)-2,2-dichloro-3,3,3- trifluoro-N,N-dimethyl propylamine is reacted with sulfuric acid to form 2,2-dichloro-3,3,3-trifluoro- propionaldehyde. The 2,2-dichloro-3,3,3-trifluoropro- pionaldehyde is then reacted with sulfur tetra- fluoride to produce 2,2-dichloro-l,1,1,3,3-penta- fluoropropane.

Synthesis of 1.2-dichloro-1.2.3.3.3-penta- luoropropane .225ba_. This isomer may be prepared by the synthesis disclosed by 0. Paleta et al., Bull Soc. Chim. Fr., (6) 920-4 (1986).

Synthesis of 1.2-dichloro-l.1.2.3.3-penta- fluoropropane (225bb The synthesis of this isomer is disclosed by M. Hauptschein and L.A. Bigelow, J. Am. Chem. Soc, (73) 1428-30 (1951). The synthesis of this compound is also disclosed by A.H. Fainberg and W.T. Miller, Jr., J. Am. Chem. Soc, (79) 4170-4, (1957).

Synthesis of 1.3-dichloro-l.1.2.2.3-penta- fluoropropane _225cb). The synthesis of this compound involves four steps.

Part A - Synthesis of 2,2,3,3-tetrafluoro- propyl-p-toluenesulfonate. 406 gm (3.08 mol) 2,2,3,3-tetrafluoropropanol, 613 gm (3.22 mol) tosylchloride, and 1200 ml water were heated to 50 C with mechanical stirring. Sodium hydroxide (139.7 gm, 3.5 ml) in 560 ml water was added at a rate such that the temperature remained less than

65°C. After the addition was completed, the mixture was stirred at 50°C until the pH of the aqueous phase was 6. The mixture was cooled and extracted with 1.5 liters methylene chloride. The organic layer was washed twice with 200 ml aqueous ammonia, 350 ml water, dried with magnesium sulfate, and distilled to give 697.2 gm (79%) viscous oil.

Part B - Synthesis of 1,1,2,2,3-pentafluoro¬ propane. A 500 ml flask was equipped with a mechanical stirrer and a Vigreaux distillation column, which in turn was connected to a dry-ice trap, and maintained under a nitrogen atmosphere. The flask was charged with 400 ml N-methylpyr¬ rolidone, 145 gm (0.507 mol) 2,2,3,3-tetrafluoro- ρropyl-p-toluenesulfonate (produced in Part A above), and 87 gm (1.5 mol) spray-dried KF. The mixture was then heated to 190-200°C for about 3.25 hours during which time 61 gm volatile product distilled into the cold trap (90% crude yield). Upon distillation, the fraction boiling at 25-28°C was collected.

Part C - Synthesis of 1,1,3-trichloro- 1,2,2,3,3-pentafluoropropane. A 22 liter flask was evacuated and charged with 20.7 gm (0.154 mol) 1,1,2,2,3-pentafluoropropane (produced in Part B above) and 0.6 mol chlorine. It was irradiated 100 minutes with a 450 W Hanovia Hg lamp at a distance of about 3 inches (7.6 cm). The flask was then cooled in an ice bath, nitrogen being added as necessary to

maintain 1 atm (101 kPa) . Liquid in the flask was removed via syringe. The flask was connected to a dry-ice trap and evacuated slowly (15-30 minutes). 5 The contents of the dry-ice trap and the initial liquid phase totaled 31.2 g (85%), the GC purity being 99.7%. The product from several runs was combined and distilled to provide a material having b.p. 73.5-74°C.

2o Part D - Synthesis of 1,3-dichloro-l,1,2,2,3- pentafluoropropane. 106.6 gm (0.45 mol) of 1,1,3- trichloro-1,2,2,3,3-pentafluoropropane (produced in Part C above) and 300 gm (5 mol) isopropanol were stirred under an inert atmosphere and irradiated 4.5

, _ς hours with a 450 W Hanovia Hg lamp at a distance of 2-3 inches (5-7.6 cm). The acidic reaction mixture was then poured into 1.5 liters ice water. The organic layer was separated, washed twice with 50 ml water, dried with calcium sulfate, and distilled to give 50.5 gm C1CF ₂ CF ₂ CHC1F, bp 54.5-56°C

20 (55%). ^λ H NMR (CDC1 ₃ ): ddd centered at 6.43 ppm. J H-C-F - 47 Hz, J H-C-C-Fa - 12 Hz, J H-C-C-Fb - 2 Hz.

