AU644551B2 - Ternary azeotropic compositions of dichloropentafluoropropane and trans-1,2-dichloroethylene with methanol or ethanol or isopropanol - Google Patents

Description

WO 91/13934 PCT/US91/00643 1 TERNARY AZEOTROPIC COMPOSITIONS OF DICHLOROPENTAFLUOROPROPANE AND TRANS-1,2-DICHLOROETHYLENE WITH METHANOL OR ETHANOL OR ISOPROPANOL Cross-Reference to Related Application This application is a continuation-in-part of U.S.S.N. 07/491,577 filed March 12, 1990.

Background of the Invention As modern electronic circuit boards evolve toward increased circuit and component densities, thorough board cleaning after soldering becomes a more important criterion. Current industrial processes for soldering electronic components to circuit boards involve coating the entire circuit side of the board with flux and therea.-er passing the flux-coated board over proheaters and through molten solder. The flux cleans the conductive metal parts and promotes solder fusion.

Commonly used solder fluxes generally consist of rosin, either used alone or with activating additives, such as amine hydrochlorides or oxalic acid derivatives.

After soldering, which thermally degrades part of the rosin, the flux-residues are often removed from the circuit boards with an organic solvent. The requirements for such solvents are very stringent. Defluxing solvents should have the following characteristics: a low boiling point, be nonflammable, have low toxicity and have high solvency power, so that flux and fluxresidues can be removed without damaging the substrate being cleaned.

WO 91/13934 PCT/US91/00643 2 While boiling point, flammability and solvent power characteristics can often be adjusted by preparing solvent mixtures, these mixtures are often unsatisfactory because they fractionate to an undesirable degree during use. Such solvent mixtures also fractionate during solvent distillation, which makes it virtually impossible to recover a solvent mixture with the original composition.

On the other hand, azeotropic mixtures, with their constant boiling points and constant compositions, have been found to be very useful for these applications.

Azeotropic mixtures exhibit either a maximum or minimum boiling point and they do not fraccionate on boiling.

These characteristics are also important when using solvent compositions to remove solder fluxes and flux-residues from printed circuit boards.

Preferential evaporation of the more volatile solvent mixture components would occur, if the mixtures were not azeotropic and would result in mixtures with changed compositions, and with attendant less-desirable solvency properties, such as lower rosin flux solvency and lower inertness toward the electrical components being cleaned. The azeotropic character is also i desirable in vapor degreasing operations, where redistilled solvent is generally employed for final rinse cleaning.

In summary, vapor defluxing and degreasing systems act as a still. Unless the solvent composition exhibits a constant boiling point, is an azeotrope, fractionation will occur and undesirable solvent distributions will result, which could detrimentally affect the safety and efficacy of the cleaning operation.

A number of chlorofluorocarbon based azeotropic compositions have been discovered and in some cases i L 1 1, r~WI i i i i WO91/13934 PCT/US91/00643 3 used as solvents for solder flux and flux-residue removal frol printed circuit boards and also for miscellaneous degreasing applications. For example: U.S. Patent No. 3,903,009 discloses the ternary azeotrope of 1,1,2-trichloro-l,2,2-trifluoroethane with ethanol and nitromethane; U.S. Patent No. 2,999,815 discloses the binary azeotrope of 1,1,2-trichloro- 1,2,2-trifluoroethane and acetone; U.S. Patent No.

2,999,817 discloses the binary azeotrope of 1,1,2trichloro-1,2,2-trifluoroethane and methylene chloride.

Such mixtures are also useful as buffing abrasive detergents, to remove buffing abrasive compounds from polished surfaces such as metal, as drying agents for jewelry or metal parts and as resist-developers in conventional circuit manufacturing techniques employing chlorine-type developing agents, and to strip photoresists (for example with addition of a chlorohydrocarbon such as 1,1,1-trichloroethane or trichloroethylene). The mixtures further are useful as refrigerants, heat transfer media, foam expansion agents, aerosol propellants, solvents and power cycle working fluids. Further, in numerous cases, the halocarbon components of these mixtures each singly are effective in these applications.

Closed-cell polyurethane foams are widely used for insulation purposes in building construction and in the manufacture of energy efficient electrical appliances.

In the construction industry, polyurethane (polyisocyanurate) board stock is used in roofing and siding for its insulation and load-carrying capabilities.

