USOO891. 1640B2

(12) United States Patent (10) Patent No.: US 8,911,640 B2 Nappa et al. (45) Date of Patent: Dec. 16, 2014

(54) COMPOSITIONS COMPRISING 5,736,063 A 4/1998 Richard et al. FLUOROOLEFNS AND USES THEREOF 5,744,052 A 4/1998 Bivens 5,788,886 A 8, 1998 Minor et al. 5,897.299 A * 4/1999 Fukunaga ...... 417.316 (71) Applicant: E I du Pont de Nemours and 5,969,198 A 10/1999 Thenappan et al. Company, Wilmington, DE (US) 6,053,008 A 4/2000 Arman et al. 6,065.305 A 5/2000 Arman et al. (72) Inventors: Mario Joseph Nappa, Newark, DE 6,076,372 A 6/2000 Acharya et al. 6,111,150 A 8/2000 Sakyu et al. (US); Barbara Haviland Minor, Elkton, 6,176,102 B1 1/2001 Novak et al. MD (US); Allen Capron Sievert, 6,258,292 B1 7/2001 Turner Elkton, MD (US) 6,300,378 B1 10/2001 Tapscott 6.426,019 B1 7/2002 Acharya et al. (73) Assignee: E I du Pont de Nemours and 6,610,250 B1 8, 2003 Tuma Company, Wilmington, DE (US) 6,858,571 B2 2/2005 Pham et al. 6,969,701 B2 11/2005 Singh et al. 7,708,903 B2 5, 2010 Sievert et al. *) Notice: Subject to anyy disclaimer, the term of this 8,012,368 B2 9/2011 Nappa et al. patent is extended or adjusted under 35 8,070,976 B2 12/2011 Nappa et al. U.S.C. 154(b) by 0 days. 2003/0042463 A1 3/2003 Arman et al. 2003/0209685 A1 11/2003 Robin et al. (21) Appl. No.: 13/850,338 2004.0089839 A1 5, 2004 Thomas et al. 2004/01 19047 A1 6/2004 Singh et al. 2004/O127383 A1 7/2004 Pham et al. (22) Filed: Mar. 26, 2013 2004/O256594 A1 12/2004 Singh et al. 2005/OO775O1 A1 4/2005 Pham et al. (65) Prior Publication Data 2005/0090698 A1 4/2005 Merkeletal. 2005/0156135 A1 7/2005 Minor et al. US 2013/021.3063 A1 Aug. 22, 2013 2005/0233923 A1 10/2005 Singh et al. 2005/0233.931 A1 10/2005 Singh et al. Related U.S. Application Data (Continued) (62) Division of application No. 13/286,765, filed on Nov. FOREIGN PATENT DOCUMENTS 1, 2011, now Pat. No. 8,425,795, which is a division of application No. 12/696,793, filed on Jan. 29, 2010, CN 1083474 C 4/2004 now Pat. No. 8,070,976, which is a division of EP O 67O 295 A1 9, 1995 application No. 1 1/589,588, filed on Oct. 30, 2006, (Continued) now Pat. No. 7,708,903. OTHER PUBLICATIONS (60) Provisional application No. 60/732,581, filed on Nov. 1, 2005. Chemical Abstracts, vol. 119, No. 10, Sep. 6, 1993, Columbus, Ohio, US; abstract No. 98469, Fujiwara et al. “2-trifluoromethyl-3,3,3- (51) Int. Cl. trifluoropropene” XP002431016. C09K3/04 (2006.01) Grzyll, L. R. et al., “Development of Nontoxic Heat Transport Fluids F25B I/O (2006.01) for Habitat Two-Phase Thermal Control Systems”. Energy Conver sion Engineering Conference, 1996. IECEC96. Proceedings of the (52) U.S. Cl. 31st Intersociety Washington, DC; Aug. 11-16, 1996, New York, NY: CPC. F25B I/00 (2013.01); C09K5/045 (2013.01); IEEE vol. 2, pp. 1506-1511 (Aug. 11, 2006). C09K2205/126 (2013.01) HaSZeldine, R. N., et al., “Free-Radical Additions to Unsaturated USPC ...... 252/67 Systems. Part SVII. Reaction of Trifluoroiodomethane with Mixtures (58) Field of Classification Search of Ethylene and Vinyl Fluoride and of Ethylene and Propene'. Chem USPC ...... 