USOO747.6331 B2

(12) United States Patent (10) Patent No.: US 7476,331 B2 Merchant et al. (45) Date of Patent: Jan. 13, 2009

(54) COMPOSITIONS COMPRISING (58) Field of Classification Search ...... 252/67, 1,1,1,2,2,3,4,5,5,6,6,7,7,7-TETRADE 252/68; 510/177 CAFLUOROHEPTANE AND USES THEREOF See application file for complete search history. (75) Inventors: Abid N. Merchant, Wilmington, DE (56)56 Refeeees Citede (US); Barbara Haviland Minor, Elkton, U.S. PATENT DOCUMENTS MD (US); Shoeb A. Moiyadi, San Jose, 5,065,990 A 1 1/1991 Durfee CA (US); Melodie A. Schweitzer, 5,171,902 A 12/1992 Krespan et al. Wilmington, DE (US); Allen Capron 5,219,651 A 6/1993 Shoji et al. Sievert, Elkton, MD (US) 5,723,701 A 3/1998 Krespan RE36,951 E 1 1/2000 Cooper et al. (73) Assignee: E I Du Pont Nemours and Company, 6,506,950 B1 1/2003 Krespan Wilmington, DE (US) 2003/0134757 A1 7/2003 Milbraith et al. (*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS patent is extended or adjusted under 35 WO WO99.63O43 * 12/1999 U.S.C. 154(b) by 461 days. WO WO 2004/OOO977 A1 12/2003 WO WO 2005/OO8819 A2 1, 2005 (21) Appl. No.: 11/347,391 WO WO 2006/086683 A3 * 8, 2006 * cited by examiner (22) Filed: Feb. 3, 2006 Primary Examiner John R Hardee (65) Prior Publication Data (74) Attorney, Agent, or Firm—Hanxing Zheng US 2006/O180785 A1 Aug. 17, 2006 (57) ABSTRACT Related U.S. Application Data The present invention relates to compositions comprising (60) Provisional application No. 60/651,720, filed on Feb. HFC-63-14mcee. The compositions may be azeotropic O 9, 2005, provisional application No. 60/651,687, filed azeotrope-like and are useful in cleaning applications, as a on Feb. 9, 2005, provisional application No. 60/651, defluxing agent, for removing oils or residues from a surface, 575, filed on Feb. 9, 2005. depositing or removing lubricants from a Surface, and as refrigerants or heat transfer fluids in refrigeration systems, (51) Int. Cl. air-conditioners and heat pumps. C09K 5/04 (2006.01) (52) U.S. Cl...... 252/68; 252/67; 510/177 18 Claims, No Drawings US 7,476,331 B2 1. 2 COMPOSITIONS COMPRISING BRIEF SUMMARY OF THE INVENTION 1,1,1,2,2,3,4,5,5,6,6,7,7,7-TETRADECA FLUOROHEPTANE AND USES THEREOF The present invention relates to a method for depositing fluorolubricant on a Surface, said method comprising: CROSS REFERENCE(S) TO RELATED a) combining fluorolubricant with solvent, that solvent APPLICATION(S) being HFC-63-14mcee, to form a lubricant-solvent combina tion; and This application claims the priority benefit of U.S. Provi b) contacting said lubricant-solvent combination with said sional Application 60/651,720, filed Feb. 9, 2005, U.S. Pro Surface; visional Application 60/651,687, filed Feb. 9, 2005, and U.S. 10 c) evaporating said HFC-63-14mcee from said surface, to Provisional Application 60/651,575, filed Feb. 9, 2005. form a fluorolubricant coating. The present invention further relates to a method for solu BACKGROUND OF THE INVENTION bilizing a fluorolubricant, said method comprising contacting HFC-63-14mcee with a fluorolubricant. 1. Field of the Invention 15 The present invention further relates to a method for The present invention relates to compositions comprising removing contaminants from a surface comprising: 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane (HFC-63 a) contacting the Surface with solvent, that solvent com 14mcee). These compositions include binary and ternary prising HFC-63-14mcee; and azeotropic or azeotrope-like compositions. These composi b) recovering the surface from the solvent. tions are useful in cleaning applications, as a defluxing agent, The present invention further relates to azeotropic or azeo for removing oils or residues from a Surface, depositing or trope-like cleaning compositions comprising: removing lubricants on or from a Surface, and as refrigerants a) HFC-63-14mcee: or heat transfer fluids in refrigeration systems, air-condition b) trans-1,2-dichloroethylene; and ers and heat pumps. c) at least one alcohol selected from the group consisting of 2. Description of Related Art 25 methanol, ethanol, and isopropanol. As electronic circuitboards evolve toward increased circuit The present invention further relates to an azeotropic or and component densities, thorough board cleaning becomes a azeotrope-like composition selected from the group consist more critical process step. After soldering, the flux-residues ing of are often removed with an organic solvent. Defluxing Sol about 38 to about 83 weight percent HFC-63-14mcee and vents should have low toxicity and have high solvency power, 30 about 62 to about 17 weight percent cyclohexane: so that the flux and flux-residues can be removed without about 39 to about 82 weight percent HFC-63-14mcee and damaging the Substrate being cleaned. Further, other types of about 61 to about 18 weight percent 2,2,3-trimethylbutane: residue. Such as oils and greases, must be effectively removed about 39 to about 82 weight percent HFC-63-14mcee and from these devices for optimal performance in use. about 61 to about 18 weight percent 2,4-dimethylpentane: Additionally, fluorolubricants are widely used in the mag 35 about 42 to about 84 weight percent HFC-63-14mcee and netic disk drive industry to decrease the friction between a about 58 to about 16 weight percent 3,3-dimethylpentane: read-write head and a digital disk to reduce wear and mini about 45 to about 86 weight percent HFC-63-14mcee and mize disk failure. Deposition of these fluorolubricants on the about 55 to about 14 weight percent 2,3-dimethylpentane: disk Surface requires a solvent capable of dissolving the fluo about 45 to about 86 weight percent HFC-63-14mcee and rolubricant and forming a Substantially uniform coating of 40 about 55 to about 14 weight percent 2-methylhexane: fluorolubricant when evaporated. about 46 to about 86 weight percent HFC-63-14mcee and Alternative, non-oZone depleting solvents have become about 54 to about 14 weight percent 3-methylhexane: available since the elimination of nearly all previous chlorof about 51 to about 89 weight percent HFC-63-14mcee and about 49 to about 11 weight percent n-heptane: luorocarbons (CFCs) and hydrochlorofluorocarbons 45 (HCFCs) as a result of the Montreal Protocol. While boiling about 48 to about 89 weight percent HFC-63-14mcee and point, flammability and solvent power characteristics can about 52 to about 11 weight percent methylcyclohexane: often be adjusted by preparing solvent mixtures, these mix about 59 to about 99 weight percent HFC-63-14mcee and tures are often unsatisfactory in the commonly used cleaning about 41 to about 1 weight percent toluene: equipment because they fractionate to an undesirable degree 50 about 49 to about 88 weight percent HFC-63-14mcee and during use. Such solvent mixtures also fractionate during about 51 to about 12 weight percent isooctane: solvent distillation, which makes it virtually impossible to about 62 to about 99 weight percent HFC-63-14mcee and recover a solvent mixture with the original composition. about 38 to about 11 weight percent n-octane; AZeotropic Solvent mixtures may possess the properties about 1 to about 68 weight percent HFC-63-14mcee and needed for these cleaning (defluxing or degreasing) applica 55 about 99 to about 32 weight percent 2-bromopropane: tions and other cleaning agent needs. AZeotropic mixtures about 19 to about 74 weight percent HFC-63-14mcee and exhibit either a maximum or a minimum boiling point and about 81 to about 26 weight percent 1-bromopropane: they do not fractionate on boiling. The constant composition about 36 to about 82 weight percent HFC-63-14mcee and in use assures that the composition will not change during use about 64 to about 18 weight percent 1,2-dichloroethane; and that solvency properties will remain constant as well. 60 about 1 to about 62 weight percent HFC-63-14mcee and The present invention provides azeotropic and azeotrope about 99 to about 38 weight percent 1,1-dichloroethane; like compositions useful in cleaning semiconductor chips and about 39 to about 85 weight percent HFC-63-14mcee and circuit boards and processes for removing oil and grease about 61 to about 15 weight percent fluorobenzene: residues from Surfaces. about 36 to about 99 weight percent HFC-63-14mcee and The present azeotropic or azeotrope-like compositions are 65 about 64 to about 1 weight percent methylene bromide: also useful as refrigerants or heat transfer fluids in refrigera about 35 to about 80 weight percent HFC-63-14mcee and tion, air conditioning and heat pump systems. about 65 to about 20 weight percent trichloroethylene; US 7,476,331 B2 3 4 about 53 to about 99 weight percent HFC-63-14mcee and about 56 to about 93 weight percent HFC-63-14mcee and about 47 to about 1 weight percent tetrachloroethylene: about 44 to about 7 weight percent methyl n-butyrate; about 70 to about 99 weight percent HFC-63-14mcee and about 59 to about 99 weight percent HFC-63-14mcee and about 30 to about 1 weight percent chlorobenzene: about 41 to about 1 weight percent butyl formate; about 1 to about 72 weight percent HFC-63-14mcee and about 68 to about 99 weight percent HFC-63-14mcee and about 99 to about 28 weight percent cis-1,2-dichloroethylene: about 32 to about 1 weight percent diethyl carbonate; about 1 to about 68 weight percent HFC-63-14mcee and about 1 to about 99 weight percent HFC-63-14mcee and about 99 to about 32 weight percent trans-1,2-dichloroethyl about 99 to about 1 weight percent 2-butanone; ene, about 1 to about 99 weight percent HFC-63-14mcee and about I to about 93 weight percent HFC-63-14mcee and 10 about 99 to about 1 weight percent 3-methyl-2-butanone; about 99 to about 7 weight percent methanol: about 1 to about 99 weight percent HFC-63-14mcee and about 58 to about 92 weight percent HFC-63-14mcee and about 99 to about 1 weight percent 2-bromo-1,1,1,4,4,5,5.5- about 42 to about 8 weight percent ethanol: octafluoro-2-(trifluoromethyl)-3 pentanone; about 69 to about 94 weight percent HFC-63-14mcee and about 1 to about 99 weight percent HFC-63-14mcee and about 31 to about 6 weight percent n-propanol; 15 about 99 to about 1 weight percent 1,1,1,2,2,3,4,5,5,5-decaf about 58 to about 91 weight percent HFC-63-14mcee and luoro-3-methoxy-4-(trifluoromethyl)-pentane; about 42 to about 9 weight percent isopropanol; about 47 to about 99 weight percent HFC-63-14mcee and about 52 to about 88 weight percent HFC-63-14mcee and about 53 to about 1 weight percent nitromethane; about 48 to about 12 weight percent 2-methyl-2-propanol: about 45 to about 85 weight percent HFC-63-14mcee and about 63 to about 92 weight percent HFC-63-14mcee and about 55 to about 15 weight percent 1,2-dimethoxyethane; about 37 to about 8 weight percent 2-methyl-2-butanol: about 50 to about 87 weight percent HFC-63-14mcee and about 64 to about 93 weight percent HFC-63-14mcee and about 50 to about 13 weight percent 2,2-dimethyl-1,3-diox about 36 to about 7 weight percent 2-butanol: olane; about 70 to about 95 weight percent HFC-63-14mcee and about 1 weight percent to about 68 weight percent HFC about 30 to about 5 weight percent isobutanol: 25 63-14mcee, about 1 weight percent to about 98 weight per about 75 to about 99 weight percent HFC-63-14mcee and cent CFOCH, and about 1 weight percent to about 98 about 25 to about 1 weight percent n-butanol: weight percent trans-1,2-dichloroethylene; about 77 to about 97 weight percent HFC-63-14mcee and about 1 weight percent to about 68 weight percent HFC about 23 to about 3 weight percent 2-methoxyethanol: 63-14mcee, about 1 weight percent to about 71 weight per about 1 to about 84 weight percent HFC-63-14mcee and 30 cent CFOCHs, and about 28 weight percent to about 98 about 99 to about 16 weight percent 2.2.2-trifluoroethanol: weight percent trans-1,2-dichloroethylene; and about 1 to about 82 weight percent HFC-63-14mcee and about 1 weight percent to about 68 weight percent HFC about 99 to about 18 weight percent 2.2.3,3,3-pentafluoro-1- 63-14mcee, about 1 weight percent to about 71 weight per propanol: cent CFOCHs about 28 weight percent to about 98 weight about 59 to about 99 weight percent HFC-63-14mcee and 35 percent trans-1,2-dichloroethylene, and about 1 weight per about 41 to about 1 weight percent 2.2.3,3-tetrafluoro-1- cent to about 30 weight percent methanol. propanol: about 1 to about 64 weight percent HFC-63-14mcee and DETAILED DESCRIPTION OF THE INVENTION about 99 to about 36 weight percent 1,1,1,3,3,3-hexafluoro 2-propanol: 40 Applicants specifically incorporate the entire contents of about 46 to about 91 weight percent HFC-63-14mcee and all cited references in this disclosure. Further, when an about 54 to about 9 weight percent acetonitrile; amount, concentration, or other value or parameter is given as about 61 to about 96 weight percent HFC-63-14mcee and either a range, preferred range, or a list of upper preferable about 39 to about 4 weight percent propionitrile; values and lower preferable values, this is to be understood as 45 specifically disclosing all ranges formed from any pair of any about 71 to about 99 weight percent HFC-63-14mcee and upper range limit or preferred value and any lower range limit about 29 to about 1 weight percent butyronitrile; or preferred value, regardless of whether ranges are sepa about 64 to about 99 weight percent HFC-63-14mcee and rately disclosed. Where a range of numerical values is recited about 36 to about 1 weight percent n-methylmorpholine: herein, unless otherwise Stated, the range is intended to about 74 to about 99 weight percent HFC-63-14mcee and 50 include the endpoints thereof, and all integers and fractions about 26 to about 1 weight percent morpholine; within the range. It is not intended that the scope of the about 34 to about 83 weight percent HFC-63-14mcee and invention be limited to the specific values recited when defin about 66 to about 17 weight percent ethyl acetate; ing a range. about 35 to about 83 weight percent HFC-63-14mcee and The fluorolubricants of the present invention comprise per about 65 to about 17 weight percent methyl propionate; 55 fluoropolyether (PFPE) compounds, or lubricant comprising about 38 to about 84 weight percent HFC-63-14mcee and X-1 PR), which is a phosphazene-containing disk lubricant. about 62 to about 16 weight percent n-propyl formate: These perfluoropolyether compounds are sometimes referred about 46 to about 89 weight percent HFC-63-14mcee and to as perfluoroalkylethers (PFAE) or perfluoropolyalky about 54 to about 11 weight percent dimethyl carbonate; lethers (PFPAE). These PFPE compounds range from simple about 44 to about 86 weight percent HFC-63-14mcee and 60 perfluorinated ether polymers to functionalized perfluori about 56 to about 14 weight percent isopropyl acetate; nated ether polymers. PFPE compounds of different varieties about 53 to about 91 weight percent HFC-63-14mcee and that may be useful as fluorolubricant in the present invention about 47 to about 9 weight percent isobutyl formate; are available from several sources. Useful fluorolubricants for about 53 to about 91 weight percent HFC-63-14mcee and the present inventive method include but are not limited to about 47 to about 9 weight percent ethyl propionate; 65 Krytox R GLP 100, GLP 105 or GLP 160 (E. I. du Pont de about 55 to about 92 weight percent HFC-63-14mcee and Nemours & Co., Fluoroproducts, Wilmington, Del., 19898, about 45 to about 8 weight percent n-propyl acetate; USA); Fomblin R. Z-Dol 2000, 2500 or 4000, Z-Tetraol, or US 7,476,331 B2 5 6 Fomblin R AM 2001 or AM 3001 (sold by Solvay Solexis The step of contacting said combination of fluorolubricant S.p.A., Milan, Italy); DemnumTMLR-200 or S-65 (offered by and solvent with the Surface may be accomplished in any Daikin America, Inc., Osaka, Japan): X-1 PR) (a partially flu manner appropriate for said surface (considering the size and orinated hexaphenoxy cyclotriphosphaZene disk lubricant shape of the surface). A hard drive disk must be supported in available from Quixtor Technologies Corporation, a subsid Some manner Such as with a mandrel or some other Support iary of Dow Chemical Co, Midland, Mich.); and mixtures that may fit through the hole in the center of the disk. The disk thereof. The KrytoxR lubricants are perfluoroalkylpolyethers will thus be held vertically such that the plane of the disk is having the general structure F(CF(CF)CFO), CFCF, perpendicular to the solvent bath. The mandrel may have wherein in ranges from 10 to 60. The Fomblin R. lubricants are different shapes including but not limited to, a cylindrical bar, functionalized perfluoropolyethers that range in molecular 10 or a V-shaped bar. The mandrel shape will determine the area weight from 500 to 4000 atomic mass units and have general of contact with the disk. The mandrel may be constructed of formula X CF. O(CF, CF. O) (CFO), CF any material strong enough to hold the disk, including but not X, wherein X may be —CH2OH, CH(O—CH2—CH),OH, limited to metal, metal alloy, plastic or glass. Additionally, a CHOCHCH(OH)CH-OH or -CHO CH-piperonyl. disk may be Supported vertically upright in a woven basket or The Deminum TM oils are perfluoropolyether-based oils rang 15 be clamped into a vertical position with 1 or more clamps on ing in molecular weight from 2700 to 8400 atomic mass units. the outer edge. The Support may be constructed of any mate The fluorolubricants of the present invention may addition rial with the strength to hold the disk, such as metal, metal ally comprise additives to improve the properties of the fluo alloy, plastic or glass. However the disk is Supported, the disk rolubricant. X-1 PR), which may serve as the lubricant itself, is will be lowered into a container holding a bath of the fluo often added to other lower cost fluorolubricants in order to rolubricant/solvent combination. The bath may be held at increase the durability of disk drives by passivating Lewis room temperature or be heated or cooled to temperatures acid sites on the disk surface responsible for PFPE degrada ranging from about 0°C. to about 50° C. tion. Alternatively, the disk may be supported as described Other common lubricant additives may be used in the fluo above and the bath may be raised to immerse the disk. In rolubricants of the present inventive methods. 