Poured and sprayed polyurethane foams are also used in construction. Sprayed polyurethane foams are widely used for insulating large structures such as storage tanks, etc. Pour-in-place polyurethane foams are used, for example, in appliances such as refrigerators and WO 91/13934 PCT/US91/00643 4 freezers plus they are used in making refrigerated trucks and railcars.

All of these various types of polyurethane foams require expansion agents (blowing agents) for their manufacture. Insulating foams depend on the use of halocarbon blowing agents, not only to foam the polymer, but primarily for their low vapor thermal conductivity, a very important characteristic for insulation value. Historically, polyurethane foams are made with CFC-11 (trichlorofluoromethane) as the primary blowing agent.

A second important type of insulating foam is phenolic foam. These foams, which have very attractive flammability characteristics, are generally made with CFC-11 and CFC-113 (1,1,2-trichloro-l,2,2-trifluoroethane) blowing agents.

A.third type of insulating foam is thermoplastic foam, primarily polystyrene foam. Polyolefin foams (polyethylene and polypropylene) are widely used in packaging. These thermoplastic foams are generally made with CFC-12.

Many smaller scale hermetically sealed, refrigeration systems, such as those used in refrigerators or window and auto air conditioners, use dichlorodifluoromethane (CFC-12) as the refrigerant.

Larger scale ctntrifugal refrigeration equipment, such as those used Aior industrial scale cooling, e.g., commercial office buildings, generally employ trichlorofluoromethane (CFC-11) or 1,1,2-trichlorotrifluoroethane (CFC-113) as the refrigerants of choice. Azeotropic mixtures, with their constant boiling points and compositions have also been found to be very useful as substitute refrigerants, for the applications cited above.

~i*cr~ -II L WO 91/13934 PC/US91/00643 5 Aerosol products have employed both individual halocarbons and halocarbonblends as propellant vapor pressure attenuators, in aerosol systems. Azeotropic mixtures, with their constant compositions and vapor pressures would be very useful as solvents and propellants in aerosol systems.

Some of the chlorofluorocarbons which are currently used for cleaning and other applications have been theoretically linked to depletion of the earth's ozone layer. As early as the mid-1970's, it was known what introduction of hydrogen into the chemical structure of previously fully-halogenated chlorofluorocarbons reduced the chemical stability of these compounds.

Hence, these now destabilized compounds would be expected to degrade in thelower atmosphere and not reach the stratospheric ozone layer in-tact. What is also needed, therefore, are substitute chlorofluorocarbons which have low theoretical ozone depletion potentials.

Unfortunately, as recognized in the art, it is not possible to predict the formation of azeotropes. This fact obviously complicates:the search for new azeotropic compositions, which'have application in the field. Nevertheless, there is a constant effort in the art to discover new azeotropic compositions, which have desirable solvency characteristics and particularly greater versatilities in solvency power.

Summary of the Invention According to the present invention, an azeotropic composition has been discovered comprising admixtures of effective amounts of dichloropentafluoropropane and trans-l,2-dichloroethylene, with an alcohol selected from the group consisting of methanol, ethanol and isopropanol. Unless otherwise stated, as used herein S- 5a dichloropentafluoropropane means a blend of 50 to 75 weight percent 1,1-dichloro- 2,2,3,3,3-pentafluoropropane and 25 to 50 weight percent 1,3-dichloro-1,1,2,2,3pentafluoropropane.

More specifically, the azeotropic mixtures are an admixture of about 47- 57 weight percent, preferably about 49-54 weight percent, dichloropentafluoropropane, about 38-48 weight percent, preferably about 40-45 weight percent, trans-1,2-dichloroethylene and about 3-9 weight percent, preferably about 4-7 weight percent, .methanol; an admixture of about 47-57 weight percent, preferably about 49-54 weight percent, dichloropentafluoropropane, about 40-50 weight percent, preferably about 42-47 weight percent, trans-1,2-dichloroethylene and about 1-5 weight percent, preferably about 2-4 weight percent, ethanol; and an admixture of about 49-59 weight percent, preferably about 49-54 weight percent, dichloropentafluoropropane, about 41-51 weight percent, preferably about 43-48 S weight percent, trans-1,2-dichloroethylene and about 0.1-1.0 weight percent, preferably about 0.5-0.7 weight percent, isopropanol.