252/67 istry Department, University of Manchester Institute of Science and See application file for complete search history. Technology, Manchester M60 1CRD. J. Chem. Soc. (C), 1970, pp. 414-421 (1970). (56) References Cited (Continued) U.S. PATENT DOCUMENTS Primary Examiner — John Hardee 2.931,840 A 4, 1960 Marquis 2.996,555 A 8, 1961 Rausch 3,683,009 A 8, 1972 Middleton (57) ABSTRACT 3,723,318 A 3, 1973 Butler 3,884.828 A 5, 1975 Butler The present invention relates to fluoroolefin compositions. 4,126,631 A 11/1978 Krespan et al. The fluoroolefin compositions of the present invention are 4,788,352 A 1 1/1988 Smutiny useful as refrigerants or heat transfer fluids and in processes 5,037,573 A 8, 1991 Merchant 5,254,280 A 10, 1993 Thomas et al. for producing cooling or heat. Additionally, the fluoroolefin 5,421,192 A 6/1995 Henry compositions of the present invention may be used to replace 5,516,946 A 5, 1996 Jackson et al. currently used refrigerant or heat transfer fluid compositions 5,532,419 A 7/1996 Van Der Puy et al. that have higher global warming potential. 5,616,275 A 4/1997 Chisolm et al. 5,679,875 A 10/1997 Aoyama et al. 5,714,655 A 2, 1998 Yamamoto et al. 12 Claims, No Drawings US 8,911,640 B2 Page 2

(56) References Cited OTHER PUBLICATIONS U.S. PATENT DOCUMENTS Henne, A. L., et al., “Fluorinated Derivatives of Propane and Propylene'. Department of Chemistry, The Ohio State University, 2005/0233932 A1 10, 2005 Singh et al. 2005/0233933 A1 10, 2005 Singh et al. vol. 68, pp. 496-497 (Mar. 1946). 2005/0233934 A1 10, 2005 Singh et al. International Search Report (Date of Mailing: May 14, 2007). 2005/0241805 A1 11, 2005 Singh et al. Knunyants, I. L., et al., “Reactions of Fluoro Olefins, Communica 2005.0245421 A1 11, 2005 Singh et al. tion 13. Catalytic Hydrogenation of Perfluoro Olefins'. Institute of 2005/0247905 A1 11/2005 Singh et al. Heteroorganic Compounds, Academy of Sciences of the USSR, 2006/0010872 A1 1, 2006 Singh et al. 2006/0022166 A1 2, 2006 Wilson et al. Otdelenie Khimicheskikh Nauk, No. 8, pp. 1312-1317. (Aug. 1960). 2006.0025322 A1 2, 2006 Wilson et al. Tarrant, P. et al., “Free Radical Additions Involving Fluorine Com 2006.0043330 A1 3, 2006 Wilson et al. pounds. IV. The Addition of Dibromodifluoromethane to Some 2006.0043331 A1 3, 2006 Shankland et al. Fluoroolefins'. Department of Chemistry, University of Florida, pp. 2007/OO96051 A1 5/2007 Nappa et al. 2783-2787 (May 20, 1955). 2007/0098646 A1 5/2007 Nappa et al. Vineyard, E. A., et al., “Selection of Ozone-Safe, Nonazeotropic 2012/0042668 A1 2, 2012 Nappa et al. Refrigerant Mixtures for Capacity Modulation in Residential Heat Pumps'. ASHRAE Transactions, Technical and Symposium Papers, FOREIGN PATENT DOCUMENTS Chicago Technical Program, vol.95, Part 1, pp. 34-46 (Jan. 29, 1989). Written Opinion of the International Searching Authority (Date of EP 1 O16839 A2 T 2000 EP 1 191080 A2 3, 2002 Mailing: May 14, 2007). EP 1686 111 A1 8, 2006 Office Action mailed Mar. 16, 2010, in co-pending U.S. Appl. No. JP O3-255.039 A 11, 1991 12,696,793. JP 4-1 10388 A 4f1992 Office Action mailed Jun. 29, 2010, in co-pending U.S. Appl. No. JP 1993O85970 A 4f1993 12,696,793. JP 11292.807 A 10, 