25 either case, the disk may then be removed from the bath The fluorolubricants of the present invention may further (either by lowering the bath or by raising the disk). Excess comprise Z-DPA (Hitachi Global Storage Technologies, San fluorolubricant/solvent combination can be drained into the Jose, Calif.), a PFPE terminated with dialkylamine end bath. groups. The nucleophilic end-groups serve the same purpose Either of the methods for contacting the fluorolubricant/ as X1 PR), thus providing the same stability without any addi 30 solvent combination with the disk surface of either lowering the disk into a bath or raising a bath to immerse the disk are tive. commonly referred to as dip coating. Other means for con The surface on which the fluorolubricant may be deposited tacting the disk with the fluorolubricant/solvent combination is any solid surface that may benefit from lubrication. Semi may be used in the present inventive method, including spray conductor materials such as silica disks, metal or metal oxide 35 ing or spin coating. Surfaces, vapor deposited carbon Surfaces or glass Surfaces When the disk is removed from the bath, the disk will have are representative of the types of surfaces for which the meth a coating of fluorolubricant and some residual solvent (HFC ods of the present invention are useful. The present inventive 63-14mcee) on its surface. The residual solvent may be method is particularly useful in coating magnetic media Such evaporated. Evaporation is usually performed at room tem as computer drive hard disks. In the manufacture of computer disks, the Surface may be a glass, or aluminum Substrate with 40 perature. However, other temperatures both above and below layers of magnetic media that is also coated by vapor depo room temperature may be used as well for the evaporation sition with a thin (10-50 Angstrom) layer of amorphous step. Temperatures ranging from about 0°C. to about 100° C. hydrogenated or nitrogenated carbon. The fluorolubricant may be used for evaporation. As the boiling point for HFC may be deposited on the Surface disk indirectly by applying 63-14mcee, which is about 96°C., is higher than for the most 45 commonly used solvents today, higher evaporation tempera the fluorolubricant to the carbon layer of the disk. tures may be needed to prevent impractically long evapora 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane, also tion time. known as HFC-63-14mcee, serves as solvent for the present The surface, or the disk if the surface is a disk, after inventive method and has CAS registry number 142347-09 completion of the coating method, will be left with a substan 9. It may be prepared by methods described in U.S. Pat. Nos. 50 tially uniform or uniform coating of fluorolubricant that is 5,171,902, 5,723,701 and 6,506,950, herein incorporated by substantially free of solvent. The fluorolubricant may be reference. HFC-63-14mcee can exist as several different ste applied to a thickness of less than about 300 nm, and alter reoisomers. HFC-63-14mcee as used herein is meant to nately to a thickness of about 100 to about 300 nm. include all stereoisomers or mixtures thereof. HFC-63-14 is believed to be an improvement over the The present invention relates to a method for depositing 55 presently used solvents for deposition offluorolubricant. Sev fluorolubricant on a Surface, said method comprising com eral solvents have been commonly used in the hard drive disk bining fluorolubricant with a solvent, that solvent being 1.1, industry. These include PF-5060 (available from 3MTM Elec 1.2.2.3.4.5,5,6,6,7,7,7-tetradecafluoroheptane, contacting tronics Markets Materials Division, St. Paul, Minn., 55144, said combination of fluorolubricant and solvent with the Sur USA), NovecTM HFE-7100 (also available from 3MTM), and face and evaporating the solvent to form a fluorolubricant 60 Vertrel RXF (available from E. I. duPont de Nemours & Co., coating on the Surface. Fluoroproducts, Wilmington, Del., 19898, USA). Vertrel(R) The first step of combining the fluorolubricant and solvent XF has been demonstrated to produce the most uniform fluo may be accomplished in any Suitable manner, Such as mixing rolubricant coatings due to its greater Solvation of the fluo in a Suitable container, Such as a beaker or other container that rolubricant molecules. Not to be bound by theory, it is may be used as a bath for the deposition method. The fluo 65 believed that the ability of a solvent to disrupt the intermo rolubricant concentration in the solvent may be from about lecular hydrogen bonds of the fluorolubricant is related to the 0.010 percent (wit/wt) to about 0.50 percent (wit/wt). Solvents ability to produce a uniform coating. US 7,476,331 B2 7 8 A uniform fluorolubricant coating is desired for proper required. Details on how these parameters effect coatings are functioning of a disk and thus areas of varying fluorolubricant given in, “Dip-Coating of Ultra-Thin Liquid Lubricant and its thickness are undesirable on the surface of the disk. As more Control for Thin-Film Magnetic Hard Disks’ in IEEE Trans and more information is being Stored on the same size disk, actions on Magnetics, vol. 31, no. 6, November 1995. the read/write head must get closer and closer to the disk in The present invention further relates to a method for clean order to function properly. If irregularities due to variation in ing Surfaces by removing contaminants from the Surface. The coating thickness are present on the Surface of the disk, the method for removing contaminants from a Surface comprises probability of contact of the head with these areas on the disk contacting the Surface having contaminants with solvent, that is much greater. While there is a desire to have enough fluo solvent comprising HFC-63-14mcee, to solubilize the con rolubricant on the disk to flow into areas where it may be 10 taminants, and recovering the Surface from the solvent. The removed by head contact or other means, coating that is too Surface is then Substantially free of contaminants. thick may cause “smear, a problem associated with the read/ In the present inventive method, the contacting may be write head picking up excess fluorolubricant. accomplished by spraying, flushing, wiping with a substrate One specific coating thickness irregularity observed in the e.g., wiping cloth or paper, that has solvent incorporated in or industry is that known as the “rabbit ears' effect. These 15 on it, or by dipping or immersing the disk in a bath of solvent. irregularities are visually detected on the surface of the disk In the present inventive method, the recovering may be by after deposition of the fluorolubricant using the existing Sol removing the surface that has been contacted from the solvent vent systems. When the disk is contacted with the solution of bath (in a similar manner as described for the method for fluorolubricant in solvent and then removed from the solu depositing a fluorolubricant on the Surface or by allowing the tion, any points where the solution may accumulate and not solvent that has been sprayed, flushed or wiped on the disk to drain readily develop drops of solution. One such point of drain away). Additionally, any residual solvent that may be drop formation is the contact point (or points) with the man left behind after the completion of the previous steps may be drel or other support device with the disk. When a V-shaped evaporated in a manner similar to that for the deposition mandrel is used, there are two contact points at which the method as well. mandrel contacts the inside edge of the disk. When solution of 25 The method for cleaning a surface may be applied to the fluorolubricant forms drops in these locations an area of same types of Surfaces as the method for deposition as greater thickness of fluorolubricant is created when the sol described previously. Semiconductor Surfaces or magnetic vent evaporates. The two points of contact with the disk media disks of silica, glass, metal or metal oxide, or carbon produces what is known as a “rabbit ears' effect, because the may have fluorolubricant removed by the method. In the areas of greater fluorolubricant thickness produce a pattern 30 method described above, contaminant may be removed from resembling rabbit ears visually detectable on the disk surface. a disk by contacting the disk with the solvent and recovering Vertrel R. XF specialty fluid, comprising 1,1,1,2,3,4,4,5.5, the disk form the solvent. 5-decafluoropentane is used widely for producing overall Contaminants of the present invention refer to compounds uniform fluorolubricant coatings. that have been found to deposit on the carbon surface of a disk HFC-63-14mcee has the same advantages as Vertrel(R) XF 35 in the environment within which the carbon is deposited. in producing uniform fluorolubricant coatings, but is advan Hydrocarbon based oils and greases and dioctylphthalate tageous because it requires a lower concentration of fluorolu (DOP) are examples of the contaminants that may be found bricant in the deposition fluorolubricant-solvent combination on the carbon-coated disks. to produce the same fluorolubricant coating thickness. There Additionally, the present invention relates to a method for fore, HFC-63-14mcee is believed to reduce the problem of 40 solubilizing a fluorolubricant, said method comprising con irregular fluorolubricant coating thickness. Not to be bound tacting HFC-63-14mcee with a fluorolubricant. HFC-63 by theory, it is believed that the higher fluorine to hydrogen 14mcee may be demonstrated to have similar solvency to that ratio on HFC-63-14mcee as compared to Vertrel R. XF, will of Vertrel(R) XF for fluorolubricants. yield a lower affinity of the solvent for the carbon surface. If The present invention further relates to compositions com the solvent is not attracted to the surface, the fluorolubricant 45 prising 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane may more readily interact with the Surface and become (HFC-63-14mcee), trans-1,2-dichloroethylene (trans-DCE) bonded there. and at least one alcohol selected from the group consisting of Lower concentrations of fluorolubricant in the lubricant methanol (MeOH), ethanol (EtOH) and isopropanol (IPA). solvent combination means that the solution of lubricant Trans-1,2-dichloroethylene, also known as trans-DCE, Solvent that remains on the edges of the disk will contain less 50 methanol, ethanol, and isopropanol are all available from fluorolubricant. It is expect that the remaining Solution in commercially sources. these areas will not have as great a negative effect on the The azeotropic or azeotrope-like compositions of the coating thickness in those surface edges once the solvent has present invention comprise: evaporated. from about 1 weight percent to about 40 weight percent HFC-63-14mcee has other advantages over existing sol 55 HFC-63-14mcee, from about 55 weight percent to about 94 vents used for deposition of fluorolubricant. The higher boil weight percent trans-DCE, and from about 1 weight percent ing point, about 96° C., will reduce evaporative loss of the to about 30 weight percent methanol; preferably, the compo solvent during use. Additionally, the high affinity for the sitions comprise from about 10 weight percent to about 30 fluorolubricant due to high fluorine to hydrogen ratio will weight percent HFC-63-14mcee, from about 60 weight per provide improved solubility of fluorolubricants thus allowing 60 cent to about 80 weight percent trans-DCE, and from about 3 use as a solvent for removing fluorolubricant from a surface. weight percent to about 15 weight percent methanol: When dip coating is used for depositing fluorolubricant on from about 1 weight percent to about 40 weight percent the Surface, the pulling-up speed (speed at which the disk is HFC-63-14mcee, from about 55 weight percent to about 94 removed from the bath), and the density of the fluorolubricant weight percent trans-DCE, and from about 1 weight percent and the Surface tension are relevant for determining the result 65 to about 30 weight percent ethanol; preferably, the composi ing film thickness of the fluorolubricant. Awareness of these tions comprise from about 10 weight percent to about 30 parameters for obtaining the desired film thickness is weight percent HFC-63-14mcee, from about 60 weight per US 7,476,331 B2 10 cent to about 80 weight percent trans-DCE, and from about 3 be changed from that of the original. Therefore, the use of weight percent to about 15 weight percent ethanol; and azeotropic or azeotrope-like compositions in these types of from about 1 weight percent to about 40 weight percent apparatus is highly recommended and makes possible recov HFC-63-14mcee, from about 55 weight percent to about 94 ery and recycle of the compositions used therein. weight percent trans-DCE, and from about 1 weight percent to about 30 weight percent isopropanol; preferably, the com The azeotropic compositions of the present invention are positions comprise from about 10 weight percent to about 30 listed in Table 1. weight percent HFC-63-14mcee, from about 60 weight per cent to about 80 weight percent trans-DCE, and from about 3 TABLE 1 weight percent to about 15 weight percent isopropanol. 10 Azeotrope Point Temp The compositions of the present invention may be prepared Components (wt %) (° C.) by any convenient method to combine the desired amounts of HFC-63-14mcee?trans-DCE MeOH 18.7f73.2,8.1 40 the individual components. A preferred method is to weigh HFC-63-14mcee?trans-DCEEtOH 21.8, 73.8/44 45 the desired component amounts and thereafter combine the HFC-63-14mcee?trans-DCEIPA 22.5, 75.02.5 45 components in an appropriate vessel. Agitation may be used, 15 if desired. An azeotropic composition is a constant boiling liquid The present inventive azeotropic compositions are effec admixture of two or more substances that behaves as a single tive cleaning agents, defluxers and degreasers. In particular, Substance, in that the vapor, produced by partial evaporation the present inventive azeotropic compositions are useful or distillation of the liquid has the same composition as the when defluxing circuit boards with components such as Flip liquid, i.e., the admixture distills without Substantial compo chip, uBGA (ball grid array), and Chip scale or other sition change. Constant boiling compositions, which are advanced high-density packaging components. Flip chips, characterized as azeotropic, exhibit either a maximum or a uBGA, and Chip scale are terms that describe high density minimum boiling point, as compared with that of the non packaging components used in the semi-conductor industry azeotropic mixtures of the same Substances. 25 and well understood by those working in the field. By “azeotrope-like composition,” also referred to as “near azeotrope is meant a constant boiling, or Substantially con In a preferred embodiment the present invention relates to stant boiling liquid admixture of two or more Substances that a process for removing residue from a Surface or Substrate, behaves as a single Substance. One way to characterize an comprising: contacting the Surface or Substrate with a com azeotrope-like composition is that the vapor produced by 30 position of the present invention and recovering the Surface or partial evaporation or distillation of the liquid has Substan Substrate from the composition. tially the same composition as the liquid from which it was In the inventive process, the surface or substrate may be an evaporated or distilled. That is, the admixture distills/refluxes integrated circuit device, in which case, the residue comprises without Substantial composition change. Another way to soldering flux or oil. The integrated circuit device may be a characterize an azeotrope-like composition is that the bubble 35 circuit board with various types of components, such as Flip point vapor pressure of the composition and the dew point chips, uBGAs, or Chip Scale packaging components. Differ vapor pressure of the composition at a particular temperature ent types of oil residues may be mineral oils, motor oils, or are Substantially the same. Herein, a composition is azeo silicone oils. The means for contacting the Surface is not trope-like if, after 50 weight percent of the composition is critical and may be accomplished by immersion of the device removed such as by evaporation or boiling off, the difference 40 in a bath containing the composition, spraying the device with in vapor pressure between the original composition and the the composition or wiping the device with a Substrate that has composition remaining after 50 weight percent of the original been wet with the composition. Alternatively, the composi composition has been removed by evaporation or boil off is tion may also be used in a vapor degreasing apparatus less than about 10 percent. designed for Such residue removal. Such vapor degreasing In cleaning apparati, including vapor degreasing and vapor 45 defluxing equipment, compositions may be lost during opera equipment is available from Suppliers such as Forward Tech tion through leaks in shaft seals, hose connections, Soldered nology (a subsidiary of the Crest Group, Trenton, N.J.), Trek joints and broken lines. In addition, the working composition Industries (Azusa, Calif.), and Ultronix, Inc. (Hatfield, Pa.) may be released to the atmosphere during maintenance pro among others. cedures on equipment. If the composition is not a pure com 50 An effective composition for removing residue from a ponent or azeotropic or azeotrope-like composition, the com surface would be one that had a Kauri-Butanol value (Kb) of position may change when leaked or discharged to the at least about 25, preferably about 100. The Kauri-Butanol atmosphere from the equipment, which may cause the com value (Kb) for a given composition reflects the ability of said position remaining in the equipment to exhibit unacceptable composition to Solubilize various organic residues (e.g., performance. Accordingly, it is desirable to use as a cleaning 55 machine and conventional oils, flux residues, and greases or composition a single fluorinated hydrocarbon or an azeotro lubricants). The Kb value may be determined by ASTM pic or azeotrope-like composition that fractionates to a neg D-1133-94. ligible degree upon leak or boil off. The present invention further relates to compositions com Vapor degreasing or vapor defluxing apparatus function in prising 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane Some aspects similarly to a distillation column. These appa 60 ratus have one or more chambers for rinsing with a compo (HFC-63-14mcee) and at least one other compound selected sition and one or more chambers for boiling with a composi from the group consisting of alcohols, amines, esters, fluoro tion. As such, if a composition that is a non-azeotropic ethers, halocarbons, hydrocarbons, ketones, nitriles, 2,2-dim mixture were to be used in Such an apparatus, the composition ethyl-1,3-dioxolane, 1,2-dimethoxyethane and nitromethane. would fractionate and the performance in removing residue 65 Table 2 lists compounds with which HFC-63-14mcee may would be altered. Further, it would not be possible to recover, be combined in order to form the present inventive composi cleanup and re-use the composition as the composition would tions. US 7,476,331 B2 11 12