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*s WO 91/13934 PCT/US91/00643 -6- 6 weight percent 1,l-dichloro-2,2,3,3,3-pentafluor propane and 25 to 50 weight percent 1,3-dichloro-l,1,2,2,3-pentafluoropropane More specifically, the azeotropi omixtures are an admixture of about 47-57 weight p ent dichloropentafluoropropane, about 38-48 weg t percent trans-1,2dichloroethylene and about -9 weight percent methanol; an admixture of about 57 weight percent dichloropentafluoropropane bout 40-50 weight percent trans- 1,2-dichloroet ene and about 1-5 weight percent ethanol; an an admixture of about 49-59 weight percent dichlor entafluoropropane, about 41-51 weight percent tra l,2-dichloroethylene and about 0.1-1.0 weight The present invention provides nonflammable azeotropic compositions which are well suited for solvent cleaning applications. The compositions of the invention can further be used as refrigerants with minor modifications in existing refrigeration equipment. They are useful in compression cycle applications including air conditioner and heat pump systems for producing both cooling and heating. The new refrigerant mixtures can be used in refrigeration applications such as described in U.S. Patent No.

4,482,465 to Gray.

The compositions of the instant invention comprise Sadmixture of effective amounts of dichloropentafluoropropane (C 3 HC12F 5 boiling point 52.5*C) and trans- 1,2-dichloroethylene (CHC1=CHC1, boiling point 48.0'C) with alcohols selected from the group consisting of methanol (CH3OH, boiling point 64.6'C) or ethanol (C2H 5 0H, boiling point 78.4"C) or isopropanol (C3H7OH, boiling point 82.4'C) to form an azeotropic composition. The aforementioned halocarbons are known WO 91/13934 PCT/US91/00643 7 as HCFC-225 and trans-HCC-1130, respectively, in the nomenclature conventional to the halocarbon field.

By azeotropic composition is meant, a constant boiling liquid admixture of three or more substances, whose admixture behaves as a single substan e, in that the vapor, produced by partial evaporation or distillation of the liquid has the same composition as the liquid, the admixture distills without substantial composition change. Constant boiling compositions, which are characterized as azeotropic, exhibit either a maximum or minimum boiling point, as compared with that of the nonazeotropic mixtures of the same substances.

By effective amount is meant the amount of e,.ch component of the instant invention admixture, which when combined, results in the formation of the azeotropic composition of the instant invention.

The language "an azeotropic composition consisting essentially is intended to include mixtures which contain all the components of the azeotrope of this invention (in any amounts) and which, if fractionally distilled, would produce an azeotrope containing all the components of this invention in at least one fraction, alone or in combination with another compound, one which distills at substantially the same temperature as said fraction.

It is possible to fingerprint, in effect, a constant boiling admixture, which may appear under many guises, depending upon the conditions chosen, by any of several criteria: The composition can be defined as an azeotrope of A, B and C, since the very term "azeotrope" is at once both definitive and limitative, and requires that effective amounts A, B and C form this unique C WO 91/13934 PCT/US91/00643 -8compos.tion of matter, which is a constant boiling admixture.

I* It is well known by those skilled in the art i that at different pressures, the composition of a given azeotrope will vary at least to some degree and changes in pressure will Ialso change at least to some degree the boiling point temperature. Thus an azeotrope of A, B and C represents a unique type of relationship but with a variable composition which depends on temperat'qe and/or pressure.

iTherefore compositional ranges, rather than fixed compositions, are often used to define azeotropes.

The composition can be defined as a particular weight percent relationship or mole percent relationship of A, B and C, while recognizing that such specific values point out only one particular such relationship and that in actuality, a series of such relationships, represented by A, B and C actually exist for a given azeotrope, varied by the influence of pressure.

