# Patent

## Title
Azeotrope-like compositions of pentafluoropropane, methanol and dichloroethylene

## Abstract

Provided are azeotrope-like compositions comprising pentafluoropropane, methanol, and dichloroethylene, and uses thereof, including use in aerosols, refrigerant compositions, refrigeration systems, and blowing agent compositions.

## Background
FIELD OF INVENTION
The present invention provides azeotrope-like compositions of pentafluoropropane, methanol, and dichloroethylene, and uses thereof.
BACKGROUND
Fluorocarbon based fluids have found widespread use in industry in a number of applications, including as refrigerants, aerosol solvents, propellants, blowing agents, heat transfer media, and gaseous dielectrics. Because of the suspected environmental problems associated with the use of some of these fluids, including the relatively high global warming potentials associated therewith, it is desirable to use fluids having low or even zero ozone depletion potential, such as hydrofluorocarbons (“HFCs”). Thus, the use of fluids that do not contain chlorofluorocarbons (“CFCs”) or hydrochlorofluorocarbons (“HCFCs”) is desirable. Additionally, the use of single component fluids or azeotropic mixtures, which do not fractionate on boiling and evaporation, is desirable. However, the identification of new, environmentally-safe, non-fractionating mixtures is complicated due to the fact that azeotrope formation is not readily predictable.
The industry is continually seeking new fluorocarbon based mixtures that offer alternatives, and are considered environmentally safer substitutes for CFCs and HCFCs. Of particular interest are mixtures containing both hydrofluorocarbons and other fluorinated compounds, both of low ozone depletion potentials. Such mixtures are the subject of this invention.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graphical depiction of the boiling points associated with various compositions comprising 1,1,1,3,3-pentafluoropropane (“HFC-245fa”), methanol (“MeOH”), and trans-1,2-dichloroethylene (“Trans”), according to one embodiment of the present invention.
FIG. 2 is a graphical depiction of the boiling points associated with various other compositions comprising HFC-245fa, MeOH, and Trans, according to another embodiment of the present invention.
FIG. 3 is a graphical depiction of the boiling points associated with various other compositions comprising HFC-245fa, MeOH, and Trans, according to yet another embodiment of the present invention.
FIG. 4 is a graphical depiction of the boiling points associated with various other compositions comprising HFC-245fa, MeOH, and Trans, according to yet another embodiment of the present invention.