TABLE 2 TABLE 2-continued Synonym Synonym (or (or Name Chemical formula abbreviation) Name Chemical formula abbreviation) Hydrocarbons n-propyl acetate CHC(O)OCH2CHCH methyl n-butyrate CHCH2CHC(O)OCH cyclohexane butyl formate HC(O)O(CH2)CH, 2,2,3- diethyl carbonate (CHCH2O)2CO trimethylbutane 10 Ketones 2,4-dimethylpentane (C 3,3-dimethylpentane 2-butanone (or CHC(O)CHCH MEK 2,3-dimethylpentane methyl ethyl ketone) 2-methylhexane 3-methyl-2- CHC(O)CH(CH3)2 MIPK 3-methylhexane butanone (or methyl n-heptane 15 isopropylketone) methylcyclohexane 2-bromo- (CF),CBrC(O)CFCF toluene 1,1,144.55,5- isooctane octafluoro-2- n-Octane (trifluoromethyl)-3- pentanone Others 2-bromopropane 1-bromopropane mixture of isomers- CFCFCFCFOCH CFOCH 1,2-dichloroethane ,1,1,2,2,3,3,4,4- and (CF)2CFCFOCH 1,1-dichloroethane nonafluoro-4- fluorobenzene methoxybutane and methylene bromide 2-(methoxy trichloroethylene TCE 25 difluoromethyl)- tetrachloroethylene PCE ,1,1,2,3,3,3- (or heptafluoropropane perchloroethylene) mixture of isomers- CFCFCFCFOCHs and CFOCHs chlorobenzene CHCI -enoxy- (CF)CFCFOCHs trans-1,2- CHC-CHCI trans-DCE ,1,2,2,3,3,4,4,4- dichloroethylene 30 nonafluorobutane cis-1,2- CHC-CHCI cis-DCE and 2-(ethoxy dichloroethylene difluoromethyl)- Alcohols ,1,1,2,3,3,3- heptafluoropropane methanol ,1,1,2,2,3,4,5,5,5- CFCF-CF (OCH)CF(CF)CF DMTP ethanol 35 decafluoro-3- n-propanol methoxy-4- Isopropanol (trifluoromethyl)- 2-methyl-2-propanol pentane 2-methyl-2-butanol 2,2-dimethyl-1,3- cyclo —OC(CH2)2OCH2CH2— 2-butanol dioxolane (or sec-butanol) 40 1,2- CHOCH2CHOCH 2-methyl-1-propanol C dimethoxyethane (or isobutanol) Nitromethane CHNO, n-butanol 2-methoxyethanol 2,2,3,3,3- The compounds listed in Table 2 may be readily prepared pentafluoro-1- propanol 45 by those skilled in the art and are also commercially available 2,2,3,3-tetrafluoro from chemical Supply houses. 1.1.1.2.2.3.4.5.5,5-decafluoro 1-propanol 3-methoxy-4-(trifluoromethyl)-pentane, CFOCH, and 1,1,1,3,3,3- hexafluoro-2- CFOCH are available from 3MTM (St. Paul, Minn.). propanol These azeotropic or azeotrope-like compositions of the 2.2.2- CH-OHCF 50 present invention may be prepared by any convenient method trifluoroethanol by combining the desired amounts of the individual compo Nitriles nents. A preferred method is to weigh the desired component Acetonitrile CHCN amounts and thereafter combining the components in an Propionitrile CHCHCN appropriate vessel. Agitation may be used, if desired. Butyronitrile CHCHCHCN 55 The azeotropic compositions of the present invention are Amines listed in Table 3. n-methylmorpholine TABLE 3 Morpholine Component Azeotrope point Azeotrope 60 B wt % Boiling ethyl acetate CHC(O)OCHCH Boiling point HFC-63- wt % Point methylpropionate CHCHC(O)OCH HFC-63-14mcee plus (B) (° C.) 14mcee (B) (° C.) n-propyl formate HC(O)OCH2CHCH Dimethyl carbonate (CHO)CO Hydrocarbons Isopropyl acetate CHC(O)OCH(CH), isobutyl formate HC(O)OCH-CH(CH), 65 cyclohexane 80.7 61.1 38.9 71.5 ethylpropionate CHCHC(O)OCHCH 2,2,3-trimethylbutane 80.9 60.8 39.2 69.5 US 7,476,331 B2 13 14 TABLE 3-continued TABLE 3-continued Component Azeotrope point Azeotrope Component Azeotrope point Azeotrope B wt % Boilin B wt % Boiling 5 Boiling point HFC-63- wt % s Boiling point HFC-63- wt % Point HFC-63-14mcee plus (B) (° C.) 14mcee (B) (C.) HFC-63-14mcee plus (B) (° C.) 14mcee (B) (° C.) Ketones 2,4-dimethylpentane 8O.S 60.6 39.4 69.4 3,3-dimethylpentane 86.1 65.1 34.9 72.8 2-butanone 79.6 94.5 5.5 96.O 2,3-dimethylpentane 89.8 68.4 31.6 75.4 10 3-methyl-2-butanone 94.5 78.0 22.O 99.9 2-methylhexane 90.1 68.3 31.7 75.4 (CF),CBrC(O)CFCF 96.5 64.6 35.4 94.1 3-methylhexane 91.9 69.6 3O4 76.4 Fluoroethers n-heptane 98.4 74.9 25.1 8O.S DMTP 96.6 6.2 93.8 90.0 methylcyclohexane 98.2 73.2 26.8 80.4 Other oluene 110.6 83.8 16.2 87.2 15 isooctane 99.2 72.9 27.1 78.9 2,2-dimethyl-1,3-dioxolane 92.5 72.2 27.8 76.2 n-Octane 98.2 88.4 11.6 90.0 1,2-dimethoxyethane 83.5 67.6 36.4 71.6 Halocarbons nitromethane 101.2 81.0 19.0 90.0