S* Azeotrope A, B and C can be characterized by defining the composition as an azeotrope characterized by a boiling point at a given i pressure, thus giving identifying character- 1 istics without unduly limiting the scope of the invention by a specific numerical composition, which is limited by and is only as accurate as the analytical equipment available.

pentafluoropropane a ir ercent trar -1,2- B L---TT=Armr4yf-pnnfn L-rrr~-r~ lll- 8a Ternary mixtures of 47-57 weight percent, preferably about 49-54 weight percent, dichloropentafluoropropane and 38-48 weight percent, preferably about 40-45 weight percent, trans-l,2-dichloroethylene and 3-9 weight percent, preferably about 4-7 weight percent, methanol are i a to et e ao i i i i a i i i j Ii e 4 t as set*** I I i o I2--L WO 91/13934 PCT/US91/00643 9 characterized as azeotropic, in that mixtures within this range exhibit a substantially constant boiling point at constant pressure. Being substantially constant boiling, the mixtures do not tend to fractionate to any great extent upon evaporation. After evaporation, only a small difference exists between the composition of the vapor and the composition of the initial liquid phase. This difference is such that the compositions of the vapor and liquid phases are considered substantially identical. Accordingly, any mixture within this range exhibits properties which are, characteristic of a true ternary azeotrope. The ternary composition consisting of about 51.6 weight percent dichloropentafluoropropane, and about 42.6 weight percent trans-1.,2-dichloroethylene and about 5.8 weight percent methanol has been established, within the accuracy of the fractional distillation method, as a true ternary azeotrope, boiling at about 43.7'C, at substantially atmospheric pressure.

mixtures of 47-57 weight percent dichloropentafluo propane and 40-50 weight percent trans-1,2-dic o 0ethylene and 1-5 weight percent ethanol are characterized as azeotropic. The terna /omp'.-ition consisting of about 51.7 weight perc dichioropentafluoropropane, and about 45.3 wet Dpo.ent trans-1,2dichloroethylene and about 3...ight percent ethanol has been established, wit the accuracy of the fractional distillati ethod, as a true ternary azeotrope, boilin about 46.5'C, at substantially atmospheric pr re.

Also a rding to the instant invention, ternary mixture 49-59 weight percent dichloropentafluoropro and 41-51 weight percent trans-1,2-dichloro- 1).

1 1 1 1 i i 9a Also according to the instant invention, ternary mixtures of 47-57 weight percent, preferably about 49-54 weight percent, dichloropentafluoropropane and 40-50 weight percent, preferably about 42-47 weight percent, trans-1,_dichloroethylene and 1-5 weight percent, preferably about 2-4 weight percent, ethanol are characterized as azeotropic. The ternary composition consisting of about 51.7 weight percent dichloropentafluoropropane, and about 45.3 weight percent trans. 1.,2-dichloroethylene and about 3.0 weight percent ethanol has been established, within the accuracy of the fractional distillation method, as a true ternary azeotrope, boiling at about 46.50 C, at substantially atmospheric pressure.

Also according to the instant invention, ternary mixtures of 49-59 weight percent, preferably about 51-56 weight percent, dichloropentafluoropropane propane .id 41-51 weight percent, preferably about 43-48 weight percent, trans- S 1,2-dichloroethylene and 0.1-1.0 weight percent, preferably about 0.3-0.7 weight percent, isopropanol are I q i i ii WO 91/13934 PCT/US91/00643 10 characterized as azeotropic. The ternary composition consisting of about 53.9 weight percent dichloropentafluoropropane, and about 45.6 weight percent trans-1,2dichloroethylene and about 0.5 weight percent isopropanol has been established, within the accuracy of the fractional distillation method, as a true ternary azeotrope, boiling at about 47.7C, at substantially atmospheric pressure.

The aforestated azeotropes have low ozonedepletion potentials and are expected to decompose almost completely, prior to reaching the stratosphere.

The azeotropic compositions of the instant invention permit easy recovery and reuse of the solvent from vapor defluxing and degreasing operations because of their azeotropic natures. As an example, the azeotropic mixtures of this invention can be used in cleaning processes such as described in U.S. Patent No.

3,881,949, or as a buffing abrasive detergent or drying agent for jewelry or metal.

In addition, the mixtures are useful as resist-developers, where chlorine-type developers would be used, and as resist stripping agents with the addition of appropriate halocarbons.

Another aspect of the invention is a refrigeration method which comprises condensing a refrigerant composition of the invention and thereafter evaporating it i in the vicinity of a body to be cooled. Similarly, still another aspect of the invention is a method for heating which comprises condensing the invention refrigerant in the vicinity of a body to be heated and thereafter evaporating the refrigerant. A further aspect of the invention includes aerosol compositions comprising an active agent and a propellant, wherein the propellant is an azeotropic mixture of the invention; and the production of these compositions by I WO 91/13934 PCT/US91/00643 11combining said ingredients. The invention further comprises cleaning solvent compositions comprising the a. azeotropic mixtures of the invention.

i The azeotropic compositions of the instant invention can be prepared by any convenient method including mixing or combining the desired component amounts. A preferred method is to weigh the desired component amounts and thereafter combine them in an appropriate container.