Synthesis of 1.1-dichloro-l.2.2.3.3-

25 pentafluoropropane (225cc). This compound may be prepared by reacting 2,2,3,3-tetrafluoro-1-propanol and p-toluenesulfonate chloride to form 2,2,3,3-tetra- fluoropropyl-p-toluesulfonate. Next, the 2,2,3,3-

30 tetrafluoropropyl-p-toluenesulfonate is reacted with potassium fluoride in N-methylpyrrolidone to form 1,1,2,2,3-pentafluoropropane. Then, the 1,1,2,2,3- pentafluoropropane is reacted with chlorine to form 1,1-dichloro-l,2,2,3,3-pentafluoropropane.

35

Synthesis of 1.2-dichloro-l,1.3.3.3-penta fluoropropane _225d.. This isomer is commercially available from P.C.R. Incorporated of Gainsville, Florida. Alternately, this compound may be prepared by adding equimolar amounts of 1,1,1,3,3-pentafluoro¬ propane and chlorine gas to a borosilicate flask that has been purged of air. The flask is then irradiated with a mercury lamp. Upon completion of the irradiation, the contents of the flask are cooled. The resulting product will be l,2-dichloro-l,l,3,3,3- pentafluoropropane.

Synthesis of 1.3-dichloro-l.1.2.3.3-penta- fluoropropane (225ea) . This compound may be prepared by reacting trifluoroethylene with dichlorotri- fluoromethane to produce l,3-dichloro-l,l,2,3,3,- pentafluoropropane and 1,1-dichloro-l,2,3,3,3-penta- fluoropropane. The l,3-dichloro-l,l,2,3,3-penta- fluoropropane is seperated from its isomers using fractional distillation and/or preparative gas chromatography.

Synthesis of 1,l-aichloro-l,2,3,3,3-penta- fluoropropane (225eb.. This compound may be prepared by reacting trifluoroethylene with dichlorodifluoro¬ methane to produce 1,3-dichloro-l,1,2,3,3-pentafluoro¬ propane and 1,1-dichloro-l,2,3,3,3-pentafluoro¬ propane. The 1,1-dichloro-l,2,3,3,3-pentafluoro¬ propane is separated from its isomer using fractional distillation and/or preparative gas chromatography. Alternatively, 225eb may be prepared by a synthesis disclosed by 0. Paleta et al., Bull. Soc Chim. Fr., (6) 920-4 (1986). The 1,1-dichloro-l,2,3,3,3-ρenta- fluoropropane can be separated from its two isomers using fractional distillation and/or preparative gas chromatography.

It should be understood that the present compositions may include additional components which form new azeotrope-like compositions. Any such compositions are considered to be within the scope of the present invention as long as the compositions are constant-boiling or essentially constant-boiling and contain all of the essential components described herein.

Inhibitors may be added to the present azeotrope-like compositions to inhibit decomposition of the compositions; react with undesirable decomposition products of the compositions; and/or prevent corrosion of metal surfaces. Any or all of the following classes of inhibitors may be employed in the invention: epoxy compounds such as propylene oxide; nitroalkanes such as nitromethane; ethers such as 1-4-dioxane; unsaturated compounds such as 1,4- butyne diol; acetals or ketals such as dipropoxy methane; ketones such as methyl ethyl ketone; alcohols such as tertiary amyl alcohol; esters such as triphenyl phosphite; and amines such as triethyl amine. Other suitable inhibitors will readily occur to those skilled in the art.

Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.

The present invention is more fully illustrated by the following non-limiting Examples.

gxample ι

This example is directed to the preparation of 5 a preferred dichloropentafluoropropane component of the invention, 1,l-dichloro-2,2,3,3,3-ρentafluoro¬ propane (225ca) .

