United States Patent
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`3,884,828
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`[45] May 20, 1975
`Butler
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`[19]
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`[111
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`[54] PROPELLANTS AND REFRIGERANTS
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`BASED ON TRIFLUOROPROPENE
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`[75]
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`Inventor:
`A1:n(t:l.1ony J. Butler, Greensboro,
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`[73] Amgnee‘ ?E:hC°'"'"g C°"’°'at'°"’ Mmland’
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`'
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`[22] Filed:
`Oct. 15, 1970
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`_
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`[21] APPL No" 8l’l23
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`[56]
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`3,067,263
`3,583,921
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`[58] Field of Search ...................... .. 252/305, 67-69,
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`252/903 260/653.3, 65 3-4. 653-5
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`References Cited
`UNITED STATES PATENTS
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`12/1962 Newport et al. ................. 260/653.3
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`Healy et al.......................... .. 252/90
`6/I971
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`'
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`Primary Exa_mirier—Herbert B. Guynn
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`Attorney, Agent, or Firm——Jack E. Moermond
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`[52] U.S. Cl. ...................... 252/305; 106/2; 252//67;
`252 68
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`[51]
`Int. Cl........H C09!‘ 3/30; Cogk 3/06; F25 9/00
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`ABSTRACT
`[57]
`-
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`Aerosol propellants and refrigerants based on tn-
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`fluoropropene (CF3CH=CH2) are disclosed.
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`10 Claims, No Drawings
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`Page 1 of 3
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`Arkema Exhibit 1138
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`Page 1 of 3
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`Arkema Exhibit 1138
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`3,884,828 ~
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`2
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`used in combination as this depends on the individual
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`needs and the particular product being formulated.
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`Another‘ aspect of this invention is the use of tri-
`fluoropropene as a refrigerant. The most common re-
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`frigeration systems today are designed to carry out a
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`process for producing cold in which a working sub-
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`stance called the refrigerant is caused to undergo a
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`physical change. The most widely used physical change
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`is that in which the refrigerant undergoes a change
`from the liquid to the vapor state.
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`Trifluoropropene can be used as the sole refrigerant
`in a system or it can be used in combination with other
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`refrigerants..By way of illustration, trifluoropropene
`can be used in admixture with fluorodichloromethane,
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`difluorochloromethane,
`fluorotrichloromethane,
`di-
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`1 ,2,2-trifluoro- 1 ,1 ,2-
`fluorodichloromethane,
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`trichloroethane,
`1,1 ,2,2-tetrafluoro-1 ,2-
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`dichloroethane, 1,1 ,2,2,2-pentafluoro-1-chloroethane,
`1 ,1-difluoro—l-chloroethane,
`1 ,1-difluoroethane, octa-
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`chloride,
`fluorocyclobutane, methylene
`1,1,1-
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`trichloroethane, tetrafluoroethylene, vinyl chloride,
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`isobutane,
`propane, n-butane,
`ethylene, dimethyl
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`ether, nitrogen, nitrous oxide, carbon dioxide and mix-
`tures thereof. No meaningful limitations can be set as
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`to the proportions to be used as the choice of a refriger-
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`ant for a specific application is determined by the ther-
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`modynamic properties, physical properties and chemi-
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`cal properties needed for that application.
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`Now in order that those skilled in the art may better
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`understand how the present invention can be practiced,
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`the following examples are given by way of illustration
`and not by way of limitation. Trifluoropropene has a
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`boiling point of about -22°C. and a vapor pressure of
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`approximately 60 pounds per square inch gauge (psig)
`at 25°C. Trifluoropropene is flammable, and acute
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`studies indicate it to be relatively non-toxic. All per-
`cents referred to herein are by weight unless otherwise
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`specified.