2-bromopropane 59.4 33.6 66.4 56.8 -bromopropane 71.O 46.0 S4.O 66.3 o Additionally, the azeotropic compositions of the present 2-dichloroethane 83.5 59.4 40.6 74.5 invention may include ternary and quaternary azeotropic 1-dichloroethane 57.0 20.7 79.3 56.4 compositions comprising compounds from Table 2. Two of fluorobenzene 84.7 64.6 35.4 75.1 these higher order azeotropic compositions are exemplified in methylene bromide 97.0 64.9 35.1 86.0 Table 4 along with the atmospheric pressure boiling points for trichloroethylene 87.5 59.7 40.3 77.0 25 the compositions. etrachloroethylene 121.2 82.6 17.4 91.4 chlorobenzene 132.O 93.6 6.4 94.1 trans-1,2-dichloroethylene 48.0 24.O 76.O 45.O TABLE 4 cis-1,2-dichloroethylene 6O.S 37.0 63.0 58.2 Azeotrope point Azeotrope Alcohols Concentrations Boiling Point 30 Composition (wt %) (° C.) methanol 65.6 47.0 53.0 65.5 ethanol 78.3 79.4 20.6 71.3 HFC-63-14mcee?CFOC2H5/trans- 12.1/16.8/71.1 50 n-propanol 97.2 86.5 13.5 82.3 DCE Isopropanol 82.3 77.9 22.1 73.5 HFC-63-14mcee?CFOCH/trans- 7.8.16.4f67.9, 7.9 40-43 2-methyl-2-propanol 82.2 73.3 26.7 71.8 DCE MeOH 2-methyl-2-butanol 102.0 82.9 17.1 82.1 35 2-butanol 98.0 83.3 16.7 81.0 The azeotrope-like compositions of the present invention Isobutanol 107.7 87.8 12.2 85.5 n-butanol 117.7 91.7 8.3 89.4 are listed in Table 5. 2-methoxyethanol 124.6 93.4 6.6 89.0 2,2,3,3,3-pentafluoro-1- 81.8 57.0 43.O 76.9 40 TABLE 5 propanol 2,2,3,3-tetrafluoro-1- 109.0 87.4 12.6 92.2 Azeotrope-Like Ranges propanol Composition wt % HFC-63-14mcee?wt % (B) 1,1,1,3,3,3-hexafluoro-2- 59.0 14.5 85.5 58.7 HFC-63-14mcee plus B: propanol Hydrocarbons 2.2.2-trifluoroethanol 78.4 62.O 38.0 73.3 45 Nitriles Cyclohexane 38-83,62-17 2,2,3-trimethylbutane 39-8261-18 2,4-dimethylpentane 39-8261-18 acetonitrile 81.5 73.6 26.4 75.1 SNEN 42-84.58-16 propionitrile 97.4 83.0 17.0 83.9 2,3-dimethylpentane 45-86, SS-14 butyronitrile 116.0 90.9 9.1 91.2 50 2-methylhexane 45-86, SS-14 Amines 3-methylhexane 46-86.54-14 o n-heptane 51-89,49-11 n-methylmorpholine 11S.O 86.3 13.7 89.6 Methylcyclohexane 48-89.52-11 morpholine 128.9 95.6 4.4 94.5 FS,e SC.; 2 Esters 55 n-Octane 62-9938-1 Halocarbons ethyl acetate 72.1 60.6 39.4 70.3 methylpropionate 87.7 61.6 38.4 71.2 2-bromopropane 1-6899-32 n-propyl formate 80.8 64.O 36.O 72.9 R 5. dimethyl carbonate 9 O.S 71.1 28.9 79.7 1,1-dichloroethane 1-6299-38 Isopropyl acetate 88.2 68.3 31.7 76.9 60 Fluorobenzene 39-85.61-15 Isobutyl formate 98.4 76.5 23.5 82.9 Methylene bromide 36-9964-1 ethylpropionate 99.1 76.6 23.4 83.0 Trichloroethylene 3S-80.6S-20 n-propyl acetate 101S 78.3 21.7 84.2 firstylene 32. methyl n-butyrate 102.6 79.0 21.0 84.7 trans-1,2-chloroethylene 1-6899-32 butyl formate 106.6 82.2 17.8 86.9 65 cis-1,2-dichloroethylene 1-72.99-28 diethyl carbonate 126.8 91.5 8.5 93.1 Alcohols US 7,476,331 B2 15 16 Any of the compositions of the present invention may TABLE 5-continued further comprise an aerosol propellant. Aerosol propellants may assist in delivering the present compositions from a Azeotrope-Like Ranges storage container to a surface in the form of an aerosol. Composition wt % HFC-63-14mcee?wt % (B) Aerosol propellant is optionally included in the present com positions in up to 25 weight percent of the total composition. Methanol 1-93,99-7 Representative aerosol propellants comprise air, nitrogen, Ethanol 58-92.f42-1 n-propanol 69-94,31-6 carbon dioxide, dimethyl ether (DME, CHOCH), difluo Isopropanol 58-91.f42-9 romethane (HFC-32, CHF), trifluoromethane (HFC-23, 2-methyl-2-propanol 52-88.48-12 10 CHF), difluoroethane (HFC-152a, CHFCH), trifluoroet 2-methyl-2-butanol 63-92.37-8 2-butanol 64-93,36-7 hane (HFC-143a, CHCF; or HFC-143, CHFCHF), tet Isobutanol 70-95.30-5 rafluoroethane (HFC-134a, CFCHF, HFC-134, n-butanol 75-99.25-1 CHF.CHF), pentafluoroethane (HFC-125, CFCHF), hep 2-methoxyethanol 77-97,23-3 tafluoropropane (HFC-227ea, CFCHFCF), pentafluoro 2.2.2-trifluoroethanol 1-8499-16 15 2,2,3,3,3-pentafluoro-1- 1-8299-18 propane (HFC-245fa, CFCHCHF), hydrocarbons, includ propanol ing propane, n-butane, isobutane, n-pentane, cyclopentane, 2,2,3,3-tetrafluoro-1-propanol 59-99;41-1 2-methylbutane, among others, and any combinations of 1,1,1,3,3,3-hexafluoro-2- 1-6499-36 those compounds in the list. propanol The present invention further relates to refrigerant or heat Nitriles transfer fluid compositions comprising 1,1,1,2,2,3,4,5,5,6,6, Acetonitrile 46-91,54-9 7,7,7-tetradecafluoroheptane (HFC-63-14mcee) and at least Propionitrile 61-96.39-4 one hydrocarbon, halocarbon, alcohol, ester, 2.2-dimethyl-1, Butyronitrile 71-99.29 3-dioxolane, or acetonitrile. Representative hydrocarbons, Amines halocarbons, alcohols, esters etc., are listed in Table 2. n-methylmorpholine 64-9936 25 The preferred refrigerant or heat transfer fluid composi Morpholine 74-9926 tions of the present invention include HFC-63-14mcee with at Esters least one compound selected from the group consisting of: ethyl acetate 34-83.66-17 cyclohexane: methylpropionate 3S-83,6S-17 2.2,3-trimethylbutane; n-propyl formate 38-84f62-16 30 2,4-dimethylpentane; dimethyl carbonate 46-8954-11 3.3-dimethylpentane: isopropyl acetate 44-86.56-14 isobutyl formate 53-91,47-9 2,3-dimethylpentane ethylpropionate 53-91,47-9 2-methylhexane; n-propyl acetate SS-92.45-8 3-methylhexane, methyl n-butyrate 56-93,44-7 35 isooctane; butyl formate 59-99: 41 diethyl carbonate 68-9932 2-bromopropane; Ketones 1-bromopropane; 1,2-dichloroethane; 2-butanone 1-9999 3-methyl-2-butanone 1-9999 1,1-dichloroethane; 40 (CF)-CBrC(O)CFCF 1-9999 fluorobenzene: Fluoroethers o-difluorobenzene: m-difluorobenzene: DMTP 1-9999 p-difluorobenzene: Other trichloroethylene; Nitromethane 47-99.53 45 methanol; 1,2-dimethoxyethane 45-85, SS-15 ethanol: 2,2-dimethyl-1,3-dioxolane SO-87 SO-13 2-methyl-2-propanol; 2,2-dimethyl-1,3-dioxolane; acetonitrile; In addition to the binary azeotrope-like compositions in the ethyl acetate; preceding table, higher order (ternary or quaternary) azeo methyl propionate; trope-like compositions are included in the present invention. n-propyl formate; Examples ofternary or higher order azeotrope-like composi dimethylcarbonate; tions are given in Table 6. isopropyl acetate; 55 2.2.2-trifluoroethanol: TABLE 6 isopropanol; Azeotrope-like Preferred 2.2.3,3,3-pentafluoro-1-propanol; Range Range 2.2.3,3-tetrafluoro-1-propanol; and Composition (Wt 9%) (Wt 9%) 1,1,1,3,3,3-hexafluoro-2-propanol. HFC-63-14mcee?CFOCH/trans- 1-68/1-98/1-98 1-601-84, 15-98 60 The refrigerant or heat transfer fluid compositions of the DCE present invention may additionally be azeotropic or azeo HFC-63-14mcee?CFOCHs. 1-681-7128-98 1-601-50, 40-80 trope-like compositions as listed in Table 3, Table 4, Table 5 trans-DCE and Table 6. HFC-63- 1-681-7128-98, 1-601-50, 40-80, 14mcee CFOC2H5f trans- 1-30 1-3O The refrigerant or heat transfer fluid compositions of the DCE methanol 65 present invention may further comprise about 0.01 weight percent to about weight percent of a stabilizer, free radical Scavenger or antioxidant. Such additives include but are not US 7,476,331 B2 17 18 limited to, nitromethane, hindered phenols, hydroxylamines, radical sites available to form covalent bonds with other radi thiols, phosphites, or lactones. Single additives or combina cals. Hydrocarbylene radicals mean divalent hydrocarbon tions may be used. radicals. In the present invention, preferable polyoxyalkylene gly The refrigerant or heat transfer fluid compositions of the col ether solubilizing agents are represented by R' (OR), present invention may further comprise about 0.01 weight OR whereinx is preferably 1-2; y is preferably 1: RandR percent to about 5 weight percent of a water scavenger (drying are preferably independently selected from hydrogen and compound). Such water scavengers may comprise ortho aliphatic hydrocarbon radicals having 1 to 4 carbonatoms; R esters such as trimethyl-, triethyl-, or tripropylorthoformate. is preferably selected from aliphatic hydrocarbylene radicals The refrigerant or heat transfer fluid compositions of the 10 having from 2 or 3 carbon atoms, most preferably 3 carbon present invention may further comprise an ultra-violet (UV) atoms; the polyoxyalkylene glycol ether molecular weight is dye and optionally a solubilizing agent. The UV dye is a preferably from about 100 to about 250 atomic mass units, useful component for detecting leaks of the refrigerant and most preferably from about 125 to about 250 atomic mass heat transfer fluid compositions by permitting one to observe units. The R' and R hydrocarbon radicals having 1 to 6 the fluorescence of the dye in the refrigerant or heat transfer 15 carbon atoms may be linear, branched or cyclic. Representa fluid compositions at a leak point or in the vicinity of refrig tive R' and Rhydrocarbon radicals include methyl, ethyl, eration or air-conditioning apparatus. One may observe the propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pen fluorescence of the dye under an ultra-violet light. Solubiliz tyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclo ing agents may be needed to increase solubility of Such UV hexyl. Where free hydroxyl radicals on the present polyoxy alkylene glycol ether solubilizing agents may be dyes in some refrigerants and heat transfer fluids. incompatible with certain compression refrigeration appara By “ultra-violet dye is meant a UV fluorescent composi tus materials of construction (e.g. Mylar R), R' and Rare tion that absorbs light in the ultra-violet or “near ultra-violet preferably aliphatic hydrocarbon radicals having 1 to 4 car region of the electromagnetic spectrum. The fluorescence bon atoms, most preferably 1 carbon atom. The Raliphatic produced by the UV fluorescent dye under illumination by a 25 hydrocarbylene radicals having from 2 to 4 carbon atoms UV light that emits radiation with wavelength anywhere from form repeating oxyalkylene radicals —(OR), that include 10 nanometer to 750 nanometer may be detected. Therefore, oxyethylene radicals, oxypropylene radicals, and oxybuty if refrigerant or heat transfer fluid containing such a UV lene radicals. The oxyalkylene radical comprising R in one fluorescent dye is leaking from a given point in a refrigeration polyoxyalkylene glycol ether Solubilizing agent molecule or air-conditioning apparatus, the fluorescence can be 30 may be the same, or one molecule may contain different R detected at the leak point. Such UV fluorescent dyes include oxyalkylene groups. The present polyoxyalkylene glycol but are not limited to naphthalimides, perylenes, coumarins, ether solubilizing agents preferably comprise at least one anthracenes, phenanthracenes, Xanthenes, thioxanthenes, oxypropylene radical. Where R' is an aliphatic or alicyclic naphthoxanthenes, fluoresceins, and derivatives or combina hydrocarbon radical having 1 to 6 carbon atoms and y bond tions thereof. Solubilizing agents of the present invention 35 ing sites, the radical may be linear, branched or cyclic. Rep comprise at least one compound selected from the group resentative R' aliphatic hydrocarbon radicals having two consisting of hydrocarbons, hydrocarbon ethers, polyoxy bonding sites include, for example, an ethylene radical, a alkylene glycol ethers, amides, nitriles, ketones, chlorocar propylene radical, a butylene radical, a pentylene radical, a bons, esters, lactones, aryl ethers, fluoroethers and 1,1,1- hexylene radical, a cyclopentylene radical and a cyclohexy trifluoroalkanes. 40 lene radical. Representative R' aliphatic hydrocarbon radi Hydrocarbon solubilizing agents of the present invention cals having three or four bonding sites include residues comprise hydrocarbons including straight chained, branched derived from polyalcohols, such as trimethylolpropane, glyc chain or cyclic alkanes or alkenes containing 5 or fewer erin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5- carbon atoms and only hydrogen with no other functional trihydroxycyclohexane, by removing their hydroxyl radicals. groups. Representative hydrocarbon Solubilizing agents 45 Representative polyoxyalkylene glycol ether solubilizing comprise propane, propylene, cyclopropane, n-butane, isobu agents include but are not limited to: CHOCH2CH(CH) tane, and n-pentane. It should be noted that if the refrigerant O(H or CH) (propylene glycol methyl (or dimethyl)ether), is a hydrocarbon, then the solubilizing agent may not be the CHOCH2CH(CH)O(H or CH) (dipropylene glycol same hydrocarbon. methyl (or dimethyl)ether), CHOICHCH(CH)O(H or Hydrocarbon ether solubilizing agents of the present 50 CH) (tripropylene glycol methyl (or dimethyl)ether), invention comprise ethers containing only carbon, hydrogen CHOCH2CHCCH)O(H or CHs) (propylene glycol ethyl and oxygen, such as dimethyl ether (DME). (or diethyl)ether), CHOCH2CH(CH)O(H or CH) Polyoxyalkylene glycol ether solubilizing agents of the (dipropylene glycol ethyl (or diethyl)ether), CHOICHCH present invention are represented by the formula (CH)O(H or CH) (tripropylene glycol ethyl (or diethyl) 55 ether), CH,OCH2CHCCH)O(H or CH 7) (propylene glycol R" (OR), OR), n-propyl (or di-n-propyl)ether), CHOICHCH(CH)O(H or CH 7) (dipropylene glycoln-propyl (or di-n-propyl)ether), wherein X is an integer from 1-3; y is an integer from 1-4; R' CH,OCH2CH(CH)O(H or CH 7) (tripropylene glycol is selected from hydrogen and aliphatic hydrocarbon radicals n-propyl (or di-n-propyl)ether), CHOCH2CHCCH)OH having 1 to 6 carbon atoms and y bonding sites; R is selected 60 (propylene glycol n-butyl ether), CHOICH-CH(CH)O from aliphatic hydrocarbylene radicals having from 2 to 4 (H or CH) (dipropylene glycol n-butyl (or di-n-butyl) carbonatoms; R is selected from hydrogen, and aliphatic and ether), CHOICHCH(CH)O(H or CH) (tripropylene alicyclic hydrocarbon radicals having from 1 to 6 carbon glycol n-butyl (or di-n-butyl) ether), (CH),COCHCH atoms; at least one of R' and R is selected from said hydro (CH)OH (propylene glycol t-butyl ether), (CH)CO carbon radical; and wherein said polyoxyalkylene glycol 65 CHCH(CH)O(H or (CH)) (dipropylene glycol t-butyl ethers have a molecular weight of from about 100 to about (or di-t-butyl)ether), (CH) COCH2CH(CH)O(H or 300 atomic mass units. As used herein, bonding sites mean (CH)) (tripropylene glycol t-butyl (or di-t-butyl) ether), US 7,476,331 B2 19 20 CHOCH2CH(CH)OH (propylene glycol n-pentyl ether), phatic and alicyclic hydrocarbon radicals having 1 to 9 carbon CHOCHCH(CH)OH (butylene glycol n-butyl ether), atoms. The molecular weight of said ketones is preferably CHOCH2CH(CHs)OH (dibutylene glycol n-butyl from about 100 to 200 atomic mass units. R' and R may ether), trimethylolpropane tri-n-butyl ether (CHC(CH2O together form a hydrocarbylene radical connected and form (CH2)CH)) and trimethylolpropane di-n-butyl ether ing a five, six, or seven-membered ring cyclic ketone, for (CHC(CHOC(CH2)CH) CH-OH). Amide solubilizing agents of the present invention com example, cyclopentanone, cyclohexanone, and cyclohep prise those represented by the formulae RC(O)NR'R'' and tanone. R' and R may optionally include substituted hydro cyclo-IRC(O)N(R)-1, wherein R', R, R and Rare inde carbon radicals, that is, radicals containing non-hydrocarbon pendently selected from aliphatic and alicyclic hydrocarbon 10 Substituents selected from halogens (e.g., fluorine, chlorine) radicals having from 1 to 12 carbonatoms; R is selected from and alkoxides (e.g. methoxy). R' and R may optionally aliphatic hydrocarbylene radicals having from 3 to 12 carbon include heteroatom-Substituted hydrocarbon radicals, that is, atoms; and wherein said amides have a molecular weight of radicals, which contain the atoms nitrogen (aza-), oxygen from about 100 to about 300 atomic mass units. The molecu (keto-, oxa-) or Sulfur (thia-) in a radical chain otherwise lar weight of said amides is preferably from about 160 to 15 composed of carbon atoms. In general, no more than three about 250 atomic mass units. R. R. R. and R may option non-hydrocarbon Substituents and heteroatoms, and prefer ally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon Substituents selected from halo ably no more than one, will be present for each 10 carbon gens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). atoms in RandR, and the presence of any such non-hydro R", R. RandR may optionally include heteroatom-substi carbon Substituents and heteroatoms must be considered in tuted hydrocarbon radicals, that is, radicals, which contain the applying the aforementioned molecular weight limitations. atoms nitrogen (aza-), oxygen (oxa-) or Sulfur (thia-) in a Representative R' and Raliphatic, alicyclic and aryl hydro radical chain otherwise composed of carbon atoms. In gen carbon radicals in the general formula RC(O)R’ include eral, no more than three non-hydrocarbon Substituents and methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, heteroatoms, and preferably no more than one, will be present 25 tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopen for each 10 carbonatoms in R', and the presence of any such tyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl non-hydrocarbon Substituents and heteroatoms must be con and their configurational isomers, as well as phenyl, benzyl, sidered in applying the aforementioned molecular weight limitations. Preferred amide solubilizing agents consist of cumenyl, mesityl, tolyl, Xylyl and phenethyl. carbon, hydrogen, nitrogen and oxygen. Representative R', 30 Representative ketone solubilizing agents include but are R. R. and Raliphatic and alicyclic hydrocarbon radicals not limited to: 2-butanone, 2-pentanone, acetophenone, buty include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec rophenone, hexanophenone, cyclohexanone, cyclohep butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, tanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohex dodecyl and their configurational isomers. A preferred 35 anone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, embodiment of amide solubilizing agents are those wherein R" in the aforementioned formula cyclo-IRC(O)N(R)- 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl may be represented by the hydrocarbylene radical (CRR), ketone. in other words, the formula cyclo-I(CRR),C(O)N(R)- Nitrile solubilizing agents of the present invention com wherein the previously-stated values for molecular weight 40 prise nitriles represented by the formula RCN, wherein R' is apply; n is an integer from 3 to 5; R is a saturated hydrocar selected from aliphatic, alicyclic orarylhydrocarbon radicals bon radical containing 1 to 12 carbon atoms; R and R7 are having from 5 to 12 carbon atoms, and wherein said nitriles independently selected (for each n) by the rules previously have a molecular weight of from about 90 to about 200 atomic offered defining R'. In the lactams represented by the for mass units. R' in said nitrile solubilizing agents is preferably mula: cyclo-(CRR),C(O)N(R)-), all Rand Rare pref 45 selected from aliphatic and alicyclic hydrocarbon radicals erably hydrogen, or contain a single Saturated hydrocarbon having 8 to 10 carbon atoms. The molecular weight of said radical among the n methylene units, and R is a saturated nitrile solubilizing agents is preferably from about 120 to hydrocarbon radical containing 3 to 12 carbon atoms. For about 140 atomic mass units. R' may optionally include sub example, 1-(saturated hydrocarbon radical)-5-methylpyrroli stituted hydrocarbon radicals, that is, radicals containing non din-2-ones. 50 hydrocarbon Substituents selected from halogens (e.g., fluo Representative amide solubilizing agents include but are rine, chlorine) and alkoxides (e.g. methoxy). R' may not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2- optionally include heteroatom-substituted hydrocarbon radi one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, cals, that is, radicals, which contain the atoms nitrogen (aza-), 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methyl piperid-2- oxygen (keto-, oxa-) or Sulfur (thia-) in a radical chain other one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 55 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpip wise composed of carbon atoms. In general, no more than erid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolac three non-hydrocarbon Substituents and heteroatoms, and tam, 1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, preferably no more than one, will be present for each 10 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, carbon atoms in R', and the presence of any such non-hydro carbon Substituents and heteroatoms must be considered in N,N-dibutylformamide and N,N-diisopropylacetamide. 60 Ketone solubilizing agents of the present invention com applying the aforementioned molecular weight limitations. prise ketones represented by the formula RC(O)R’, wherein Representative R' aliphatic, alicyclic and aryl hydrocarbon R" and Rare independently selected from aliphatic, alicyclic radicals in the general formula RCN include pentyl, isopen and aryl hydrocarbon radicals having from 1 to 12 carbon tyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, atoms, and wherein said ketones have a molecular weight of 65 octyl, nonyl, decyl, undecyl, dodecyl and their configura from about 70 to about 300 atomic mass units. R' and R in tional isomers, as well as phenyl, benzyl, cumenyl, mesityl, said ketones are preferably independently selected from ali tolyl, xylyl and phenethyl. Representative nitrile solubilizing US 7,476,331 B2 21 agents include but are not limited to: 1-cyanopentane, 2.2- dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane,