DESCRIPTION OF PREFERRED EMBODIMENTS
The present inventors have developed several compositions that help to satisfy the continuing need for alternatives to CFCs and HCFCs. According to certain embodiments, the present invention provides azeotrope-like compositions comprising 1,1,1,3,3-pentafluoropropane (“HFC-245fa”), methanol (“MeOH”), and trans-1,2-dichloroethylene (“Trans”).
The preferred compositions of the invention provide environmentally desirable, zero ozone depletion potential replacements for currently used CFCs and HCFCs. Additionally, in certain embodiments the compositions of the invention exhibit characteristics that make the compositions better CFC and HCFC substitutes than any of HFC-245fa, MeOH, and Trans alone.
Additionally, applicants have recognized surprisingly that azeotrope-like compositions of HFC-245fa, MeOH, and Trans can be formed. Accordingly, in other embodiments, the present invention provides methods of producing an azeotrope-like composition comprising combining HFC-245fa, MeOH, and Trans in amounts effective to produce and azeotrope-like composition.
Applicants have further recognized that the azeotrope-like compositions of the present invention exhibits properties that make that make them advantageous for use as solvents and/or propellants in sprayable compositions, including aerosols. Accordingly, in yet other embodiments, the present invention provides solvents, propellants, and sprayable compositions comprising an azeotrope-like composition of HFC-245fa, MeOH, and Trans.
In yet other embodiments, the present invention provides refrigerants and blowing agents comprising an azeotrope-like composition of the present invention.
Azeotrope-like Compositions
As used herein, the term “azeotrope-like” is intended in its broad sense to include both compositions that are strictly azeotropic and compositions that behave like azeotropic mixtures. From fundamental principles, the thermodynamic state of a fluid is defined by pressure, temperature, liquid composition, and vapor composition. An azeotropic mixture is a system of two or more components in which the liquid composition and vapor composition are equal at the stated pressure and temperature. In practice, this means that the components of an azeotropic mixture are constant-boiling and cannot be separated during a phase change.
The azeotrope-like compositions of the invention may include additional components that do not form new azeotrope-like systems, or additional components that are not in the first distillation cut. The first distillation cut is the first cut taken after the distillation column displays steady state operation under total reflux conditions. One way to determine whether the addition of a component forms a new azeotrope-like system so as to be outside of this invention is to distill a sample of the composition with the component under conditions that would be expected to separate a non-azeotropic mixture into its separate components. If the mixture containing the additional component is non-azeotrope-like, the additional component will fractionate from the azeotrope-like components. If the mixture is azeotrope-like, some finite amount of a first distillation cut will be obtained that contains all of the mixture components that is constant boiling or behaves as a single substance.
It follows from this that another characteristic of azeotrope-like compositions is that there is a range of compositions containing the same components in varying proportions that are azeotrope-like or constant boiling. All such compositions are intended to be covered by the terms “azeotrope-like” and “constant boiling”. As an example, it is well known that at differing 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. It follows that, for azeotrope-like compositions, there is a range of compositions containing the same components in varying proportions that are azeotrope-like. All such compositions are intended to be covered by the term azeotrope-like as used herein.
It is well-recognized in the art that it is not possible to predict the formation of azeotropes. (See, for example, U.S. Pat. No. 5,648,017 (column 3, lines 64-65) and U.S. Pat. No. 5,182,040 (column 3, lines 62-63), both of which are incorporated herein by reference). Applicants have discovered unexpectedly that HFC-245fa, MeOH, and Trans form azeotrope-like compositions.
According to certain preferred embodiments, the azeotrope-like compositions of the present invention comprise, and preferably consist essentially of, effective amounts of HFC-245fa, MeOH, and Trans. The term “effective amounts” as used herein refers to the amount of each component which upon combination with the other components, results in the formation of an azeotrope-like composition of the present invention. Preferably, the present azeotrope-like compositions comprise, and preferably consist essentially of, from about 50 to less than 100 weight percent of HFC-245fa, from greater than zero to about 25 weight percent of MeOH, and from greater than zero to about 30 weight percent of Trans. More preferably, the azeotrope-like compositions comprise, and preferably consist essentially of, from about 65 to less than 100 weight percent of HFC-245fa, from greater than zero to about 15 weight percent of MeOH, and from greater than zero to about 20 weight percent of Trans, and even more preferably from about 75 to less than 100 weight percent of HFC-245fa, from greater than zero to about 10 weight percent of MeOH, and from greater than zero to about 15 weight percent of Trans. Unless otherwise indicated, the weight percents disclosed herein are based on the total weight of HFC-245fa, MeOH, and Trans in a composition.