Part A - Synthesis of 2,2,3,3,3-pentafluoro- o propyl-p-toluenesulfonate. To p-toluenesulfonate chloride (400.66g, 2.10mol) in water at 25°C was added 2,2,3,3,3-pentafluoro-l-propanol(300.8g) . The mixture was heated to 50 C in a 5 liter, 3-neck separatory funnel-type reaction flask, under m mechanical stirring. Sodium hydrcxide(92.56g,

2.31mol) in 383ml water(6M solution) was added dropwise to the reaction mixture via addition funnel over a period of 2.5 hours, keeping the temperature below 55°C. Upon completion of this addition, when the pH of the aqueous phase was approximately 6, the organic phase was drained from the flask while still warm, and allowed to cool to 25°C. The crude product was recrystallized from petroleum ether to afford 500.7 gm (1.65 mol, 82.3%) white needles of

2,2,3,3,3-pentafluoropropyl-p-toluenesulfonate (mp 47.0-52.5°C). ¹ H NMR: 2.45 ppm (S,3H), 4.38 ppm (t,2H, J - 12 Hz), 7.35 ppm (d,2H, J - 6 Hz); ¹⁹ F

NMR: + 83.9 ppm (S,3F), + 123.2 (t,2F,J-12 Hz), upfield from CFC1 ₃ . 0 Part B - Synthesis of l-chloro-2,2,3,3,3-penta- fluoropropane. A 1 liter flask fitted with a thermometer, Vigreaux column and distillation receiving head was charged with 248.5g(0.82mol) 2,2,3,3,3-penta-fluoropropyl-p-toluenesulfonate(produce 5 d in Part A above), 375ml N-methylpyrrolidone, and 46.7 g(l.lmol) lithium chloride. The mixture was then heated with stirring to 140°C at which point, product began to distill over. Stirring and heating

were continued until a pot temperature of 198°C had been reached at which point, there was no further distillate being collected. The crude product was re-distilled to give 107.2g (78%) of product (bp

2 277 5-28°C) H NMR: 3.81 ppm (t,J - 13.5 Hz) 19, F NMR: 83.5 and 119.8 ppm upfield from CFC1 ₃ .

Part C - Synthesis of 1,l-dichloro-2,2,3,3,3- pentafluoropropane. Chlorine(289ml/min) and l-chloro-2,2,3,3,3-pentafluoro-ρropane(produced in Part B above), (1.72g/min) were fed simultaneously into a 1 inch(2.54cm) X 2 inches(5.08cm) monel reactor at 300°C. The process was repeated until 184g crude product had collected in the cold traps exiting the reactor. After washing the crude product with 6 M sodium hydroxide and drying with sodium sulfate, it was distilled to give 69.2g starting material and 46.8g l,l-dichloro-2,2,3,3,3-pentafluoro¬ propane (bp 48-50.5°C). ^λ H NMR: 5.9 (t, J-7.5 H) ppm; ¹⁹ F NMR: 79.4 (3F) and 119.8 (2F) ppm upfield from CFC1 ₃ .

The compositional range over which 225cb, methanol and 2-methyl-2-propanol exhibit constant- boiling behavior was determined. This was accomplished by charging approximately 92 weight percent 225cb and 8 weight percent methanol into an ebulliometer. The ebulliometer consisted of a heated sump in which the 225cb/methanol binary mixture was brought to a boil. The upper part of the ebulliometer connected to the sump was cooled thereby acting as a condenser for the boiling vapors, allowing the system to operate at total reflux.

After bringing the 225cb/methanol binary mixture to a boil at atmospheric pressure, measured amounts of

2-methanol-2-propanol were titrated into the ebulliometer. The change in boiling point was measured with a platinum resistance themometer.

To normalize observed boiling points during different days to 760 millimeters of mercury pressure, the approximate normal boiling points of

225cb-based mixtures were estimated by applying a barometric correction factor of about 26 mmHg/°C, to the observed values. However, it is to be noted that this corrected boiling point is generally accurate up to ± 0.4°C and serves only as a rough comparison of boiling points determined on different days.

The results indicated that compositions of 225cb/methanol/2-methyl-2-propanol of about 92/8/1 weight percent respectively and preferably compositions of about 92/8/0.5 weight percent respectively exhibited constant boiling behavior at 48.6°C ± about 0.6°C at 760 mm Hg.