1999 Office Action mailed Jul. 13, 2010, in co-pending U.S. Appl. No. JP 2002-228307. A 8, 2002 12,696,793. JP 2002318038 A 10, 2002 Office Action mailed Dec. 6, 2010, in co-pending U.S. Appl. No. RU 2O73058 C1 2, 1997 12,696,793. WO 93.16O23 A1 8, 1993 Office Action mailed Mar. 16, 2010, in co-pending U.S. Appl. No. WO 97.31080 A1 8, 1997 WO 98.43933 A 10, 1998 12,696,839. WO 2004/O37752 A2 5, 2004 Office Action mailed Jul. 13, 2010, in co-pending U.S. Appl. No. WO 2004/O37913 A2 5, 2004 12,696,839. WO 2005/042663 A1 5, 2005 Office Action mailed Nov. 1, 2010, in co-pending U.S. Appl. No. WO 2005/049761 A1 6, 2005 12,696,839. WO 2005/067558 A2 7/2005 WO 2005/083O27 A1 9, 2005 * cited by examiner US 8,911,640 B2 1. 2 COMPOSITIONS COMPRISING roalkyl groups, and wherein the total number of carbons FLUOROOLEFNS AND USES THEREOF in the compound is at least 5; (ii) cyclic fluoroolefins of the formula cyclo-CX—CY CROSS REFERENCE(S) TO RELATED (CZW), , wherein X, Y, Z, and W, independently, are APPLICATION(S) H or F, and n is an integer from 2 to 5; and (iii) fluoroolefins selected from the group consisting of This application is a divisional application of and claims 2,3,3-trifluoro-1-propene(CHFCF=CH-); 1,1,2-trif the priority benefit of U.S. patent application Ser. No. 13/286, luoro-1-propene (CHCF=CF); 1,2,3-trifluoro-1- 765 filed Nov. 1, 2011, now U.S. Pat. No. 8,425,795, which is propene(CHFCF=CF); 1,1,3-trifluoro-1-propene 10 (CHFCH=CF); 1,3,3-trifluoro-1-propene a division of U.S. patent application Ser. No. 12/696,793 filed (CHF.CH=CHF); 1.1.1.2.3.4.4.4-octafluoro-2- Jan. 29, 2010, and issued as U.S. Pat. No. 8,070,976, which is butene (CFCF–CFCF); 1,1,2,3,3,4,4,4-oc a division of U.S. patent application Ser. No. 1 1/589,588, tafluoro-1-butene (CFCFCF–CF); 1,1,1,2,4,4,4- filed Oct. 30, 2006, and issued as U.S. Pat. No. 7,708,903, heptafluoro-2-butene (CFCF–CHCF); 1.2.3.3.4.4, which claims the priority benefit of U.S. Provisional Appli 15 4-heptafluoro-1-butene (CHF=CFCFCF); 1,1,1,2, cation 60/732,581, filed Nov. 1, 2005. 3,4,4-heptafluoro-2-butene (CHFCF–CFCF); 1.3, 3,3-tetrafluoro-2-(trifluoromethyl)-1-propene FIELD OF THE INVENTION ((CF)C=CHF); 1.1.3.3.4.4.4-heptafluoro-1- butene (CF=CHCFCF); 1.1.2.3.4.4.4-hep The present invention relates to compositions for use in tafluoro-1-butene (CF–CFCHFCF); 1,1,2,3,3,4,4- refrigeration, air-conditioning or heat pump systems wherein heptafluoro-1-butene (CF–CFCFCHF); 2.3.3.4. 4.4-hexafluoro-1-butene (CFCFCF–CH); 1.3.3. the composition comprises at least one fluoroolefin. The com 4.4.4-hexafluoro-1-butene (CHF=CHCFCF); 1.2, positions of the present invention are useful in processes for 3.4.4.4-hexafluoro-1-butene (CHF=CFCHFCF); producing refrigeration or heat, as heat transfer fluids and 1,2,3,3,4,4-hexafluoro-1-butene many other uses. 25 (CHF-CFCFCHF); 1,1,2,3,4,4-hexafluoro-2- butene (CHF.CF–CFCHF); 1,1,1,2,3,4- BACKGROUND OF THE INVENTION hexafluoro-2-butene (CHFCF=CFCF); 1,1,1,2,4, 4-hexafluoro-2-butene (CHFCH=CFCF); 1,1,1,3, The refrigeration industry has been working for the past 4.4-hexafluoro-2-butene (CFCH=CFCHF); 1.1.2, few decades to find replacement