The azeotrope-like compositions described herein preferably have a boiling point of from about 14° C. to about 17° C. at a pressure of about 14 to 15 psia. In certain more preferred embodiments, the present azeotrope-like compositions have a boiling point of from about 14° C. to about 16° C. at a pressure of about 14 to 15 psia, and in even more preferred embodiments, from about 14° C. to about 15° C. at a pressure of about 14 to 15 psia.
The azeotrope-like compositions of the present invention can be produced by combining effective amounts of HFC-245fa, MeOH, and Trans. Any of a wide variety of methods known in the art for combining two or more components to form a composition can be adapted for use in the present methods to produce an azeotrope-like composition. For example, HFC-245fa, MeOH, and Trans can be mixed, blended, or otherwise contacted by hand and/or by machine, as part of a batch or continuous reaction and/or process, or via combinations of two or more such steps. In light of the disclosure herein, those of skill in the art will be readily able to prepare azeotrope-like compositions according to the present invention without undue experimentation.
Uses of the Compositions
The present compositions have utility in a wide range of applications. For example, one embodiment of the present invention relates to the use of the present compositions as solvents and/or propellants in sprayable compositions. In general, sprayable compositions comprise a material to be sprayed and a propellant, solvent or mixtures of two or more thereof. For a sprayable composition to be useful, it is necessary that the material to be sprayed be relatively or substantially soluble in the solvents to be used. While many HFCs alone, such as HFC-245fa, are poor solvents for many conventionally sprayable materials, applicants have recognized that the compositions of the present invention tend to exhibit relatively high solubility with such materials, while also tending to remain non-flammable.
Any of a wide range of sprayable materials can be used in conjunction with the compositions of the present invention to produce a sprayable composition according to the present invention. Examples of suitable materials include, without limitation, oils and other lubricants, release agents, cleaners, polishing agents, medicinal materials, such as, anti-asthma and anti-halitosis medicines, as well as, cosmetic materials, such as, deodorants, perfumes, hair sprays, and the like. The sprayable compositions of the present invention may further comprise any of a wide range of inert ingredients, additional solvents, and other materials used conventionally in sprayable compositions.
In certain other embodiments, the compositions of the present invention are used as, or in, refrigerant compositions. Refrigerant compositions of the present invention may be used in any of a wide variety of refrigeration systems including air-conditioning, refrigeration, heat-pump systems, and the like. In certain preferred embodiments, the compositions of the present invention are used in refrigeration systems originally designed for use with an HFC-refrigerant. The preferred compositions of the present invention tend to exhibit many of the desirable characteristics of other HFC-refrigerants, including non-flammability, and a GWP that is as low, or lower than that of conventional HFC-refrigerants. In addition, the relatively constant boiling nature of the compositions of the present invention makes them even more desirable than certain conventional CFCs, HCFCs, and/or HFCs for use as refrigerants in many applications.
Yet another embodiment of the present invention relates to a blowing agent comprising one or more azeotrope-like compositions of the invention. In other embodiments, the invention provides foamable compositions, and preferably polyurethane and polyisocyanurate foam compositions, and methods of preparing foams. In such foam embodiments, one or more of the present azeotrope-like compositions are included as a blowing agent in a foamable composition, which composition preferably includes one or more additional components capable of reacting and foaming under the proper conditions to form a foam or cellular structure, as is well known in the art. Any of the methods well known in the art, such as those described in “Polyurethanes Chemistry and Technology,” Volumes I and II, Saunders and Frisch, 1962, John Wiley and Sons, New York, N.Y., which is incorporated herein by reference, may be used or adapted for use in accordance with the foam embodiments of the present invention.
Other uses of the present azeotrope-like compositions include use as non-aerosol solvents, cleaning agents, and the like. Those of skill in the art will be readily able to adapt the present compositions for use in such applications without undue experimentation.
EXAMPLES
The invention is further illustrated in the following examples that are intended to be illustrative, but not limiting in any manner.
Example 1
An ebulliometer comprising a vacuum jacketed tube with a condenser on top, which condenser is further equipped with a thermometer is used. About 5 grams of a mixture consisting of 99.5 wt. % HFC-245fa and 0.5 wt. % of MeOH is charged to the ebulliometer and then Trans is added in small, measured increments. The boiling point temperatures of the resulting ternary mixtures were recorded (see Table 1). Temperature depression is observed when Trans is added to the HFC-245fa/MeOH mixture, indicating a ternary minimum boiling azeotrope is formed. From greater than about 0 to about 30 weight percent Trans, the boiling point of the composition changed by about 1° C. or less. The compositions exhibit azeotrope and/or azeotrope-like properties over this range. FIG. 1 is a graphical depiction of the data listed in Table 1.