Example 3

The compositional range over which 225cb, ethanol and 2-methyl-2-propanol exhibit constant boiling behavior was determined by repeating the experiment outlined in Example 2 above except that a 95.5/4.5 weight percent mixture of 225cb and ethanol respectively was initially charged to the ebulliometer and 2-methyl-2-propanol was added. Observed boiling points were normalized by following the procedure outlined in Example 2. The results indicated that compositions of 225cb/ethanol/2-methyl- 2-propanol of about 95.5/4.5/1 weight percent respectively and preferably compositions of about

95.5/4.5/0.5 weight percent respectively exhibited constant boiling behavior at 53.9°C ± about 0.5°C at 760 mm Hg.

Example 4

The compositional range over which 225cb, 2-propanol and 2-methyl-2-propanol exhibit constant boiling behavior was determined by repeating the experiment outlined in Example 2 above except that a 97/3 weight percent mixture of 225cb and 2-ρropanol respectively was initially charged to the ebulliometer and 2-methyl-2-propanol was added. Observed boiling points were normalized by following the procedure outlined in Example 2. The results indicated that compositions of 225cb/2-ρroρanol/2- methyl-2-propanol of about 97/3/1 weight percent respectively and preferably compositions of about

97/3/0.5 weight percent respectively exhibited ccoonnssttaanntt bbooiilling behavior at 55.6°C ± about 0.4°C at 760 mm Hg.

Example 5

The compositional range over which 225cb, 1-ρropanol and 2-methyl-2-propanol exhibit constant boiling behavior was determined by repeating the experiment outlined in Example 2 above except that a 99.5/0.5 weight percent mixture of 225cb/l-propanol respectively was initially charged to the ebullimeter and 2-methyl-2-propanol was added. Observed boiling points were normalized by following the procedure outlined in Example 2. The results indicated that compositions of 225cb/l-ρropanol/2-methyl-2-propanol of about 99.5/0.5/1 weight percent respectively and preferably compositions of about 99.5/0.5/0.5 weight percent respectively exhibited constant boiling bbeehhaavviioorr aat about 56.0°C ± about 0.2°C at 760 mm Hg.

Examples 6 - 12

The azeotropic properties of the compositions listed in Table I are studied by repeating the experiment outlined in Example 2 above. In each case the boiling point versus composition curve indicates a range over which the compositions are constant boiling.

Mixture of Ethanol 2M2P* Boiling Pressure 225ca/cb .wt%) ^«« fwt%, pQjnt( C) (mm Hg)

85.6- 1- 0.01- 52.1 ± 2.2 760 99 13.9 0.5

89.5- 1.5- 0.01- 52.1 ± 2.2 760 98.5 JLfi i _5

225d Ethanol 2M2P* Boiling Point Pressure (wt%) fwt%- (wt%) L ⁰ £ (mm Hg)

91.5- 1- 0, 01- 49.8 ± 0.7 760 99 8 0. 5

94.5- 1- 0.01- 49.8 ± 0.7 760 21 _5_ 0-5

*Note "2M2P" - 2-methyl-2-propanol

**The amount of HCFC-225ca and HCFC-225cb within said mixture is varied from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99 weight percent HCFC-225cb.

Examples 13 - 19

The azeotropic properties of the compositions listed in Table II are studied by repeating the experiment outlined in Example 2 above. In each case the boiling point versus composition curve indicates a range over which the compositions are constant boiling.

Mixture of Methanol 2M2P* Boiling Pressure 225ca/Cb (wt%) (Wt%) (Wt%) PointC C) (mm Hσ^

81.7- 3- 0.01- 47.2 ± 1.8 760 97 17.8 0.5

87.6- 5- 0.01- 47.2 ± 1.8 760 25 11.9 J __2

*Note "2M2P" - 2-methyl-2-proρanol

**The amount of HCFC-225ca and HCFC-225cb within said mixture is varied from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99 weight percent HCFC-225cb.

Examples 19 - 24

The azeotropic properties of the compositiions listed in Table III are studied by repeating the experiment outlined in Example 2 above. In each case the boiling point versus composition curve indicates a range over which the compositions are constant boiling.

*Note "2M2P" » 2-methyl-2-propanol

**The amount of HCFC-225ca and HCFC-225cb within said mixture is varied from about 0.01 to about 99.99 weight percent HCFC-225ca and from about 0.01 to about 99.99 weight percent HCFC-225cb.