1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanode cane, 2-cyanodecane, 1-cyanoundecane and 1-cyanodode CaC. Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RCl, wherein X is 1 or 2: R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and 10 wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general 15 formula RCl, include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. Representative chlorocarbon Solubilizing agents include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3- methylpentane, 1-chlorohexane, 1,6-dichlorohexane, 1-chlo roheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane. 25 Ester Solubilizing agents of the present invention comprise esters represented by the general formula RC(O)OR, These lactones contain the functional group —C(O)C)—in wherein RandR are independently selected from linear and a ring of six (A), or preferably five atoms (B), wherein for cyclic, Saturated and unsaturated, alkyl and aryl radicals. structures A and B. R through Rs are independently Preferred esters consist essentially of the elements C, Hand 30 selected from hydrogen or linear, branched, cyclic, bicyclic, O, have a molecular weight of from about 80 to about 550 saturated and unsaturated hydrocarbyl radicals. Each R atomic mass units. though Rs may be connected forming a ring with another R Representative esters include but are not limited to: (CH) through Rs. The lactone may have an exocyclic alkylidene CHCHO(O)C(CH2)(O)COCHCH(CH), (diisobutyl group as in structure C, wherein R through R are indepen dibasic ester), ethylhexanoate, ethylheptanoate, n-butyl pro 35 dently selected from hydrogen or linear, branched, cyclic, bicyclic, Saturated and unsaturated hydrocarbyl radicals. pionate, n-propyl propionate, ethyl benzoate, di-n-propyl Each R though Re may be connected forming a ring with phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, another R through R. The lactone solubilizing agents have a “Exxate 700' (a commercial C, alkyl acetate), “Exxate 800 molecular weight range of from about 80 to about 300 atomic (a commercial Cs alkyl acetate), dibutyl phthalate, and tert 40 mass units, preferred from about 80 to about 200 atomic mass butyl acetate. units. Lactone solubilizing agents of the present invention com Representative lactone solubilizing agents include but are prise lactones represented by structures A, B, and C: not limited to the compounds listed in Table 7.

TABLE 7

Molecular Molecular Additive Molecular Structure Formula Weight (amu)

(E,Z)-3-ethylidene-5-methyl- O O C7H10O2 126 dihydro-furan-2-one

(E,Z)-3-propylidene-5-methyl- O O C8H12O2 140 dihydro-furan-2-one

(E,Z)-3-butylidene-5-methyl- O O CoH4O2 154 dihydro-furan-2-one

US 7,476,331 B2 27 28

TABLE 7-continued

Molecular Molecular Additive Molecular Structure Formula Weight (amu) cis-3-octyl-5-methyl-dihydro-furan 212 2-one

cis-3-(3,5,5-trimethylhexyl)-5- 226 methyl-dihydro-furan-2-one

cis-3-cyclohexylmethyl-5-methyl 196 dihydro-furan-2-one

5-methyl-5-hexyl-dihydro-furan-2 184 Ole

5-methyl-5-octyl-dihydro-furan-2- 212 Ole

Hexahydro-isobenzofuran-1-one 140

delta-decalactone 170

delta-undecalactone 184

delta-dodecalactone 198 US 7,476,331 B2 29

TABLE 7-continued

Molecular Molecular Additive Molecular Structure Formula Weight (amu) mixture of 4-hexyl-dihydrofuran-2- CoH18O2 170 one and 3-hexyl-dihydro-furan-2- Ole