Without further elaboration, it i.s believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest ii extent. The following preferred specific embodiments Sare, therefore, to be construed as merely illustrative, i and not limitative of the remainder of the disclosure in any way whatsoever.

SIn the foregoing and in the following examples, all temperatures are set forth uncorrected in degrees J Celsius and unless otherwise indicated, all parts and percentages are by weight.

The entire disclosure of all applications, patents I and publications, cited above and below, are hereby incorporated by reference.

WO 91/13934 PCT/US91/00643 -12-

EXAMPLES

Example 1 A solution which contains 55.0 weight percent dichloropentafluoropropane (gas chromatographic weight percent isomer distribution is: HCFC-225ca (CHC12CF2CF 3 71.4 HCFC-225cb (CC1F2CF2CHC1F)= 40.0 weight percent trans-1,2-dichloroethylene and 5.0 weight percent methanol is prepared in a suitable container and is mixed thoroughly.

The solution is distilled in a Perkin-Elmer Model 251 Autoannular Spinning Band Still (200 plate fractionating capability), using about a 10:1 reflux to take-off ratio. Head temperatures are read directly to 0.1'C. All temperatures are adjusted to 760 mm pressure. Distillate compositions are determined by gas chromatography. Results obtained are summarized in Table 1.

TABLE 1 DISTILLATION OF: (55.0 40.0 DICHLOROPENTAFLUOROPROPANE (DCPFP), TRANS-1, 2-DICHLOROETHYLENE (T-DCE) AND METHANOL (MEOH)

WT.%

DISTILLED

TEMPERATURE, *C OR CUTS HEAD RECOVERED DCPFP T-DCE MEOH 1 42.3 6.4 44.5 49.4 6.1 2 42.4 11.8 50.6 43.5 5.9 3 42.6 18.0 50.7 43.4 5.9 4 44.4 28.3 52.2 42.1 5.7 44.3 39.6 51.9 42.3 5.8 6 44.6 51.8 52.3 42.0 5.7 7 42.0 62.3 50.5 43.3 6.2 8 42.9 72.7 58.1 36.9 HEEL 86.7 69.8 28.6 1.6 Analysis of the above data indicates very small differences between temperatures and distillate compositions, as the distillation progresses. A statistical WO 91/13934 PCT/US91/00643 -13 analysis of the data indicates that the true ternary azeotrope of dichloropentafluoropropane, trans-1,2dichloroethylene and methanol has the following characteristics at atmospheric pressure (99 percent confidence limits): Dichloropentafluoropropane 51.6 3.8 wt.% Trans-l,2-Dichloroethylene 42.6 3.5 wt.% Methanol 5.8 0.3 wt.% Boiling point, 'C 43.7 4.9 Example 2 A solution which contains 59.1 weight percent dichloropentafluoropropane (gas chromatographic weight percent isomer distribution was: HCFC-225ca 71.4%; HCFC-225cb 37.3 weight percent trans-1,2dichloroethylene and 3.6 weight percent ethanol is prepared in a suitable container and mixed thoroughly.

The solution is distilled in a Perkin-Elmer Model 251 Autoannular Spinning Band Still (200 plate fractionating capability), using about a 10:1 reflux to take-off ratio. Head temperatures are read directly to O.I'C. All temperatures are adjusted to 760 mm pressure. Distillate compositions are determined by gas chromatography. Results obtained are summarized in Table 2.

wo 91/13934 PCT/US91/00643 14 TABLE 2 DISTILLATION OF: (59.1 37.3 3.6) DICHLOROPENTAFLUOROPROPANE (DCPFP), TRANS-1,2-DICHLOROETHYLENE (T-DCE) AND ETHANOL (ETOH)