TABLE 1







HFC-245fa/MeOH/Trans compositions at 14.42 psia










Wt. % Trans (with




remainder being HFC-



245fa/MeOH mixture



in 99.5:0.5 ratio)
Temperature (° C.)














0.00000
14.324733



1.874525
14.255234



3.680066
14.218267



5.420362
14.20977



7.098887
14.220521



8.718874
14.249896



10.28333
14.294988



11.79506
14.350909



13.2567
14.414025



14.67068
14.469872



16.0393
14.542105



17.36471
14.605315



18.64893
14.67205



19.89384
14.731918



21.10123
14.786563



22.27275
14.8467



23.41
14.891907



24.51445
14.944701



25.5875
14.983561



26.63047
15.03836



27.6446
15.084299



28.63108
15.111737



29.59103
15.138144



30.52549
15.164986



31.43548
15.188504



32.32193
15.21308



33.18576
15.237798



34.02781
15.275908



34.84891
15.303219



35.64981
15.326635



36.43126
15.36948



37.19396
15.372878



37.93858
15.395723



38.66575
15.433039



39.37607
15.43316



40.07013
15.459317



40.74848
15.45859



41.41164
15.491919



42.06012
15.501624



42.69441
15.511375



43.31496
15.530083



43.92221
15.542162



44.51659
15.560614



45.0985
15.579288



45.66833
15.591573



46.22645
15.606808



46.77323
15.616341



47.309
15.630337










Example 2
An ebulliometer comprising a vacuum jacketed tube with a condenser on top, which condenser is further equipped with a thermometer is used. About 5 grams of a mixture consisting of 99 wt. % HFC-245fa and 1 wt. % of MeOH is charged to the ebulliometer and then Trans is added in small, measured increments. The boiling point temperatures of the resulting ternary mixtures were recorded (see Table 2). Temperature depression is observed when Trans is added to the HFC-245fa/MeOH mixture, indicating a ternary minimum boiling azeotrope is formed. From greater than about 0 to about 30 weight percent Trans, the boiling point of the composition changed by about 1° C. or less. The compositions exhibit azeotrope and/or azeotrope-like properties over this range. FIG. 2 is a graphical depiction of the data listed in Table 2.







TABLE 2







HFC-245fa/MeOH/Trans compositions at 14.55 psia










Wt. % Trans (with




remainder being HFC-



245fa/MeOH mixture



in 99:1 ratio)
Temperature (° C.)














0.00000
14.560875



1.881539
14.51505



3.693583
14.446242



5.43991
14.418792



7.124033
14.430813



8.749217
14.461814



10.3185
14.509962



11.83473
14.56614



13.30053
14.636285



14.7184
14.709037



16.09063
14.784681



17.4194
14.85534



18.70675
14.92799



19.95457
14.991131



21.16467
15.044294



22.33872
15.101542



23.47832
15.153657



24.58496
15.208391



25.66004
15.260273



26.70491
15.284395



27.72081
15.332457



28.70893
15.370247



29.6704
15.40032



30.60628
15.416988



31.51758
15.42089



32.40526
15.435677



33.27022
15.45826



34.11332
15.488271



34.93538
15.496955



35.73718
15.516719



36.51947
15.549104



37.28293
15.566483



38.02825
15.603293



38.75606
15.606917



39.46698
15.633639



40.16158
15.651954



40.84042
15.662793



41.50403
15.682942



42.15292
15.704715



42.78757
15.704413



43.40844
15.736451



44.01599
15.754755



44.61063
15.781732



45.19277
15.79035



45.7628
15.796134



46.32109
15.837646



46.86801
15.853533



47.4039
15.891707



47.92908
15.890446



48.44388
15.89914



48.9486
15.912785



49.44353
15.924059



49.92896
15.937334



50.40516
15.945772



50.87238
15.982232



51.33088
15.974255



51.78091
16.024206



52.22268
16.015691



52.65644
16.034227



53.08239
16.051006



53.50075
16.058578



53.91171
16.088404










Example 3
An ebulliometer comprising a vacuum jacketed tube with a condenser on top, which condenser is further equipped with a thermometer is used. About 5 grams of a mixture consisting of 98 wt. % HFC-245fa and 2 wt. % of MeOH is charged to the ebulliometer and then Trans is added in small, measured increments. The boiling point temperatures of the resulting ternary mixtures were recorded (see Table 3). Temperature depression is observed when Trans is added to the HFC-245fa/MeOH mixture, indicating a ternary minimum boiling azeotrope is formed. From greater than about 0 to about 30 weight percent Trans, the boiling point of the composition changed by about 1° C. or less. The compositions exhibit azeotrope and/or azeotrope-like properties over this range. FIG. 3 is a graphical depiction of the data listed in Table 3.