Lactone solubilizing agents generally have a kinematic general formula CFR', wherein R' is selected from aliphatic viscosity of less than about 7 centistokes at 40° C. For and alicyclic hydrocarbon radicals having from about 5 to instance, gamma-undecalactone has kinematic viscosity of about 15 carbon atoms, preferably primary, linear, Saturated 5.4 centistokes and cis-(3-hexyl-5-methyl)dihydrofuran-2- alkyl radicals. Representative 1,1,1-trifluoroalkane solubiliz one has viscosity of 4.5 centistokes, both at 40° C. Lactone ing agents include but are not limited to: 1,1,1-trifluorohex solubilizing agents may be available commercially or pre ane and 1,1,1-trifluorododecane. pared by methods as described in U.S. patent application Ser. Solubilizing agents of the present invention may be present No. 10/910,495 (inventors being P. J. Fagan and C. J. Bran 25 as a single compound, or may be present as a mixture of more denburg), filed Aug. 3, 2004, incorporated herein by refer than one solubilizing agent. Mixtures of solubilizing agents CCC. may contain two solubilizing agents from the same class of Aryl ether solubilizing agents of the present invention compounds, say two lactones, or two solubilizing agents from comprise aryl ethers represented by the formula ROR, two different classes, such as a lactone and a polyoxyalkylene wherein: R is selected from arylhydrocarbon radicals having 30 glycol ether. from 6 to 12 carbon atoms; R is selected from aliphatic In the present compositions comprising refrigerant and UV hydrocarbon radicals having from 1 to 4 carbon atoms; and fluorescent dye, or comprising heat transfer fluid and UV wherein said aryl ethers have a molecular weight of from fluorescent dye, from about 0.001 weight percent to about 1.0 about 100 to about 150 atomic mass units. Representative R' weight percent of the compositions is UV dye, preferably aryl radicals in the general formula R'OR include phenyl, 35 from about 0.005 weight percent to about 0.5 weight percent, biphenyl, cumenyl, mesityl, tolyl. Xylyl, naphthyl and and most preferably from 0.01 weight percent to about 0.25 pyridyl. Representative Raliphatic hydrocarbon radicals in weight percent. the general formula R'OR include methyl, ethyl, propyl, Solubility of these UV fluorescent dyes in refrigerants and isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Represen heat transfer fluids may be poor. Therefore, methods for intro tative aromatic ether solubilizing agents include but are not 40 ducing these dyes into the refrigeration or air-conditioning limited to: methyl phenyl ether (anisole), 1,3-dimethyoxy apparatus have been awkward, costly and time consuming. benzene, ethyl phenyl ether and butyl phenyl ether. U.S. Pat. No. RE 36,951 describes a method, which utilizes a Fluoroether solubilizing agents of the present invention dye powder, solid pellet or slurry of dye that may be inserted comprise those represented by the general formula into a component of the refrigeration or air-conditioning R'OCFCF-H, wherein R' is selected from aliphatic and 45 apparatus. As refrigerant and lubricant are circulated through alicyclic hydrocarbon radicals having from about 5 to about the apparatus, the dye is dissolved or dispersed and carried 15 carbon atoms, preferably primary, linear, Saturated, alkyl throughout the apparatus. Numerous other methods for intro radicals. Representative fluoroether solubilizing agents ducing dye into a refrigeration or air-conditioning apparatus include but are not limited to: CH-OCFCFH and 50 are described in the literature. CHOCFCFH. It should be noted that if the refrigerant is Ideally, the UV fluorescent dye could be dissolved in the a fluoroether, then the Solubilizing agent may not be the same refrigerant itself thereby not requiring any specialized fluoroether. method for introduction to the refrigeration or air-condition Fluoroether solubilizing agents may further comprise ing apparatus. The present invention relates to compositions ethers derived from fluoro-olefins and polyols. The fluoro 55 including UV fluorescent dye, which may be introduced into olefins may be of the type CF=CXY, wherein X is hydro the system in the refrigerant. The inventive compositions will gen, chlorine or fluorine, and Y is chlorine, fluorine, CF or allow the storage and transport of dye containing refrigerant OR wherein Ris CF, CFs, or C.F. Representative fluoro and heat transfer fluid even at low temperatures while main olefins are tetrafluoroethylene, chlorotrifluoroethylene, taining the dye in solution. hexafluoropropylene, and perfluoromethylvinyl ether. The 60 In the present compositions comprising refrigerant, UV polyols may be of the type HOCHCRR'(C)(CHOH),CH fluorescent dye and solubilizing agent, or comprising heat (CHOH), wherein Rand Rare hydrogen, or CH, or C.Hs transfer fluid, UV fluorescent dye and solubilizing agent, and wherein X is an integer from 0-4, y is an integer from 0-3 from about 1 to about 50 weight percent, preferably from and Z is either Zero or 1. Representative polyols are trimethy about 2 to about 25 weight percent, and most preferably from lol propane, pentaerythritol, butanediol, and ethylene glycol. 65 about 5 to about 15 weight percent of the combined compo 1,1,1-Trifluoroalkane solubilizing agents of the present sition is solubilizing agent in the refrigerant or heat transfer invention comprise 1,1,1-trifluoroalkanes represented by the fluid. In the compositions of the present invention the UV US 7,476,331 B2 31 32 fluorescent dye is present in a concentration from about 0.001 Leak detection also helps one contain chemicals used in the weight percent to about 1.0 weight percent in the refrigerant operation of the apparatus. or heat transfer fluid, preferably from 0.005 weight percent to The method comprises providing the composition com about 0.5 weight percent, and most preferably from 0.01 prising refrigerant and ultra-violet fluorescent dye, or com weight percent to about 0.25 weight percent. prising heat transfer fluid and ultra-violet fluorescent dye as Optionally, commonly used refrigeration or air-condition described herein, and optionally, a solubilizing agent as ing system additives may be added, as desired, to composi described herein, to refrigeration and air-conditioning appa tions of the present invention in order to enhance performance ratus and employing a suitable means for detecting the UV and system stability. These additives are known in the field of fluorescence at a leak point. Suitable means for detecting the refrigeration and air-conditioning, and include, but are not 10 dye include, but are not limited to, ultra-violet lamp, often limited to, antiwear agents, extreme pressure lubricants, cor referred to as a “black light” or “blue light'. Such ultra-violet rosion and oxidation inhibitors, metal Surface deactivators, lamps are commercially available from numerous sources free radical scavengers, and foam control agents. In general, specifically designed for this purpose. Once the ultra-violet these additives are present in the inventive compositions in fluorescent dye containing composition has been introduced Small amounts relative to the overall composition. Typically 15 to the refrigeration or air-conditioning apparatus and has been concentrations of from less than about 0.1 weight percent to allowed to circulate throughout the system, a leak can be as much as about 3 weight percent of each additive are used. found by shining said ultra-violet lamp on the apparatus and These additives are selected on the basis of the individual observing the fluorescence of the dye in the vicinity of any system requirements. These additives include members of the leak point. triaryl phosphate family of EP (extreme pressure) lubricity The present invention further relates to a method of using additives, such as butylated triphenyl phosphates (BTPP), or the compositions of the present invention for producing other alkylated triaryl phosphate esters, e.g. Syn-0-Ad 8478 refrigeration or heat, wherein the method comprises produc from Akzo Chemicals, tricresyl phosphates and related com ing refrigeration by evaporating said composition in the pounds. Additionally, the metal dialkyldithiophosphates (e.g. vicinity of a body to be cooled and thereafter condensing said Zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1375 and 25 composition; or producing heat by condensing said compo other members of this family of chemicals may be used in sition in the vicinity of the body to be heated and thereafter compositions of the present invention. Other antiwear addi evaporating said composition. tives include natural product oils and asymmetrical polyhy Mechanical refrigeration is primarily an application of droxyl lubrication additives, such as Synergol TMS (Interna thermodynamics wherein a cooling medium, Such as a refrig tional Lubricants). Similarly, stabilizers such as antioxidants, 30 erant, goes through a cycle so that it can be recovered for free radical scavengers, and water Scavengers may be reuse. Commonly used cycles include vapor-compression, employed. Compounds in this category can include, but are absorption, Steam-jet or steam-ejector, and air. not limited to, butylated hydroxy toluene (BHT) and Vapor-compression refrigeration systems include an epoxides. evaporator, a compressor, a condenser, and an expansion Solubilizing agents such as ketones may have an objection 35 device. A vapor-compression cycle re-uses refrigerant in mul able odor, which can be masked by addition of an odor mask tiple steps producing a cooling effect in one step and a heating ing agent or fragrance. Typical examples of odor masking effect in a different step. The cycle can be described simply as agents or fragrances may include Evergreen, Fresh Lemon, follows. Liquid refrigerant enters an evaporator through an Cherry, Cinnamon, Peppermint, Floral or Orange Peel, all expansion device, and the liquid refrigerant boils in the commercially available, as well as d-limonene and pinene. 40 evaporator at a low temperature to form a gas and produce Such odor masking agents may be used at concentrations of cooling. The low-pressure gas enters a compressor where the from about 0.001% to as much as about 15% by weight based gas is compressed to raise its pressure and temperature. The on the combined weight of odor masking agent and solubi higher-pressure (compressed) gaseous refrigerant then enters lizing agent. 45 the condenser in which the refrigerant condenses and dis The present invention further relates to a method of using charges its heat to the environment. The refrigerant returns to the refrigerant or heat transfer fluid compositions further the expansion device through which the liquid expands from comprising ultraviolet fluorescent dye, and optionally, Solu the higher-pressure level in the condenser to the low-pressure bilizing agent, in refrigeration or air-conditioning apparatus. level in the evaporator, thus repeating the cycle. The method comprises introducing the refrigerant or heat 50 There are various types of compressors that may be used in transfer fluid composition into the refrigeration or air-condi refrigeration applications. Compressors can be generally tioning apparatus. This may be done by dissolving the UV classified as reciprocating, rotary, jet, centrifugal, Scroll, fluorescent dye in the refrigerant or heat transfer fluid com screw or axial-flow, depending on the mechanical means to position in the presence of a solubilizing agent and introduc compress the fluid, or as positive-displacement (e.g., recip ing the combination into the apparatus. Alternatively, this 55 rocating, scroll or screw) or dynamic (e.g., centrifugal orjet), may be done by combining solubilizing agent and UV fluo depending on how the mechanical elements act on the fluid to rescent dye and introducing said combination into refrigera be compressed. tion or air-conditioning apparatus containing refrigerant and/ Either positive displacement or dynamic compressors may or heat transfer fluid. The resulting composition may be used be used in the present inventive process. A centrifugal type in the refrigeration or air-conditioning apparatus. 60 compressor is the preferred equipment for the present refrig The present invention further relates to a method of using erant compositions. the refrigerant or heat transfer fluid compositions comprising A centrifugal compressor uses rotating elements to accel ultraviolet fluorescent dye to detect leaks. The presence of the erate the refrigerant radially, and typically includes an impel dye in the compositions allows for detection of leaking refrig ler and diffuser housed in a casing. Centrifugal compressors erant in the refrigeration or air-conditioning apparatus. Leak 65 usually take fluid in at an impeller eye, or central inlet of a detection helps to address, resolve or prevent inefficient circulating impeller, and accelerate it radially outward. Some operation of the apparatus or system or equipment failure. static pressure rise occurs in the impeller, but most of the US 7,476,331 B2 33 34 pressure rise occurs in the diffuser section of the casing, HFC-63-14mcee and fluorobenzene: where velocity is converted to static pressure. Each impeller HFC-63-14mcee and o-difluorobenzene: diffuser set is a stage of the compressor. Centrifugal compres HFC-63-14mcee and m-difluorobenzene: sors are built with from 1 to 12 or more stages, depending on HFC-63-14mcee and p-difluorobenzene: the final pressure desired and the volume of refrigerant to be HFC-63-14mcee and trichloroethylene; handled. HFC-63-14mcee and methanol: The pressure ratio, or compression ratio, of a compressoris HFC-63-14mcee and ethanol: the ratio of absolute discharge pressure to the absolute inlet HFC-63-14mcee and 2-methyl-2-propanol: pressure. Pressure delivered by a centrifugal compressor is HFC-63-14mcee and 2,2-dimethyl-1,3-dioxolane; practically constant over a relatively wide range of capacities. 10 HFC-63-14mcee and acetonitrile; Positive displacement compressors draw vapor into a HFC-63-14mcee and ethyl acetate; chamber, and the chamber decreases in Volume to compress HFC-63-14mcee and methyl propionate: the vapor. After being compressed, the vapor is forced from HFC-63-14mcee and n-propyl formate; the chamber by further decreasing the volume of the chamber HFC-63-14mcee and dimethylcarbonate: to Zero or nearly Zero. A positive displacement compressor 15 HFC-63-14mcee and isopropyl acetate; can build up a pressure, which is limited only by the volumet HFC-63-14mcee and 2.2.2-trifluoroethanol: ric efficiency and the strength of the parts to withstand the HFC-63-14mcee and isopropanol: pressure. HFC-63-14mcee and 2,2,3,3,3-pentafluoro-1-propanol: Unlike a positive displacement compressor, a centrifugal HFC-63-14mcee and 2,2,3,3-tetrafluoro-1-propanol; and compressor depends entirely on the centrifugal force of the HFC-63-14mcee and 1,1,1,3,3,3-hexafluoro-2-propanol. high-speed impeller to compress the vapor passing through These above-listed compositions are also suitable for use in the impeller. There is no positive displacement, but rather a multi-stage centrifugal compressor, preferably a two-stage what is called dynamic-compression. centrifugal compressor apparatus. The pressure a centrifugal compressor can develop The compositions of the present invention may be used in depends on the tip speed of the impeller. Tip speed is the speed 25 stationary air-conditioning, heat pumps or mobile air-condi of the impeller measured at its tip and is related to the diam tioning and refrigeration systems. Stationary air-conditioning eter of the impeller and its revolutions perminute. The capac and heat pump applications include window, ductless, ducted, ity of the centrifugal compressor is determined by the size of packaged terminal, chillers and commercial, including pack the passages through the impeller. This makes the size of the aged rooftop. Refrigeration applications include domestic or compressor more dependent on the pressure required than the 30 home refrigerators and freezers, ice machines, self-contained capacity. coolers and freezers, walk-in coolers and freezers and trans Because of its high-speed operation, a centrifugal com port refrigeration systems. pressor is fundamentally a high Volume, low-pressure The compositions of the present invention may addition machine. A centrifugal compressor works best with a low ally be used in air-conditioning, heating and refrigeration pressure refrigerant, such as trichlorofluoromethane (CFC 35 systems that employ fin and tube heat exchangers, micro 11) or 1.2.2-trichlorotrifluoroethane (CFC-113). channel heat exchangers and Vertical or horizontal single pass Large centrifugal compressors typically operate at 3000 to tube or plate type heat exchangers. 7000 revolutions per minute (rpm). Small turbine centrifugal Conventional microchannel heat exchangers may not be compressors are designed for high speeds, from about 40,000 ideal for the low pressure refrigerant compositions of the to about 70,000 (rpm), and have small impeller sizes, typi 40 present invention. The low operating pressure and density cally less than 0.15 meters. result in high flow velocities and high frictional losses in all A multi-stage impeller may be used in a centrifugal com components. In these cases, the evaporator design may be pressor to improve compressor efficiency thus requiring less modified. Rather than several microchannel slabs connected power in use. For a two-stage system, in operation, the dis in series (with respect to the refrigerant path) a single slab? charge of the first stage impeller goes to the Suction intake of 45 single pass heat exchanger arrangement may be used. There a second impeller. Both impellers may operate by use of a fore, a preferred heat exchanger for the low pressure refrig single shaft (or axle). Each stage can build up a compression erants of the present invention is a single slab? single pass heat ratio of about 4 to 1; that is, the absolute discharge pressure exchanger. can be four times the absolute Suction pressure. An example In addition to two-stage or other multi-stage centrifugal of a two-stage centrifugal compressor System, in this case for 50 compressor apparatus, the following compositions of the automotive applications, is described in U.S. Pat. No. 5,065, present invention are Suitable for use in refrigeration or air 990, incorporated herein by reference. conditioning apparatus employing a single slab? single pass The compositions of the present invention suitable for use heat exchanger: in a refrigeration or air-conditioning systems employing a HFC-63-14mcee and cyclohexane: centrifugal compressor comprise at least one of 55 HFC-63-14mcee and 2,2,3-trimethylbutane: HFC-63-14mcee and cyclohexane: HFC-63-14mcee and 2,4-dimethylpentane: HFC-63-14mcee and 2,2,3-trimethylbutane: HFC-63-14mcee and 3.3-dimethylpentane: HFC-63-14mcee and 2,4-dimethylpentane; HFC-63-14mcee and 2,3-dimethylpentane HFC-63-14mcee and 3.3-dimethylpentane; HFC-63-14mcee and 2-methylhexane: HFC-63-14mcee and 2,3-dimethylpentane 60 HFC-63-14mcee and 3-methylhexane, HFC-63-14mcee and 2-methylhexane: HFC-63-14mcee and isooctane; HFC-63-14mcee and 3-methylhexane, HFC-63-14mcee and 2-bromopropane: HFC-63-14mcee and isooctane; HFC-63-14mcee and 1-bromopropane: HFC-63-14mcee and 2-bromopropane; HFC-63-14mcee and 1,2-dichloroethane; HFC-63-14mcee and 1-bromopropane; 65 HFC-63-14mcee and 1,1-dichloroethane; HFC-63-14mcee and 1,2-dichloroethane; HFC-63-14mcee and fluorobenzene: HFC-63-14mcee and 1,1-dichloroethane; HFC-63-14mcee and o-difluorobenzene: US 7,476,331 B2 35 36 HFC-63-14mcee and m-difluorobenzene: absorbing heat. A vapor compression refrigeration system is HFC-63-14mcee and p-difluorobenzene: one example of such a heat sink. HFC-63-14mcee and trichloroethylene; HFC-63-14mcee and methanol: EXAMPLES HFC-63-14mcee and ethanol: HFC-63-14mcee and 2-methyl-2-propanol: In the following examples, HFC-63-14mcee is 1,1,1,2,2,3, HFC-63-14mcee and 2,2-dimethyl-1,3-dioxolane; 4.5,5,6,6,7,7,7-tetradecafluoroheptane, trans-DCE is trans-1, HFC-63-14mcee and acetonitrile; 2-dichloroethylene, MeOHis methanol, EtOH is ethanol, and HFC-63-14mcee and ethyl acetate; IPA is isopropanol. HFC-63-14mcee and methyl propionate; 10 HFC-63-14mcee and n-propyl formate; Example 1 HFC-63-14mcee and dimethylcarbonate; HFC-63-14mcee and isopropyl acetate; Fluorolubricant Solubility HFC-63-14mcee and 2.2.2-trifluoroethanol: HFC-63-14mcee and isopropanol: 15 The ability of HFC-63-14mcee to solubilize a fluorolubri HFC-63-14mcee and 2.2.3,3,3-pentafluoro-1-propanol: cant was determined in the following experiment. A known HFC-63-14mcee and 2,2,3,3-tetrafluoro-1-propanol; and amount of HFC-63-14mcee solvent was added to a beaker. A HFC-63-14mcee and 1,1,1,3,3,3-hexafluoro-2-propanol. known amount of lubricant (Krytox R GPL 100) was then The compositions of the present invention are particularly added to the beaker. More lubricant was added in incremental useful in Small turbine centrifugal compressors, which can be steps until the mixture was approximately 50 weight percent used in auto and window air-conditioning or heat pumps as solvent and 50 weight percent lubricant. The solution well as other applications. These high efficiency miniature remained clear with no haziness, cloudiness, or phase sepa centrifugal compressors may be driven by an electric motor ration. This experiment indicates that the Krytox R GPL 100 and can therefore be operated independently of the engine fluorolubricant is completely soluble in the HFC-63-14mcee speed. A constant compressor speed allows the system to 25 solvent at 50 weight percent and below. provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for efficiency improve Example 2 ments especially at higher engine speeds as compared to a conventional R-134a automobile air-conditioning system. Comparative Example When the cycling operation of conventional systems at high 30 driving speeds is taken into account, the advantage of these Disks are coated with fluorolubricant using two different low pressure systems becomes even greater. solvent systems. The solutions being used are 0.05 percent Some of the low pressure refrigerant fluids of the present (weight/weight) Fomblin Z-DolR) in Vertrel R. XF and 0.05 invention may be suitable as drop-in replacements for CFC percent (weight/weight) Fomblin Z-DolR) in HFC-63 113 in existing centrifugal equipment. 35 14mcee. In both cases, the fluorolubricant is completely mis The present invention further relates to a process for pro cible with the solvent. The disks are standard magnetic media, ducing refrigeration comprising evaporating the composi which are 95-mm nickel-phosphorus (NiP. about 10um thick) tions of the present invention in the vicinity of a body to be plated aluminum Substrates with magnetic coatings. On top of cooled, and thereafter condensing said compositions. the magnetic coatings are deposited a diamond-like-carbon The present invention further relates to a process for pro 40 (DLC) film. The disks are mounted vertically on a V-shaped ducing heat comprising condensing the compositions of the mandrel and dip coated in a bath of each of the solutions. The present invention in the vicinity of a body to be heated, and disks are pulled vertically out of the bath at a steady speed of thereafter evaporating said compositions. 1 mm/s. Evaporation of the solvent is accomplished using The present invention further relates to a process for trans standard techniques at about 40°C. fer of heat from a heat source to a heat sink wherein the 45 The resulting disks are examined visually and the presence compositions of the present invention serve as heat transfer of any irregularities is noted. The disk coated using the HFC fluids. Said process for heat transfer comprises transferring 63-14mcee? Fomblin. Z-DolR solution shows no evidence of the compositions of the present invention from a heat Source “rabbit ears’, while the disk coated with from the Vertrel(R) to a heat sink. XF/Fomblin Z-DolR solution exhibits the “rabbit ears' phe Heat transfer fluids are utilized to transfer, move or remove 50 OO. heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or Example 3 convection. A heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heat Distillation of HFC-63-14mcee?trans-DCE/methanol ing) from a remote refrigeration (or heating) system. In some 55 composition systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or con A solution containing about 24 weight percent HFC-63 dense). Alternatively, evaporative cooling processes may uti 14mcee, about 70 weight percent trans-1,2-dichloroethylene lize heat transfer fluids as well. (trans-DCE), and about 6 weight percent methanol (MeOH) Aheat Source may be defined as any space, location, object 60 was prepared in a suitable container and mixed thoroughly. or body from which it is desirable to transfer, move or remove The solution was distilled in a five plate Oldershaw distilla heat. Examples of heat Sources may be spaces (open or tion column (7 cm diameter, 40 cm height) using reflux ratio enclosed) requiring refrigeration or cooling, such as refrig as noted below. Head and pottemperatures were read directly erator or freezer cases in a Supermarket, building spaces to 1° C. The distillation was performed at a pressure of 760 requiring air-conditioning, or the passenger compartment of 65 mm Hg with 30 minutes between cuts. Distillate composi an automobile requiring air-conditioning. A heat sink may be tions were determined by gas chromatography. Results are defined as any space, location, object or body capable of summarized in Table 8. US 7,476,331 B2 38

TABLE 8

Composition (weight percent) Flask HFC-63-14mcee 21.8 + 0.1 weight percent Trans-DCE 73.8 + 0.2 weight percent HFC-63- Trans- Reflux temp Head Ethanol 4.4 + 0.06 weight percent Sample 14mcee DCE MeOH ratio (C.) temp (C.)

Cut 1 1834 73.53 8.13 20:1 40 40 Cut 2 18.30 73.55 8.15 20:1 40 40 Example 5 10 Cut 3 1894 73.04 8.02 15:1 40 40 Cut 4 19.09 72.92 7.99 10:1 40 40 Distillation of Cut S 1864 73.13 8.23 10:1 42 40 HFC-63-14mcee/trans-DCE/isopropanol Heel 27.66 67.73 4.61 Na l l8 composition 15 Analysis of the above data indicates small differences in A solution containing about 24 weight percent HFC-63 head temperatures and distillate compositions as the distilla 14mcee, about 70.0 weight percent trans-1,2-dichloroethyl tion progressed. A statistical analysis of the data demonstrates ene (trans-DCE), and about 6 weight percent isopropanol that the true ternary azeotrope of HFC-63-14mcee, trans (IPA) was prepared in a suitable container and mixed thor DCE, and methanol has the following characteristics at atmo oughly. The solution was distilled in a five plate Oldershaw spheric pressure: distillation column (7 cm diameter, 40 cm height) using a reflux ratio of 10:1. Head and pot temperatures were read directly to 1°C. The distillation was performed at a pressure HFC-63-14mcee 18.7 + 0.4 weight percent 25 of 760 mm Hg with 30 minutes between cuts. Distillate com Trans-DCE 73.2 + 0.3 weight percent positions were determined by gas chromatography. Results Methanol 8.1 + 0.1 weight percent are summarized in Table 10.

TABLE 10 30 Example 4 Composition (weight percent Distillation of HFC-63-14mcee?trans-DCE/ethanol HFC-63- Flask Head composition Sample 14mcee Trans-DCE IPA temp (C.) temp (C.) 35 Cut 1 22.46 75.11 2.43 46 45 Cut 2 22.55 7497 2.48 46 45 A solution containing about 24 weight percent HFC-63 Cut 3 22.60 74.91 2.49 46 45 14mcee, about 70 weight percent trans-1,2-dichloroethylene Cut 4 22.56 74.92 2.52 46 45 Cut S 22.61 74.84 2.55 46 45 (trans-DCE), and about 6 percent ethanol (EtOH) was pre Heel 26.OS 63.83 10.12 l8 l8 pared in a suitable container and mixed thoroughly. The solu tion was distilled in a five plate Oldershaw distillation column 40 (7 cm diameter, 40 cm height) using a reflux ratio of 10:1. Analysis of the above data indicates small differences in Head and pot temperatures were read directly to 1° C. The head temperatures and distillate compositions as the distilla distillation was performed at a pressure of 760 mm Hg with tion progressed. A statistical analysis of the data demonstrates 30 minutes between cuts. Distillate compositions were deter 45 that the true ternary azeotrope of HFC-63-14mcee, trans mined by gas chromatography. Results are summarized in DCE, and isopropanol has the following characteristics at Table 9. atmospheric pressure:

TABLE 9 50 Composition (weight percent HFC-63-14mcee 22.5 + 0.6 weight percent Trans-DCE 75.0 + 0.1 weight percent HFC-63- Flask Head Isopropanol 2.5 + 0.05 weight percent Sample 14mcee Trans-DCE EtOH temp (C.) temp (C.)