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`Example 1
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`Prior to the actual preparation of any aerosol prod-
`ucts it was desirable to know the vapor pressure of the
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`propellant to be used. To obtain this information vary-
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`and
`ing percentages of
`trifluoropropene
`1,1,1-
`trichloroethane (Chlorothene) were placed in aerosol
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`cans and the vapor pressures measured at 70°F. The re-
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`sults of these measurements are set forth in the follow-
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`ing table. These results show that trifluoropropene can
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`be used in combination with other propellants for mak-
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`ing aerosol products.
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`Percent
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`Trifluoropropene ,
`1,1,1-_trich1oroethan_e
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`10
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`90
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`20
`80 ,
`30
`70
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`40
`60
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`50
`50
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`60
`40
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`70
`30
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`80
`20
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`90
`10
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`Vapor Pressure
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`(psig)
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`20
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`31
`41
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`49
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`54
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`60
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`67
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`71
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`82
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`1
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`PROPELLANTS AND REFRIGERANTS BASED ON
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`TRIFLUOROPROPENE
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`This invention relates to an aerosol product which
`includes a propellant wherein the improvement com-
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`prises employing trifluoropropene as 1 to 100 percent
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`by weight of the propellant.
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`This invention also relates to a refrigeration system '
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`in which the refrigerant undergoes a change from the
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`liquid to the vapor state wherein the improvement
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`comprises employing trifluoropropene as 1 to 100 per-
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`cent by weight of the refrigerant.
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`With the ever increasing number of aerosol products
`being marketed there is an increasing demand for new
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`propellants to solve the problems encountered indis-
`pensing the materials and to meet the needs involved
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`with specific products and uses.
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`Similarly, with improvements in existing refrigeration
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`systems, and the designing of new refrigeration sys-
`tems, there is an increasing demand for new refriger-
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`ants which will function satisfactorily.
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`Most aerosol products contain three major compo-
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`nents. These are the active ingredient, the solvent and
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`the propellant. While these components have been re-
`ferred to in the singular, it is believed obvious that each
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`“component” can consist of more than one ingredient.
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`One aspect of the present invention is directed to the
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`propellant used in aerosol products. It has been found
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`that trifluoropropene can be employed as 1 to 100 per-
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`cent by weight of the propellant. That is, trifluoropro-
`pene can be used alone as the propellant in an aerosol
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`or it can be used in combination with other propellants
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`in an aerosol. It should be noted at this point that while
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`the function of the trifluoropropene is basically and pri-
`marily that of a propellant that it may also perform an
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`incidental function as a solvent and this is within the
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`scope of the term propellant as used in this specifica-
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`tion and claims.
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`The propellant provides the pressure that forces the
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`aerosol product from the container when the valve is
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`opened. Also,
`the propellant has an influence on
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`whether the product is discharged in the form of a
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`spray, stream, or as a foam. Variations in the propellant
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`can also influence, for example, whether one obtains a
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`course or fine spray or whether one obtains a good or
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`poor foam. Thus it can be seen that the discovery that
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`trifluoropropene can be employed as a propellant gives
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`the aerosol manufacturer greater latitude in preparing
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`products than heretofore available to him.
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`As noted above, trifluoropropene can be used as the
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`sole propellant or in combination with other known
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`propellants. Examples of suitable propellants which
`can be employed in combination with trifluoropropene
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`include
`fluorodichlorom ethane ,
`difluorochlorome-
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`thane,
`fluorotrichloromethane, difluorodichlorome-
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`thane, 1,2,2-trifluoro-1,1,2-trichloroethane,
`1,1,2,2-
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`tetrafluoro-1 ,2-dichloroethane,
`1 ,1 ,2,2,2-pentafluoro-
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`1-chloroethane,
`1 ,1-difluoro-1-chloroethane,
`1 ,1-
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`difluoroethane,
`octafluorocyclobutane, methylene
`chloride
`1 , l , l-trichloroethane,
`tetrafluoroethylene,
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`vinyl chloride, propane, n-butane, isobutane, ethylene,
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`dimethyl ether, nitrogen, nitrous oxide, carbon dioxide
`and mixtures thereof. It will be noted from the exam-
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`ples given that the trifluoropropene can be employed
`in combination not only with other liquified gas propel-
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`lants but also in combination with compressed gas pro-
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`pellants. No meaningful limitations can be set as to the
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`relative proportions of the individual propellants to be
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`10
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`15
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`20
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`25
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`30
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`35
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`40
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`45
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`50
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`55
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`60
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`65
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`Example 2
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`Six units of three different aerosol products were
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`packaged using trifluoropropene as the propellant.