TABLE 3







HFC-245fa/MeOH/Trans compositions at 14.56 psia










Wt. % Trans (with




remainder being HFC-



245fa/MeOH mixture



in 98:2 ratio)
Temperature (° C.)














0.00000
14.591277



1.892873
14.563341



3.715417
14.54399



5.471782
14.548524



7.164638
14.581501



8.798208
14.628102



10.37528
14.678294



11.89874
14.742496



13.37127
14.813788



14.79539
14.854977



16.17344
14.916289



17.50763
14.984128



18.80001
15.026536



20.05252
15.096852



21.26698
15.136507



22.44509
15.184695



23.58847
15.216237



24.69862
15.272987



25.77698
15.312193



26.82489
15.335533



27.84362
15.356987



28.83437
15.398328



29.79829
15.438179



30.73644
15.476011



31.64985
15.487076



32.53948
15.532612



33.40625
15.57818



34.25103
15.589618



35.07464
15.620276



35.87788
15.639918



36.66148
15.663562



37.42617
15.682445



38.1726
15.684817



38.90145
15.720893



39.6133
15.740252



40.30876
15.759583



40.98839
15.784468



41.65271
15.80168



42.30224
15.831784



42.93747
15.841793



43.55887
15.862217



44.16687
15.870884



44.76192
15.889942



45.34442
15.909451



45.91476
15.934654



46.47332
15.940821



47.02046
15.961336



47.55653
15.98724



48.08186
16.011146



48.59677
16.019877



49.10156
16.047012



49.59654
16.096498



50.08198
16.107891



50.55817
16.1061



51.02535
16.148877



51.48378
16.175016



51.93372
16.191049



52.37538
16.199324



52.80901
16.213993



53.2348
16.2523



53.65298
16.253063



54.06375
16.265377



54.46731
16.304252



54.86383
16.329281



55.25351
16.349336



55.63651
16.372544



56.01302
16.408122



56.38319
16.415054



56.74718
16.450079



57.10514
16.462111



57.45723
16.482437



57.80358
16.518946



58.14435
16.55335



58.47965
16.573452



58.80962
16.585997



59.13439
16.603632



59.45408
16.608104



59.7688
16.625504










Example 4
An ebulliometer comprising a vacuum jacketed tube with a condenser on top, which condenser is further equipped with a thermometer is used. About 5 grams of a mixture consisting of 96.5 wt. % HFC-245fa and 3.5 wt. % of MeOH is charged to the ebulliometer and then Trans is added in small, measured increments. The boiling point temperatures of the resulting ternary mixtures were recorded (see Table 4). Temperature depression is observed when Trans is added to the HFC-245fa/MeOH mixture, indicating a ternary minimum boiling azeotrope is formed. From greater than about 0 to about 30 weight percent Trans, the boiling point of the composition changed by about 1° C. or less. The compositions exhibit azeotrope and/or azeotrope-like properties over this range. FIG. 4 is a graphical depiction of the data listed in Table 4.







TABLE 4







HFC-245fa/MeOH/Trans compositions at 14.65 psia










Wt. % Trans (with




remainder being HFC-



245fa/MeOH mixture



in 96.5:3.5 ratio)
Temperature (° C.)