refrigerants for the ozone 30 3,3,4-hexafluoro-1-butene (CF–CFCFCHF); 1.1, depleting chlorofluorocarbons (CFCs) and hydrochlorofluo 2,3,4,4-hexafluoro-1-butene (CF–CFCHFCHF); 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene rocarbons (HCFCs) being phased out as a result of the Mon (CH=C(CF)); 1,1,1,2,4-pentafluoro-2-butene treal Protocol. The solution for most refrigerant producers has (CHFCH=CFCF); 1,1,1,3,4-pentafluoro-2-butene been the commercialization of hydrofluorocarbon (HFC) (CFCH=CFCHF); 3.3.4.4.4-pentafluoro-1-butene refrigerants. The new HFC refrigerants, HFC-134a being the 35 (CFCF-CH=CH-); 1,1,1,4,4-pentafluoro-2-butene most widely used at this time, have Zero oZone depletion (CHFCH=CHCF); 1,1,1,2,3-pentafluoro-2- potential and thus are not affected by the current regulatory butene (CHCF=CFCF): 2,3,3,4,4-pentafluoro-1- phase out as a result of the Montreal Protocol. butene (CH=CFCFCHF); 1,1,2,4,4-pentafluoro Further environmental regulations may ultimately cause 2-butene (CHF.CF–CHCHF); 1,1,2,3,3- global phase out of certain HFC refrigerants. Currently, the 40 pentafluoro-1-butene (CHCFCF–CF); 1,1,2,3,4- automobile industry is facing regulations relating to global pentafluoro-2-butene (CHFCF=CFCHF); 1,1,3,3, warming potential for refrigerants used in mobile air-condi 3-pentafluoro-2-methyl-1-propene (CF=C(CF) tioning. Therefore, there is a great current need to identify (CH)): 2-(difluoromethyl)-3,3,3-trifluoro-1-propene new refrigerants with reduced global warming potential for (CH=C(CHF) (CF)); 2.3.4.4.4-pentafluoro-1- the mobile air-conditioning market. Should the regulations be 45 butene (CH=CFCHFCF); 1.2.4.4.4-pentafluoro more broadly applied in the future, an even greater need will 1-butene (CHF=CFCHCF); 1.3.4.4.4-pen be felt for refrigerants that can be used in all areas of the tafluoro-1-butene (CHF=CHCHFCF); 1,3,3,4,4- refrigeration and air-conditioning industry. pentafluoro-1-butene (CHF=CHCFCHF); 1,2,3,4, Currently proposed replacement refrigerants for HFC 4-pentafluoro-1-butene (CHF=CFCHFCHF); 3.3, 134a include HFC-152a, pure hydrocarbons such as butane or 50 4,4-tetrafluoro-1-butene (CH2=CHCFCHF); 1,1- propane, or “natural” refrigerants such as CO. Many of these difluoro-2-(difluoromethyl)-1-propene (CF–C Suggested replacements are toxic, flammable, and/or have (CHF)(CH)); 1,3,3,3-tetrafluoro-2-methyl-1- low energy efficiency. Therefore, new alternative refrigerants propene (CHF=C(CF)(CH)); 3.3-difluoro-2- are being sought. (difluoromethyl)-1-propene (CH=C(CHF)); 1.1, 1,2-tetrafluoro-2-butene(CFCF-CHCH); 1,1,1,3- The object of the present invention is to provide novel 55 tetrafluoro-2-butene(CHCF=CHCF); 1,1,1,2,3,4, refrigerant compositions and heat transfer fluid compositions 4.5.5,5-decafluoro-2-pentene(CFCF-CFCFCF); that provide unique characteristics to meet the demands of 1.1.2.3.3.4.4.5.5,5-decafluoro-1-pentene low or Zero oZone depletion potential and lower global warm (CF=CFCFCFCF); 1,1,1,4,4,4-hexafluoro-2- ing potential as compared to current refrigerants. (trifluoromethyl)-2-butene((CF)2C=CHCF); 1.1, 60 1.2.4.4.5.5.5-nonafluoro-2-pentene BRIEF