Cut 1 21.78 73.86 4.36 44 45 55 Cut 2 21.78 73.82 4.40 44 45 Example 6 Cut 3 21.71 73.88 4.41 44 45 Cut 4 21.88 73.64 4.48 44 45 Cut S 22.02 73.48 4...SO 44 45 Solubility Heel 26.68 65.56 7.76 l l8 60 Compositions of the present invention were tested for room Analysis of the above data indicates small differences in temperature solubility with mineral oil, motor oil (600W. head temperatures and distillate compositions as the distilla non-detergent) and rosin (water white). Solubility, in weight tion progressed. A statistical analysis of the data demonstrates percent, was measured by weighing and placing an amount of that the true ternary azeotrope of HFC-63-14mcee, trans 65 fluid in a suitable container, then slowly adding a composition DCE, and ethanol has the following characteristics at atmo of the present invention until the fluid is completely dis spheric pressure: solved. Results are shown in Table 11 below. US 7,476,331 B2 39 40 considered to be the solubility point or saturation point for TABLE 11 that residue in the present composition and is reported in grams residue per 100 grams of the present composition or Solubility (weight percent weight percent solubility. Composition (wt %) Mineral oil Motor oil Rosin HFC-63-14mcee?trans- 17 13 18 TABLE 13 DCE MeOH (20/746) Components Concentration (wt %) Kb value HFC-63-14mcee?trans- 11 14 HFC-63-14mcee?trans-DCE, MeOH 24.070.06.0 103 DCE MeOH 10 HFC-63-14mcee?trans-DCE, MeOH 18.773.28.1 >164 (24/70/6) HFC-63-14mcee?trans-DCE 20.080.0 66 HFC-63-14mcee?trans- 2O 21 HFC-63-14mcee?trans-DCE 24.076.0 59 DCE MeOH HFC-63-14mcee?CFOCH/trans- S.O.f40.O.S.S.O 46 (18.7/73.2/8.1) DCE HFC-63-14mcee?trans- 12 9 14 HFC-63-14mcee?CFOCHs/trans- 13.0/17.0/70.0 66 DCEEtOH 15 DCE (21.8/73.8/44) HFC-63-14mcee?CFOCHs/trans- 8,16.68.8 >2OO HFC-63-14mcee?trans-DCEFIPA 9 7 13 DCE MeOH (22.5/75.0/2.5)

The results show good solvency power of the present com Example 7 positions as demonstrated by high Kb values. Defluxing Performance Example 9 The compositions of the present invention are effective for cleaning ionic contamination (flux residue) from a surface. 25 Flammability The test used to determine surface cleanliness involved the following steps: The flammability of the compositions of the present inven 1. A rosin flux was painted liberally onto a FR-4 test board (an tion was evaluated by the Tag Closed Cup (ASTM D-56-82) epoxy printed wiring board with tracing made of tinned 30 test. The results are given in Table 14. copper). 2. The board so treated was then heated in an oven at about TABLE 1.4 175°C. for about 1-2 minutes to activate the rosin flux. 3. The board was then immersed in solder (Sné3, a 63/37 Composition Flash point Sn/lead solder) at about 200° C. for about 10 seconds. 35 No flash point 4. The board was then cleaned by immersion in the boiling cleaning composition for about 3 minutes and providing No flash point gentle movement of the board. The board was then immersed in a fresh bath of cleaning composition to rinse for about 2 minutes. 40 5. The board was then tested for residual ionics with an Example 10 Omega Meter 600 SMD ionic analyzer. The results are given in Table 12. Impact of Vapor Leakage TABLE 12 45 A vessel is charged with an initial composition at a tem Residual Ionics perature of 50° C., and the vapor pressure of the composition (Igrams NaCl sqin) is measured. The composition is allowed to leak from the Composition Flux - Alpha 611F (wt %) Board # (RMA) vessel, while the temperature is held constant at 50° C., until 50 50 weight percent of the initial composition is removed, at HFC-63-14mceef 1 14.9 which time the vapor pressure of the composition remaining Trans-DCE MeOH 2 16.4 (18.7/73.2/8.1) 3 11.4 in the vessel is measured. Mathmatically predicted results are 4 10.4 summarized in Table 15 below. 5 1O.S AVG 12.7 55 TABLE 1.5 Initial Initial After 50% After 50% Composition Pres. Pres. Leak Leak Delta Example 8 wt % (Psia) KPa Psia kPa P9%

Solvency Power 60 HFC-63-14mcee/trans-DCE/MeOH (50° C.) 1,945 2O.OS 138.2 18.60 128.2 7.2% A measure of “solvency power the ability of a solvent to 40.59.1 18.04 124.4 16.75 115.5 7.2% 1.69.30 20.03 138.1 18.38 126.7 8.2% dissolve an organic residue is the Kauri-Butanol value (Kb) 25/55/20 1981 136.6 18:42 127.0 7.0% determined by ASTM D-1133-94. The test was run by mea 10,7020 2011 138.7 19.70 135.8 2.0% Suring 10 grams of the present composition and adding an 65 10,80.10 2016 139.0 2011 138.7 O.2% oil/grease/fluid drop-wise until the solution becomes hazy 20/75/5 19.74 136.1 19.27 132.9 2.4% and non-homogeneous. The point of non-homogeneity is US 7,476,331 B2 41 42

TABLE 15-continued TABLE 16-continued Initial Initial After 50% After 50% Vapor Pressure Composition Pres. Pres. Leak Leak Delta wt % (Psia) KPa Psia kPa P9% A. er 50% After 50% Composition Initial P Initial P Leak Leak Delta P 20,65.15 2O.OO 37.9 9.70 35.8 1.5% (wt % A?wt % B) (Psia) (kPa) (Psia) (kPa) (%) 2079, 8.22 25.6 6.69 S.1 8.4% HFC-63-14mcee/trans-DCE/EtOH (50° C.) 39,61 4.65 O1.O 3.66 94.2 6.8% 38.62 4.65 O1.O 2.97 89.4 11.5% 1,945 6.94 6.8 6.84 6.1 O.6% 10 HFC-63-14mcee, 2,4-dimethylpentane (69.4° C.) 40,59. 7.13 8.1 6.67 4.9 2.7% 1779.20 6.65 4.8 5.94 O9.9 4.3% 60.639.4 4.70 O1.4 4.70 101.4 O.0% 25/55/20 7.12 8.O 6.OS 0.7 6.3% 7030 4.68 O1.2 4.61 100.7 O.S90 10,7020 7.14 8.2 S.90 O9.6 7.2% 75/25 4.63 OO.9 4.36 99.0 1.8% 10,80.10 7.40 2O.O 7.05 7.6 2.0% 80.2O 453 OO.2 3.68 94.3 5.8% 20.75/5 7.58 21.2 7.54 20.9 O.2% 15 82.18 4.45 99.6 3.15 90.7 9.0% 20,65.15 7.38 9.8 6.95 6.9 2.5% 83/17 4.41 99.4 2.79 88.2 11.2% 2079, 7.05 7.6 6.73 5.4 1.9% 50/50 4.69 O1.3 4.65 101.0 O.3% HFC-63-14mcee/trans-DCE/IPA (50° C.) 40.60 4.66 O1.1 4.16 97.6 3.4% 39,61 4.66 O1.1 3.80 95.1 5.9% 1,945 6.24 2.0 6.19 1.6 O.3% 38.62 4.66 O1.1 3.09 90.3 10.7% 40,59. 6.58 4.3 6.47 3.6 O.7% HFC-63-14mcee/3,3-dimethylpentane (72.8° C.) 1779.20 5.71 O8.3 4.92 O2.9 S.0% 25/55/20 S.82 O9.1 4.38 99.1 9.1% 65.1,34.9 4.68 O1.2 4.68 101.2 O.0% 10,7020 5.95 O.O 4.91 O2.8 6.5% 75/25 4.64 OO.9 4...SO 1OOO 1.0% 10,80.10 6.42 3.2 6.13 1.2 1.8% 80.2O 4.SS OO.3 4.OS 96.9 3.4% 20.75/5 6.68 S.O 6.65 4.8 O.2% 8416 4.41 99.4 3.13 90.5 8.9% 20,65.15 6.21 1.8 S.61 O7.6 3.7% 85.15 4.35 98.9 2.75 87.9 11.1% 2079, 6.63 4.7 6.60 4.5 O.2% 25 50/50 4.65 O1.O 4.SS 100.3 O.7% 42.58 4.62 OO.8 3.26 91.4 9.3% HFC-63-14mcee, 2,3-dimethylpentane (75.4° C.) Analysis of the above data shows the difference in vapor pressure between the original composition and the composi 68.431.6 4.66 O1.1 4.66 101.1 O.0% tion remaining after 50 weight percent has been removed is 80.2O 4.57 OO.S 4.27 98.4 2.1% 30 85.15 4.40 99.3 3.30 91.7 7.6% less then about 10 percent for compositions of the present 86.14 4.34 98.9 2.95 89.3 9.7% invention. 87.13 4.27 98.4 2.53 86.4 12.2% 50/50 4.61 OO.7 4.44 99.6 1.2% Example 11 45/55 4.59 OO.6 3.51 93.1 7.4% 4456 4.58 OO.S 2.38 85.4 15.1% Impact of Vapor Leakage on Vapor Pressure 35 HFC-63-14mcee, 2-methylhexane (75.4° C.) 68.3:31.7 4.70 O1.4 4.70 101.4 O.0% A vessel is charged with an initial composition at a speci 80.2O 4.61 OO.7 4.30 98.6 2.1% fied temperature, and the initial vapor pressure of the compo 85.15 4.44 99.6 3.33 91.9 7.70% 86.14 4.38 99.1 2.97 89.4 9.8% sition is measured. The composition is allowed to leak from 40 50/50 4.65 O1.O 4.48 99.8 1.2% the vessel, while the temperature is held constant, until 50 45/55 4.63 OO.9 3.58 93.6 7.2% weight percent of the initial composition is removed, at which 4456 4.62 OO.8 2.50 86.2 14.5% time the vapor pressure of the composition remaining in the HFC-63-14mcee/3-methylhexane (76.4° C.) vessel is measured. Mathematically predicted results are summarized in Table 16 below. 45 69.630.4 4.69 O1.3 4.69 101.3 O.0% 80.2O 4.61 OO.7 4.37 99.1 1.6% 86.14 4.40 99.3 3.2O 91.0 8.3% TABLE 16 87.13 4.33 98.8 2.82 88.4 10.5% 50/50 4.62 OO.8 4.41 99.4 1.4% Vapor Pressure 46, SS 4.6O OO.7 3.49 93.0 7.6% After 50% After 50% 50 45/55 4.6O OO.7 2.25 84.5 16.1% Composition Initial P Initial P Leak Leak Delta P HFC-63-14mceein-heptane (80.5°C.) (wt % A?wt % B) (Psia) (kPa) (Psia) (kPa) (%) 74.9.25.1 4.71 O1.4 4.71 101.4 O.0% HFC-63-14mcee? cyclohexane (71.5°C.) 85.15 4.58 OO.S 4.18 97.8 2.7% 89.11 4.35 98.9 3.14 90.6 8.4% 61.138.9 14.69 101.3 4.69 101.3 O.0% 55 90.10 4.25 98.3 2.72 87.7 10.7% 80.2O 14.42 99.4 3.63 94.0 5.5% 60,40 4.64 OO.9 4.51 1OOO O.9% 82.18 14.32 98.7 3.19 90.9 7.9% 55.45 4.61 OO.7 4.38 99.1 1.6% 83/17 14.25 98.3 2.92 89.1 9.3% S1.49 4.58 OO.S 3.80 95.1 5.3% 8416 14.17 97.7 2.60 86.9 11.1% 50/50 4.58 OO.S 3.02 89.8 10.7% 40, 60 14.63 100.9 4.28 98.5 2.4% 39, 61 14.62 100.8 4.O3 96.7 4.0% HFC-63-14mcee? methylcyclohexane (80.4° C.) 38.62 14.62 100.8 3.38 92.3 8.5% 60 HFC-63-14mcee, 2,2,3-trimethylbutane (69.5°C.) 73.2.26.8 4.71 O1.4 4.71 101.4 O.0% 85.15 4.52 OO.1 4.OO 96.5 3.6% 60.8.39.2 14.70 101.4 4.70 101.4 O.0% 88.12 4.32 98.7 3.25 91.4 7.59% 80.2O 14.53 1OO.2 3.70 94.5 5.7% 89.11 4.23 98.1 2.91 89.0 9.3% 82.18 14.45 99.6 3.17 90.8 8.9% 60,40 4.65 O1.O 4.54 100.3 O.8% 83/17 14.41 99.4 2.82 88.4 11.0% 65 50/50 4.58 OO.S 4.33 98.8 1.7% 40, 60 14.66 101.1 4.OS 96.9 4.2% 48,52 4.57 OO.S 3.91 95.9 4.5%

US 7,476,331 B2 49 50 less difference between the vapor pressure of the original TABLE 16-continued composition and the composition remaining after 50% has been removed. Vapor Pressure

After 50% After 50% Example 12 Composition Initial P Initial P Leak Leak Delta P (wt % A?wt % B) (Psia) (kPa) (Psia) (kPa) (%) Distillation of a HFC-63-14mcee/trans-DCE composition 60,40 3.77 94.9 2.86 88.7 6.6% 6436 3.61 93.8 2.36 85.2 9.2% 10 65.35 3.57 93.6 2.2O 84.1 10.1% A solution containing about 20 weight percent HFC-63 HFC-63-14mcee? (CF)2CBrC(O)CFCF (94.1° C.) 14mcee and about 80 weight percent trans-1,2-dichloroeth 64.635.4 4.69 101.3 4.69 101.3 O.0% ylene (trans-DCE) was prepared in a suitable container and 80.2O 4.63 100.9 4.63 100.9 O.0% mixed thoroughly. The solution was distilled in a five plate 15 90.10 453 1OO.2 4.52 100.1 O.1% Oldershaw distillation column (7 cm diameter, 40 cm height) 99.1 4.38 99.1 4.38 99.1 O.0% using a 10:1 reflux ratio. Head and pottemperatures were read 40, 60 4.54 100.3 4.52 100.1 O.1% 20.80 4.18 97.8 4.13 97.4 O.4% directly to 1°C. The distillation was performed at a pressure 10.90 3.90 95.8 3.86 95.6 O.3% of 760 mm Hg with about 30 minutes between cuts. Distillate 1.99 3.59 93.7 3.58 93.6 O.1% compositions were determined by gas chromatography. HFC-63-14mcee/DMTP (90.0° C.) Results are summarized in Table 17.