CUTS

1 2 3 4 6 7

HEEL

TEMPERATURE,*C

HEAD

46.4 46.4 46.4 46.4 46.5 46.6 46.8

WT.%

DISTILLED

OR

RECOVERED

1.1 10.2 18.0 26.9 36.2 42.8 50.9 89.0

DCPFP

54.0 51.9 51.8 51.6 51.6 51.7 52.4 69.8

T-DCE

43.0 45.0 45.1 45.4 45.4 45.3 44.7 25.6

ETOH

3.1 3.1 2.9 4.6 Analysis of the above data indicates very small differences between temperatures and distillate compositions, as the distillation progresses. A statistical analysis of the data indicates that the true ternary azeotrope of dichloropentafluoropropane, trans-1,2dichloroethylene and ethanol has the following characteristics at atmospheric pressure (99 percent confidence limits): Dichloropentafluoropropane 51.7 0.9 wt.% Trans-1,2-Dichloroethylene 45.3 1.2 wt.% Ethanol 3.0 0.4 wt.% Boiling point, 'C 46.5 0.4 WO 91/13934 PCT/US91/00643 15 Example 3 A solution which contained 58.1 weight percent dichloropentafluoropropane, (gas chromatographic weight percent isomer distribution is: HCFC-225ca 71.4%; HCFC-225cb 39.1 weight percent trans-1,2dichloroethylene and 2.8 weight percent isopropanol prepared in a suitable container and mixed thoroughly.

The solution is distilled in a Perkin-Elmer Model 251 Autoannular Spinning Band Still (200 plate fractionating capability), using about a 10:1 reflux to take-off ratio. Head temperatures are read directly to 0.1'C. All temperatures are adjusted to 760 mm pressure. Distillate compositions are determined by gas chromatography. Results obtained are summarized in Table 3.

TABLE 3 DISTILLATION OF: (58.1 39.1 2.8) DICHLOROPENTAFLUOROPROPANE (DCPFP), TRANS-1,2-DICHLOROETHYLENE (T-DCE) AND ISOPROPANOL (IPROH)

WT.%

DISTILLED

TEMPERATURE, 'C OR CUTS HEAD RECOVERED DCPFP T-DCE IPROH 1 47.7 9.7 55.2 44.4 0.4 2 47.7 19.1 54.1 45.4 3 47.7 28.9 54.0 45.5 4 47.7 38.5 54.0 45.5 47.7 47.9 53.9 45.7 6 47.7 58.0 53.9 45.7 7 47.7 66.8 54.4 45.2 0.4 HEEL 92.4 68.2 22.6 9.2 WO 91/13934 PCT/US91/00643 16 Analysis of the above data indicates very small differences between temperatures and distillate compo- V sitions, as the distillation progressed. A statistical analysis of the data indicates that the true ternary azeotrope of dichloropentafluoropropane, trans-1,2dichloroethylene and isopropanol has the following characteristics at atmospheric pressure (99 percent confidence limits): Dichloropentafluoropropane 53.9 0.3 wt.% Trans-1,2-Dichloroethylene 45.6 0.4 wt.% Isopropanol 0.5 0.1 wt.% Boiling point, *C 47.7 0.0 Example 4 SSeveral single sided circuit boards are coated with activated rosin flux and soldered by passing the boards over a preheater, to obtain top side board temperatures of approximately 200'F and then through 500'F (260'C) molten solder. The soldered boards are defluxed separately, with the azeotropic mixtures cited in Examples 1, 2 and 3 above, by suspending a circuit board, first, for three minutes in the boiling sump, which contains the azeotropic mixture, then, for one minute in the rinse sump, which contains the same azeotropic mixture, and finally, for one minute in the solvent vapor above the boiling sump.

The boards cleaned in each azeotropic mixture have no visible residue remaining thereon.

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics i)-er~ WO 91/13934 PCT/US91/00643 17 of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

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Claims (4)

18- The claims defining the invention are as follows:- 1. An azeotropic composition consisting essentially of: about 47-57 weight percent dichloropentafluoropropane consisting essentially of a blend of about 50 to 75 weight percent 1,1-dichloro-2,2,3,3,3-pentafluoropropane and about 25 to 50 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane, about 38-48 weight percent trans-1,2-dichloroethylene and about 3-9 weight percent methanol, wherein the composition has a boiling point of about 43.7'C. when the pressure is adjusted to substantially atmospheric pressure, or about 47-57 weight percent dichloropentafluoropropane S consisting essentially of about 50 to 75 weight percent 1,1- dichloro-2,2,3,3,3-pentafluoropropane and about 25 to 50 weight Spercent 1,3-dichloro-1,1,2,2,3-pentafluoropropane. about weight percent trans-1,2-dichloroethylene and about 1-5 weight percent ethanol, wherein the composition has a boiling point of about 46.5'C. when the pressure is adjusted to substantially atmospheric pressure, or about 49-59 weight percent dichloropentafluoropropane 20 consisting essentially of about 50 to 75 weight por,~tt 1,1- dichloro-2,2,3,3,3-pentafluoropropane and about 25 to 50 weight percent 1,3-dichloro-l,1,2,2,3-pentafluoropropane, about 41-51 weight percent trans-1,2-dichloroethylene and about 0.1-1.0 weight percent isopropanol wherein the composition has a boiling point of about 47.7'C. when the pressure is adjusted to substantially atmospheric pressure. 2. The azeotropic composition of claim 1, consisting essentially of about 47-57 weight percent of the dichloropentafluoropropane blend, about