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`Page 2 of 3
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`Page 2 of 3
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`3,884,828
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`4 -
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`Continued
`1% trifluoropropene
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`99% fluorotrichloromethane
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`(F)
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`That which is claimed is:
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`1. In an aerosol product which consists essentially of
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`an active ingredient, a solvent and a propellant in a
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`container, the improvement comprising employing tri-
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`fluoropropene as 1 to 100 percent by weight of the pro-
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`pellant, the balance of the propellant being selected
`from the group consisting of fluorodichloromethane,
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`difluorochloromethane,
`fluorotrichloromethane,
`di-
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`1 ,2,2-trifluoro-1,1 ,2-
`fluorodichloromethane ,
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`trichloroethane,
`1 ,1 ,2,2-tetrafluoro-1 ,2-
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`dichloroethane, 1,1,2,2,2-pentafluoro-1-chloroethane,
`l , 1 -difluoro- l -chloroethane,
`1 ,1-difluoroethane, octa-
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`chloride,
`fluorocyclobutane, methylene
`1 ,1 ,1-
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`trichloroethane,
`tetrafluoroethylene, vinyl chloride,
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`isobutane,
`propane, n-butane,
`ethylene, dimethyl
`ether, nitrogen, nitrous oxide, carbon dioxide and mix-
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`tures thereof.
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`2. An aerosol product as defined in claim 1 wherein
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`trifluoropropene constitutes 100 percent of the propel-
`lant.
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`3. An aerosol product as defined in claim 1 wherein
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`the trifluoropropene constitutes less than 100 percent
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`of the propellant.
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`4. An aerosol product as defined in claim 3 wherein
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`the trifluoropropene constitutes less than 100 percent
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`of the propellant, and the balance of the propellant is
`1,1,1-trichloroethane.
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`5. An aerosol product as defined in claim 3 wherein
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`the trifluoropropene constitutes less than 100 percent
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`of the propellant, and the balance of the propellant is
`fluorotrichloromethane.
`‘
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`6. An aerosol product as defined in claim 3 wherein
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`the trifluoropropene constitutes less than 100 percent
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`of the propellant, and the balance of the propellant is
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`1 ,1 ,2,2-tetrafluoro-1 ,2-dichloroethane.
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`7. An aerosol product as defined in claim 3 wherein
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`the trifluoropropene constitutes less than 100 percent
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`of the propellant, and the balance of the propellant is
`1 ,2,2-trifluoro- 1 , 1 ,2-trichloroethane.
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`8. In a process of expelling an aerosol product which
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`consists essentially of an active ingredient, a solvent
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`and a propellant from a container by means of the pro-
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`pellant the improvement comprising employing as the
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`propellant a composition consisting essentially of from
`1 to 100 percent by weight of trifluoropropene, the bal-
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`ance of the propellant being selected from the group
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`consisting
`fluorodichloromethane,
`difluoro-
`of
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`chloromethane,
`fluorotrichloromethane , difluorodi-
`
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`1,2,2-trifluoro-1,1,2—trich1oroethane,
`chloromethane,
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`1,1,2,2-tetrafluoro-1,2-dichloroethane,
`1,1,2,2,2—
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`1 , 1 -difluoro- 1 -
`pentafluoro-1-chloroethane,
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`chloroethane, 1,1-difluoroethane, octafluorocyclobu-
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`tane, methylene chloride, 1,1,1-trichloroethane, tetra-
`
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`
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`fluoroethylene, vinyl chloride, propane, n-butane, iso-
`
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`butane, ethylene,‘dimethyl ether, nitrogen, nitrous ox-
`ide, carbon dioxide and mixtures thereof.