6.293.8 1.89 82.O 1.89 82.O O.0% TABLE 17 1.99 1.89 82.O 1.89 82.O O.0% Of 100 1.89 82.O 1.89 82.O O.0% 20.80 1.91 82.1 1.91 82.1 O.0% 25 Composition (weight percent) in 40, 60 1.98 82.6 1.98 82.6 O.0% cut Head 60,40 2.12 83.6 2.11 83.5 O.1% 80.2O 2.31 84.9 2.30 84.8 O.1% Sample HFC-63-14mcee Trans-DCE temp (C.) 90.10 2.45 85.8 2.45 85.8 O.0% 99.1 2.54 86.5 2.54 86.5 O.0% 30 Cut 1 24.03 75.97 45 1OOO 2.55 86.5 2.55 86.5 O.0% Cut 2 23.84 76.16 45 HFC-63-14mcee?CFOCH/trans-DCE (50° C.) Cut 3 23.48 76.52 45 Cut 4 23.49 76.51 45 1 98.1 O.84 74.7 O.S3 72.6 2.9% Cut S 23.62 76.38 45 1.1.98 6.OS 0.7 5.94 109.9 O.7% 2O2O60 6.79 5.8 6.70 115.1 O.S90 35 Heel 17.07 79.71 l8 10.10.80 6.73 5.4 6.63 114.7 O.6% 3O3O40 6.47 3.6 5.81 109.0 4.0% 4020.40 6.37 2.9 5.67 108.0 4.3% Analysis of the above data indicates small differences in 20:40, 40 6.59 4.4 6.O1 110.4 3.5% head temperatures and distillate compositions as the distilla 2O.S.O.30 6.13 1.2 4.91 102.8 7.6% 40 tion progressed. A statistical analysis of the data demonstrates SOf 10.40 6.28 2.2 S.62 107.7 4.1% that the true azeotrope of HFC-63-14mcee and trans-DCE has 60.1,39 6.2O 1.7 5.57 107.4 3.9% 65,1.34 6.09 O.9 S.OO 103.4 6.8% the following characteristics at atmospheric pressure: 68.1,31 6.OO O.3 4.46 99.7 9.6% 1,80.19 5.27 O5.3 3.97 96.3 8.5% 45 1,83.16 4.83 O2.2 340 92.4 9.6% HFC-63-14mcee 23.7 + 0.2 weight percent 1,84f15 4.66 O1.1 3.2O 91.0 10.0% Trans-DCE 76.3 + 0.2 weight percent HFC-63-14mcee?CFOCHs/trans-DCE (50° C.)

1.1.98 6.OS 0.7 5.93 109.8 O.7% 50 2O2O60 6.93 6.7 6.86 116.2 O.4% Example 13 10.10.80 6.81 5.9 6.66 114.9 O.9% 4020.40 6.59 4.4 6.10 111.0 3.0% Distillation of a HFC-63-14mcee? trans-DCE/ 3O3O40 6.72 5.3 6.26 112.1 2.8% CFOCHs composition 20:40, 40 6.83 6.O 6.40 113.1 2.6% 2O.S.O.30 6.56 4.2 5.24 105.1 8.0% 55 SO2O3O 6.29 2.3 5.79 108.9 3.1% A solution containing about 20 weight percent HFC-63 SOf 10.40 6.42 3.2 5.89 109.6 3.2% 14mcee, about 60 weight percent trans-1,2-dichloroethylene 60.1,39 6.22 1.8 5.60 107.6 3.8% (trans-DCE), and about 20 weight percent CFOCHs was 68.1,31 6.02 O.S 4.51 1OOO 9.4% prepared in a suitable container and mixed thoroughly. The 1, 70.29 6.62 4.6 S.18 104.7 8.7% 60 1,71 28 6.56 4.2 4.95 103.1 9.7% solution was distilled in a five plate Oldershaw distillation column (7 cm diameter, 40 cm height) using a 10:1 reflux ratio. Head and pot temperatures were read directly to 1° C. The mathematically predicted results show the difference The distillation was performed at a pressure of 760 mm Hg in vapor pressure between the original composition and the 65 with about 30 minutes between cuts. Distillate compositions composition remaining after 50 weight percent has been were determined by gas chromatography. Results are sum removed. Compositions of the invention have about a 10% or marized in Table 18. US 7,476,331 B2 52 The above data illustrates the usefulness of the present com TABLE 18 positions for removing different types of oil residues.

Composition (weight percent) Example 15 in cut Defluxing Performance HFC-63- Trans- Head Following the procedure of Example 7, the defluxing effi Sample 14mcee DCE CFOC2H5 temp (C.) ciency of the HFC-63-14mcee/trans-DCE azeotrope was 10 tested using Alpha 611F RMA flux. Cut 1 11.14 72.96 15.90 44 The residual ionics found on the board are given in Table Cut 2 11.82 71.44 16.74 45 2O. Cut 3 12.44 70.57 16.99 45 Cut 4 12.44 70.43 17.13 45 TABLE 20 15 Cut S 12.55 70.38 17.07 45 Residual Ionics Heel 30.49 43.63 25.88 Na (grams NaCl sqin) Composition Flux - Alpha 611F (wt %) Board # (RMA) Analysis of the above data indicates small differences in HFC-63- 1 26.3 14mcee?trans- 2 49.8 head temperatures and distillate compositions as the distilla DCE 3 28.7 tion progressed. A statistical analysis of the data demonstrates (24/76) 4 3O.O that the true ternary azeotrope of HFC-63-14mcee, trans 5 3O.O DCE, and CFOCH has the following characteristics at AVG 33.2 atmospheric pressure: 25 Example 16 HFC-63-14mcee 12.1 + 0.6 weight percent Cleaning Trans-DCE 71.1 + 1.0 weight percent 30 CFOCHs 16.8 + 0.5 weight percent The compositions of the present invention are effective for cleaning ionic contamination (flux residue) from a Surface. A similar procedure to the one described for Example 15 was Example 14 used to apply the residue and then remove it from the surface. 35 The cleaning ability was determined by weighing the board Solubility prior to deposition of the flux, after the deposition of the flux and then after the cleaning procedure. Compositions of the present invention were tested for room The results for Alpha 611F RMA are given in Table 21. temperature solubility with mineral oil, silicone oil (DC 200, 40 Dow Corning, Midland, Mich.), and hydraulic fluid (mineral TABLE 21 oil based). Solubility, in weight percent, was measured by Post dry weighing and placing an amount of fluid in a suitable con Composition Dry weight Wet weight weight % soil tainer, then slowly adding a composition of the present inven (wt %) (grams) (grams) (grams) removed tion until the fluid is completely dissolved. Results, in weight 45 HFC-63- 21.4973 21.506S 21.4976 97% 14mcee 21.4113 214211 21.4116 97% percent soluble, are shown in Table 19 below. trans-DCE 21.0752 21.0878 21.0755 98% (24/76) 21.76O1 21.7756 21.7604 98% TABLE 19 21.0745 21.0946 21.0752 97% Average 97% Solubility (weight percent 50 Mineral DC 200 DC 200 Hydraulic Composition (wt %) oil (5 cSt) (350 cSt) Fluid Example 17 HFC-63-14mcee?trans- 7 l l8 l DCE 55 Metal Cleaning Efficacy (20/80) HFC-63-14mcee?trans- 4 >88 13 4 DCE Stainless steel (type 316)2"x3" coupons that have been grit (24/76) blasted to provide an unpolished surface were pre-cleaned HFC-63-14mcee?trans- 17 >90 >90 17 and oven dried to remove any residual soil. Each coupon was DCE/CFOCHs (13/70/17) 60 weighed to 4 places to obtain a tare weight. A small amount of HFC-63-14mcee?trans- 11 >90 >90 11 mineral oil was applied with a Swab, the coupon is then DCE/CFOCH weighed to obtain the “loaded weight. The coupon was then (5/40/55) cleaned by immersion into a boiling cleaning composition for HFC-63-14mcee?trans- 29 >90 >90 27 DCE/CFOCH/MeOH 1 minute, held in vapor for 30 seconds and then air dried for (8/68/16/8) 65 1 minute. The coupon was then weighed and the percent of soil removed is calculated using the 3 recorded weights. The results are shown in Table 22. US 7,476,331 B2 53 54 a. 18.7 weight percent HFC-63-14mcee, 73.2 weight per TABLE 22 cent trans-1,2-dichloroethylene, and 8.1 weight percent methanol having a vapor pressure of about 14.7 psia Post Dry (101 kPa) at a temperature of about 40°C.; Composition Dry weight Wet weight weight Percent Soil b. 21.8 weight percent HFC-63-14mcee, 73.8 weight per (wt %) (grams) (grams) (grams) removed cent trans-1,2-dichloroethylene, and 4.4 weight percent HFC-63- 21.4973 21.506S 21.4976 97 ethanol having a vapor pressure of about 14.7 psia (101 14mcee? 21.4113 21.4211 21.4116 97 trans-DCE 21.0752 21.0878 21.0755 98 kPa) at a temperature of about 45° C.; and (24/76) 21.76O1 21.7756 21.7604 98 c. 22.5 weight percent HFC-63-14mcee, 75.0 weight per 21.0745 21.0946 21.0752 97 10 cent trans-1,2-dichloroethylene, and 2.5 weight percent Average 97 isopropanol having a vapor pressure of about 14.7 psia HFC-63- 214974 21.5133 21.4976 99 14mcee? 21.76OO 21.7730 21.76O2 98 (101 kPa) at a temperature of about 45° C. CFOC2H5. 21.4112 2142O6 21.4114 98 4. A process for removing residue from a surface or Sub trans-DCE 21.0750 21.0957 21.0752 99 strate, comprising: (13/17/70) 21.5529 21.5724 21.5531 99 15 a. contacting the Surface or Substrate with the composition Average 99 of claims 1, 2, or 3, and b. recovering the Surface or Substrate from the composition. The results show efficient removal of mineral oil residue from 5. An azeotropic or azeotrope-like composition compris 1ng: stainless steel Surfaces by the compositions of the present about 1 to about 68 weight percent HFC-63-14mcee and invention. about 99 to about 32 weight percent trans-1,2-dichloro Example 18 ethylene. 6. The composition of claim 5, wherein said composition is Flammability an azeotrope comprising: 25 24.0 weight percent HFC-63-14mcee and 76.0 weight per The flammability of the compositions of the present inven cent trans-1,2-dichloroethylene having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about tion was evaluated by the Tag Closed Cup (ASTM D-56-82) 45.0° C. test. The results are given in Table 24. 7. A process for removing residue from a surface, compris 30 1ng: TABLE 23 a. contacting the Surface with the composition of claim 5 or Composition Flash point 6, and b. recovering the Surface from the composition. HFC-63-14mcee?trans-DCE. No flash point CFOCHs 8. The process of claim 7 wherein said residue comprises (13/70/17) 35 an oil. HFC-63-14mcee?trans-DCE. No flash point 9. The process of claim 7 wherein said residue comprises a CFOCH/MeOH rosin flux. (8/68/16/8) 10. The process of claim 7 wherein the surface is an inte grated circuit device. 40 11. The composition of claim 5, or 6, further comprising a What is claimed is: stabilizer, a water scavenger, and/or an odor masking agent. 1. An azeotropic or azeotrope-like composition compris 12. The composition of claim 11 wherein said stabilizer is ing: selected from the group consisting of nitromethane, hindered a. HFC-63-14mcee: phenols, hydroxylamines, thiols, phosphites and lactones. b. trans-1,2-dichloroethylene; and 45 13. The composition of claim 11 wherein said water scav c. at least one alcohol selected from the group consisting of enger is an ortho ester. methanol, ethanol, and isopropanol. 14. The composition of claim 1, 2,5 or 6 further comprising 2. The composition of claim 1, wherein said azeotropic or an aerosol propellant. azeotrope-like composition is selected from the group con 15. The composition of claim 14 further comprising an sisting of: 50 aerosol propellant selected from the group consisting of air, a. from about 1 weight percent to about 40 weight percent nitrogen, carbon dioxide, dimethylether, difluoromethane, of HFC-63-14mcee, from about 55 weight percent to trifluoromethane, difluoroethane, trifluoroethane, tetrafluo about 94 weight percent trans-1,2-dichloroethylene, and roethane, pentafluoroethane, heptafluoropropane, and pen from about 1 weight percent to about 30 weight percent tafluoropropane. methanol; 55 16. The composition of claim 5 or 6 further comprising at b. from about 1 weight percent to about 40 weight percent least one ultra-violet fluorescent dye selected from the group of HFC-63-14mcee, from about 55 weight percent to consisting of naphthalimides, perylenes, coumarins, about 94 weight percent trans-1,2-dichloroethylene, and anthracenes, phenanthracenes, Xanthenes, thioxanthenes, from about 1 weight percent to about 30 weight percent naphthoxanthenes, fluoresceins, derivatives of said dye and ethanol; and 60 combinations thereof. c. from about 1 weight percent to about 40 weight percent 17. The composition of claim 16, further comprising at of HFC-63-14mcee, from about 55 weight percent to least one solubilizing agent selected from the group consist about 94 weight percent trans-1,2-dichloroethylene, and ing of hydrocarbons, dimethylether, polyoxyalkylene glycol from about 1 weight percent to about 30 weight percent ethers, amides, ketones, nitriles, chlorocarbons, esters, lac isopropanol. 65 tones, aryl ethers, hydrofluoroethers, and 1,1,1-trifluoroal 3. The composition of claim 1, wherein said composition is kanes; and wherein the refrigerant and solubilizing agent are an azeotrope selected from the group consisting of not the same compound. US 7,476,331 B2 55 56 18. The composition of claim 17, wherein said solubilizing h) fluoroethers represented by the formula R'OCFCF.H. agent is selected from the group consisting of: wherein R' is selected from aliphatic and alicyclic a) polyoxyalkylene glycol ethers represented by the for hydrocarbon radicals having from about 5 to about 15 mula R' (OR), OR l, wherein: X is an integer from 1 to carbon atoms; or wherein said fluoroethers are derived 3; y is an integer from 1 to 4: R is selected from hydro from fluoro-olefins and polyols, wherein said fluoro gen and aliphatic hydrocarbon radicals having 1 to 6 olefins are of the type CF-CXY, wherein X is hydro carbon atoms and y bonding sites; R is selected from gen, chlorine or fluorine, and Y is chlorine, fluorine, CF aliphatic hydrocarbylene radicals having from 2 to 4 or OR, wherein R, is CF, CFs, or CF; and said carbon atoms; R is selected from hydrogen, and ali polyols are of the type HOCHCRR'(CH4)(CHOH), phatic and alicyclic hydrocarbon radicals having from 1 10 CH(CH-OH), wherein R and Rare hydrogen, CH, or to 6 carbon atoms; at least one of R' and R is selected CHs, X is an integer from 0-4, y is an integer from 0-3 from said hydrocarbon radicals; and wherein said poly and Z is either Zero or 1; and oxyalkylene glycol ethers have a molecular weight of i) lactones represented by structures B, C, and ID: from about 100 to about 300 atomic mass units: b) amides represented by the formulae RC(O)NR'R'' and 15 cyclo-IRC(O)N(R)-1, wherein R', R, R and Rare independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbonatoms, and at most one aromatic radical having from 6 to 12 carbonatoms; R is selected from aliphatic hydrocarby lene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units: c) ketones represented by the formula RC(O)R’, wherein R" and R are independently selected from aliphatic, 25 alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units: d) nitriles represented by the formula RCN, wherein R' is 30 selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units: e) chlorocarbons represented by the formula RCI, wherein 35 X is 1 or 2: R is selected from aliphatic and alicyclic 2. hydrocarbon radicals having from 1 to 12 carbonatoms; aR6 IV-5 and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units: 40 wherein, R through Rs are independently selected from f) aryl ethers represented by the formula R'OR, wherein: hydrogen, linear, branched, cyclic, bicyclic, Saturated and R" is selected from aryl hydrocarbon radicals having unsaturated hydrocarbyl radicals; and the molecular weight is from 6 to 12 carbonatoms; R is selected from aliphatic from about 100 to about 300 atomic mass units; and hydrocarbon radicals having from 1 to 4 carbon atoms; j) esters represented by the general formula RC(O)CR, and wherein said aryl ethers have a molecular weight of 45 wherein R' and Rare independently selected from lin from about 100 to about 150 atomic mass units: ear and cyclic, Saturated and unsaturated, alkyl and aryl g) 1,1,1-trifluoroalkanes represented by the formula radicals; and wherein said esters have a molecular CFR', wherein R' is selected from aliphatic and alicy weight of from about 80 to about 550 atomic mass units. clic hydrocarbon radicals having from about 5 to about 15 carbon atoms; k k k k k