38-48 weight percent trans-1,2-dichloroethylene and about 3-9 weight percent t i m I i (1 i- I -19- ol. t 3. The azeotropic composition of claim 1, consisting essentially of about 47-57 weight percent of the dichloropentafluoropropane blend, about

40-50 weight percent trans-1,2-dichloroethylene and about 1-5 weight percent ethanol. *I 4I 1 4. The azeotropic composition of claim 1, consisting essentially of about 49-59 weight percent of the dichloropentafluoropropane blend, about

41-51 weight percent trans-1,2-dichloroethylene and about 0.1-1.0 weight percent isopropanol. The azeotropic composition of claim 1, consisting essentially of about 51.6 weight percent of the dichloropentafluoropropane blend, and about 42.6 weight percent trans-1,2-dichloroethylene and about 5.8 weight percent mcthanol. 6. The azeotropic composition of claim 1, consisting essentially of about 51.7 weight percent of the dichloropentafluoropropane blend, and about 45.3 weight percent trans-1,2-dichloroethylene and about 3.0 weight percent ethanol. I 7. The azeotropic composition of claim 1, consisting essentially of about 53.9 weight percent of the dichloropentafluoropropane blend, and about 45.6 weight percent trans-1,2-dichloroethylene and about 0.5 weight percent isopropanol. 8. A process for cleaning a solid surface which comprises treating said surface with an azeotropic composition of claim 1. 9. The process of claim 8, wherein the solid surface is a printed circuit board contaminated with flux and flux-residue,. The process of claim 9, wherein the solid surface is a metal. 11. An azeotropic composition consisting essentially of: about 49-54 weight iercent dichloropentafluoropropane consisting essentially of about 50 to 75 weight percent 1,1- 4 Yh~- T- i i_ h 1 i 9 44 j4 dichloro-2,2,3,3,3-pentafluoropropane and about 25 to 50 weight percent 1,3-dichloro-l,1,2,2,3-pentafluoropropane, about 40-45 weight percent trans-1,2-dichloroethyiene and about 4-7 weight percent methanol, wherein the composition has a boiling point of about 43.7'C. when the pressure is adjusted to substantially atmospheric pressure, or about 49-54 weight percent dichloropentafluoropropane consisting essentially of about 50 to 75 weight percent 1,1- dichloro-2,2,3,3,3-pentafluoropropane and about 25 to 50 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane, about 42-47 weight percent trans-1,2-dichloroethylene and about 2-4 weight percent ethanol, wherein the composition has a boiling point of about 46.5'C. when the pressure is adjusted to substantially atmospheric pressure, or about 51-56 weight percent dichloropentafluoropropane consisting essentially of about 50 to 75 weight percent 1,1- dichloro-2,2,3,3,3-pentafluoropropane and about 25 to 50 weight percent 1,3-dichloro-1,1,2,2,3-pentafluoropropane, about 43-48 weight percent trans-1,2-dichloroethylene and about 0.3-0.7 weight 20 percent isopropanol, wherein the composition has a boiling point of about 47.7'C. when the pressure is adjusted to substantially atmospheric pressure. :12. A process for producing refrigeration which comprises evaporating a mixture of claim 1 in the vicinity of a body to be cooled. 13. A process for producing heat which comprises condensing a composition of claim 1 in the vicinity of a body to be heated. 14. In a process for preparing a polymer foam comprising expanding a polymer with a blowing agent, the improvement wherein the blowing agent is a composition of claim 1. 9. S 1 -21- In an aerosol composition comprising a propellant and an active agent, the improvement wherein the propellant is a composition of claim 1. 