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`9. A process as defined in claim 8 wherein the tri-
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`fluoropropene constitutes 100 percent of the propel-
`lant.
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`10. A process as defined in claim 8 wherein the tri-
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`
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`
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`fluoropropene constitutes less than 100 percent of the
`
`propellant.
`>16
`*
`*
`=l<
`*
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`10
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`15
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`20
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`25
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`30
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`35
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`40
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`45
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`50
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`55
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`60
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`65
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`3
`Two control units were prepared for purpose of com-
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`parison with each set and were identical in every re-
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`spect except that difluorodichloromethane was used as
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`the propellant. The aerosol products were a release
`agent for cooking utensils (Pan Shield), a water repel-
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`lent agent for leather goods (Shoe Saver), and a textile
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`treating agent‘(Fabriglide). Three units and one con-
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`trol of each set were stored ‘at room temperature and
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`three units and one control were stored at l00°F. The
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`first examples (one from room temperature and one
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`from 100°F.) were opened and examined after two
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`weeks, the second samples were checked a month later,
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`and the final samples with controls a month after that.
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`After 2‘/2 months of shelf-life all products were stable
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`with no deviations from the control units. There was no
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`change in the product color nor any attack on the aero-
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`sol container. Pressures remained relatively constant,
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`and weight losses were negligible. It was noted that the
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`trifluoropropene had a light characteristic odor which
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`could be masked with perfume if found objectionable.
`Although the vapor pressure of trifluoropropene is
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`lower than that of difluorodichloromethane, in combi-
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`nation with such materials as 1,1,1-trichloroethane,
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`currently available data indicates that it gives a slightly
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`higher pressure
`than that of
`similar difluorodi-
`chloromethane combinations. Therefore, that data in-
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`dicates that it is possible to use less trifluoropropene
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`than difluorodichloromethane in an aerosol product to
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`attain the desired pressure.
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`"Example 3
`When the following propellants are substituted for
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`trifluoropropene in the aerosol products of Example 2,
`similar results are obtained:
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`1%
`99%
`50%
`50%
`50%
`50%
`65%
`35%
`80%
`20%
`65%
`35%
`75%
`10%
`15%
`45%
`45%
`10%
`91%
`9%
`
`
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`trifluoropropene
`
`difluorodichloromethane
`
`trifluoropropene
`
`1 ,1 ,1—trich1oroethane
`
`
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`trifluoropropene
`
`fluorotrichloromethane
`
`trifluoropropene
`
`1,1 ,2,2-tetrafluoro-1 ,2-dichloroethane
`
`
`trifluoropropene
`
`1,2,2-trifluoro-1 ,1 ,2-trichloroethane
`
`
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`trifluoropropene
`'
`
`vinyl chloride
`
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`trifluoropropene
`
`fluorotrichloromethane
`dimethyl ether
`
`
`trifluoropropene
`
`fluorotrichloromethane
`
`isobutane
`
`trifluoropropene
`
`propane
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`’ (A) 5
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`(B)
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`(C)
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`(D)
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`(E)
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`(F)
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`(G)
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`(H)
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`(1)
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`Example 4
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`When the following refrigerants are used in a refrig-
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`eration system in which the refrigerant undergoes a
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`change from the liquid to the vapor state, such as the
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`refrigeration systems found in refrigerators and freez-
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`ers, good cooling is obtained:
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`100%
`90%
`10%
`80%
`20%
`50%
`50%
`45%
`45%
`10%
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`(A)
`(B)
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`(C)
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`(D)
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`(E)
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`Page 3 of 3
`
`trifluoropropene
`trifluoropropene
`difluorodichloromethane
`
`trifluoropropene
`
`1,2,2-trifluoro- I ,1 ,2-trichloroethane
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`
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`trifluoropropene
`
`fluorotrichloromethane
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`trifluoropropene
`
`fluorotrichloromethane
`isobutane
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`Page 3 of 3