0.00000
14.731811



1.904343
14.69272



3.737512
14.616791



5.503422
14.591727



7.20571
14.578382



8.847751
14.557459



10.43269
14.593235



11.96345
14.643081



13.44277
14.702296



14.8732
14.776435



16.25711
14.839809



17.59675
14.917078



18.89421
14.990399



20.15144
15.054305



21.37028
15.119122



22.55428
15.175226



23.69965
15.236056



24.81334
15.291126



25.89498
15.336807



26.94595
15.390322



27.96752
15.430787



28.96091
15.477335



29.92728
15.495534



30.8677
15.530907



31.78322
15.554562



32.67481
15.595807



33.54339
15.626446



34.38985
15.659309



35.21502
15.682632



36.01968
15.704625



36.80461
15.732975



37.5705
15.752819



38.31806
15.775374



39.04792
15.788448



39.76072
15.789786



40.45703
15.804674



41.13743
15.815627



41.80246
15.833471



42.45263
15.83819



43.08843
15.857033



43.71034
15.880328



44.3188
15.883979



44.91425
15.88083



45.49709
15.895206



46.06773
15.921987



46.62655
15.935088



47.17391
15.958388



47.71015
15.9749



48.23561
15.996772



48.75062
16.015236



49.25549
16.021737



49.7505
15.990765



50.23595
16.003396



50.71211
16.027484



51.17924
16.035907



51.6376
16.078185



52.08743
16.0628



52.52898
16.077378



52.96246
16.094515



53.38809
16.103289



53.80609
16.129645



54.21666
16.139903



54.62
16.135387



55.01629
16.142765



55.40572
16.158141



55.78847
16.153889



56.1647
16.179065



—
—

## Claims

1. A ternary azeotrope-like composition consisting of effective amounts of HFC-245fa, MeOH, and trans-1,2-dichloroethylene.

2. The azeotrope-like composition of claim 1 which consists of from about 50 to less than 100 weight percent of HFC-245fa, from greater than zero to about 25 weight percent of MeOH, and from greater than zero to about 30 weight percent of trans-1,2-dichloroethylene.

3. The azeotrope-like composition of claim 1 which consists of from about 65 to less than 100 weight percent of HFC-245fa, from greater than zero to about 15 weight percent of MeOH, and from greater than zero to about 20 weight percent of trans-1,2-dichloroethylene.

4. The azeotrope-like composition of claim 1 which consists of preferably from about 75 to less than 100 weight percent of HFC-245fa, from greater that zero to about 10 weight percent of MeOH, and from greater than zero to about 15 weight percent of trans-1,2-dichloroethylene.

5. The azeotrope-like composition of claim 1 having a boiling point of from about 14° C. to about 17° C. at a pressure of from about 14 to about 15 psia.

6. The azeotrope-like composition of claim 1 having a boiling point of from about 14° C. to about 16° C. at a pressure of from about 14 to about 15 psia.

7. The azeotrope-like composition of claim 1 having a boiling point of from about 14° C. to about 15° C. at a pressure of from about 14 to about 15 psia.

8. The azeotrope-like composition of claim 2 having a boiling point of from about 14° C. to about 15° C. at a pressure of from about 14 to about 15 psia.

9. A method of producing a ternary azeotrope-like composition consisting of combining effective amounts of HFC-245fa, MeOH, and trans-1,2-dichloroethylene.

10. The method of claim 9 consisting of combining from about 50 to less than 100 weight percent of HFC-245fa, from greater than zero to about 25 weight percent of MeOH, and from greater than zero to about 30 weight percent of trans-1,2-dichloroethylene to form an azeotrope-like composition.

11. A sprayable composition comprising a material to be sprayed and a solvent comprising an azeotrope-like composition of claim 1.

12. The sprayable composition according to claim 11 wherein the sprayable composition is an aerosol.

13. The sprayable composition according to claim 12 wherein the sprayable composition is selected from the group consisting of oils, release agents, cleaners, polishing agents, medicinal materials, cosmetic materials, and combinations of two or more thereof.

14. A refrigerant composition comprising an azeotrope-like composition of claim 1.

15. A refrigeration system comprising a refrigerant of claim 14.

16. A method for cooling an article which comprises condensing a refrigerant composition of claim 14 and thereafter evaporating said refrigerant composition in the vicinity of the article to be cooled.

17. A method for heating an article which comprises condensing a refrigerant composition of claim 14 in the vicinity of the article to be heated and thereafter evaporating said refrigerant composition.

18. A blowing agent comprising an azeotrope-like composition of claim 1.