16. A process for preparing aerosol formulations comprising conden~sing an active ingredient i an a'erosol container with an effective amonowt of the composition of claim '1 as a prujpellant. DATED this 22nd day of April 1993. E.I. DU PONT DE NEMOUIS AND COMPANY By their Patent Attorneys: CALLINAN LAWRIE C* I C II II C I 6-' CI CI C CI C 9* eC S C C. INTERNATIONAL SEARCH REPORT International Aotrlicalion No PTA~~/r/' 1. CLASSIFICATION OF SUBJECT MATTER (it several classiicalion symbols apply, indicate all) 3 A ccurd t Ilenajonal Patent Classification CPCi or to both/Jtional Classification and IPC W 9/1; 0W 1a; 7/X 7/50; (23 5/M2 US I! 252/171 II. FIELDS SEARCHED Minimum Documentation Searched Classification System Classilication Symbols L CIL. 62/114; 134/1.2,31,38,39,40; 25Z/67,69,162,170,171; 252/172,305,364, DIM; 521/98,13 Documentation Searched other than Minimum Documentation to the Extenit that sucti Documents ire Included In the Fields Searched 111, DOCUMENTS CONSIDERED TO BE RELEVANT Ii Categ 1 ory Citlilon o! Document, 111 with indication, where appropriate, of the relevant passages 17 Relevant to Claim No. li' X EP, A, 347,924 (AS4H aIASS CC7'PANY IM.) 27 MEMIiM 1989 1-16 1F-20 Y See pae 2, lines 40-41, pae 3, line 19-38 andi 51-53, pae 4 line 17 2 -d lines 16-19 X,P A, 90/08815 (ASU{ Q.ASS (flIFANY ID.) 09~ Agat 1990 1-14 YP See pag 5, lines 12-20, page 8 lines 11-12 a- 21-24, pae 9 5-19 X,P JP, A, 2-207033 (AS4ai QIASS KO) 16 A.§.st 1999 1-17 YP See clatirrs an pae 2 column 1, lines 24-25 and eaple 1 18419 (dm- earple a-hr g es 2 ar-d 3). Special categories of cited documents! later Uocument Published alter the international filint inlte document defining the general state ot the art which is not or priority cole and not in conflict with the application but considerea to oe of iparticular relevance cited to understand file principle or theory underlying the invention "E earlier dlocu~ment out published on or after the international document of particular relevance; lie claimed Invention filing date cannot be ccrnsidereo novel or cannot bo considered to document which nmay throw cdoublas on piority claim(s) or involve an inventive step whic h is cited to tistablish the ,ublication date of another document of Particular relevance; the claimedinnl~ cittio oroter oecalreao~ asspeifid)cannot be considered to involve an Inventive step when, there 0O' document referring to an oral disclosure, use, exhibition or document is combined witn one or more other such d-cu-I other means ments, such conroination being obvious to a person Wriled document puotlidheO Prior to the international filing data but in the art, later than tine oriority diate claimed document member of~ the same patent family IV, CERTIFICAT'ON Date of the Actual Completion of the International Search 2Date of Mailing of this Inlernational Search Report AFF 199 22 APR 1991 International Searlching Authority I ta lre of Authorized 0. car '11 *isAA DQ. X/ -1 Form PCT/ISA/21O (second sheet) (May 1986) '4cr~E"lla International Application No/CTS t/0X43 Ill. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category Citation of Document, i with indication, where appropriate. of the relevant passages 1 Relevant to Claim No A 3, A, 1,562,026 (IW CIECAL CFPANW) 05 MiRCH 1980 1 17 =E PAE 1. A US, A, 4,465,69 I(=SLT AL) 14AL 1984 1 15-16 SEE AI3SIFtPW. A,P tJZ, A, 4,947,881 (M66IZErAL) 14AUT 1990 1 &11-13 SEE AS31-ATCF. JP, A, 2-207032 (AS4Ia GASS KK) 16 A=FT 1990 1-20 SEE QADE A,P JP, A, 2-237947 (ASUI QASS KK) 20 SEP]R3 1990 1-20 A,P LIS, A, 4,91,869 (FaMS Er AQ 09 OMR 1990 1-20 SEE AMSMR6J. Form PCT/ISA/210 (extra sheet) (May 1986)