SUMMARY OF THE INVENTION (CFCF-CHCFCF): 1,1,1,3,4,4,5,5.5- nonafluoro-2-pentene(CFCH=CFCFCF); 1.2.3, The present invention relates to a refrigerant or heat trans 3.4.4.5.5.5-nonafluoro-1-pentene fer fluid composition comprising at least one compound (CHF CFCFCFCF); 1,1,3,3,4,4,5,5.5- selected from the group consisting of: 65 nonafluoro-1-pentene(CF=CHCFCFCF); 1.1.2, (i) fluoroolefins of the formula E- or Z-R'CH=CHR, 3.3.4.4.5.5-nonafluoro-1-pentene wherein R' and Rare, independently, C, to Ce perfluo (CF–CFCFCFCHF); 1,1,2,3,4,4,5,5.5-

US 8,911,640 B2 10 The present invention provides fluoroolefins having the about 5 carbon atoms in the molecule. Exemplary, non-lim formula E- or Z R'CH=CHR (Formula I), wherein R' and iting Formula I compounds are presented in Table 1. TABLE 1

Chemical Name 44.4-hexafluoro-2-butene 4,4,5,5,5-octafluoro-2-pentene 445,5,6,6,6-decafluoro-2-hexene 4.55,5-heptafluoro-4-(trifluoromethyl)-2-pentene 2,2,5,5,6,6,6-decafluoro-3-hexene 445,5,6,6,7,7,7-dodecafluoro-2-heptene 4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)-2-hexene 4.5,5,6,6,6-nonfluoro-4-(trifluoromethyl)-2-hexene 5,55-hexafluoro-44-bis(trifluoromethyl)-2-pentene 2,2,5,5,6,6,7,7,7-dodecafluoro-3-heptene ,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)-3-hexene 445,5,6,6,7,7,8,8,8-tetradecafluoro-2-octene 4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)-2-heptene 5,5,6,6,6-octafluoro-44-bis(trifluoromethyl)-2-hexene 2,2,5,5,6,6,7,7,8,8,8-tetradecafluoro-3-octene ,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)-3-heptene ,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)-3-heptene .2.2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)-3-hexene 2,2,3,3,6,6,7,7,8,8,8-tetradecafluoro-4-octene ,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)-3-hexene ,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)-3-heptene 445,5,6,6,7,7,8,8,9,9.9-hexadecafluoro-2-nonene 4.5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)-2-heptene 6,6,6-octafluoro-44-bis(trifluoromethyl)-2-heptene 2,2,5,5,6,6,7,7,8,8,9,9.9-hexadecafluoro-3-nonene ,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)-3-octene .2.2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)-3-heptene 2,2,3,3,6,6,7,7,8,8,9,9.9-hexadecafluoro-4-nonene ,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)-4-octene ,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)-4-octene 5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)-3-heptene 2.5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)-3-octene ,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)-3-heptene ,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)-3-heptene 2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)-3-hexene 2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluoro-3-decene ,2,2,5,6,6,7,7,8,8,9,9.9-pentadecafluoro-5-(trifluoromethyl)-3-nonene .2.2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)-3-octene 2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluoro-4-decene ,2,2,3,3,6,6,7,7,8,9,9.9-pentadecafluoro-8-(trifluoromethyl)-4-nonene ,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)-4-octene ,2,5,5,6,6,7,7,8,8,9,9.9-pentadecafluoro-2-(trifluoromethyl)-3-nonene ,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl-3-octene 2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)-3-heptene 2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene ,2,3,3,6,6,7,7,8,8,9,9.9-pentadecafluoro-2-(trifluoromethyl)-4-nonene ,2,2,3,6,6,7,7,8,8,9,9.9-pentadecafluoro-3-(trifluoromethyl)-4-nonene 5,5,6,6,7,7,8,8,8-dodecafluoro-2,2-bis(trifluoromethyl)-3-octene ,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)-4-octene ,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)-4-octene 5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)-3-heptene ,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)-4-octene ,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)-3-heptene 6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)-3-hexene

55 R are, independently, C, to Ce perfluoroalkyl groups. Compounds of Formula I may be prepared by contacting a Examples of RandR groups include, but are not limited to, perfluoroalkyl iodide of the formula R'I with a perfluoroalky ltrihydroolefin of the formula RCH=CH to form a trihy CF, CFs, CFCFCF, CF(CF), CFCFCFCF, droiodoperfluoroalkane of the formula RCHCHIR. This CF(CF)CFCF CFCF (CF), C(CF). 60 trihydroiodoperfluoroalkane can then be dehydroiodinated to CFCFCFCFCF, CFCFCF (CF), C(CF)CFs, form R'CH=CHR. Alternatively, the olefin R'CH=CHR CFCFCFCFCFCF, CF(CF) CFCFCF, and may be prepared by dehydroiodination of a trihydroiodoper C(CF)CFCFs. In one embodiment the fluoroolefins of fluoroalkane of the formula RCHICHR formed in turn by Formula I, have at least about 3 carbonatoms in the molecule. reacting a perfluoroalkyl iodide of the formula RI with a In another embodiment, the fluoroolefins of Formula I have at 65 perfluoroalkyltrihydroolefin of the formula R'CH=CH2. least about 4 carbon atoms in the molecule. In yet another Said contacting of a perfluoroalkyl iodide with a perfluo embodiment, the fluoroolefins of Formula I have at least roalkyltrihydroolefin may take place in batch mode by com US 8,911,640 B2 11 12 bining the reactants in a suitable reaction vessel capable of cated from glass, ceramic, or metal and is preferably agitated operating under the autogenous pressure of the reactants and with an impeller or stirring mechanism. products at reaction temperature. Suitable reaction vessels Temperatures suitable for the dehydroiodination reaction include fabricated from stainless steels, in particular of the are from about 10° C. to about 100° C., preferably from about austenitic type, and the well-known high nickel alloys such as 20° C. to about 70°C. The dehydroiodination reaction may be Monel(R) nickel-copper alloys, Hastelloy(R) nickel based carried out at ambient pressure or at reduced or elevated alloys and Inconel(R) nickel-chromium alloys. pressure. Of note are dehydroiodination reactions in which Alternatively, the reaction may take be conducted in semi the compound of Formula I is distilled out of the reaction batch mode in which the perfluoroalkyltrihydroolefin reac vessel as it is formed. tant is added to the perfluoroalkyl iodide reactant by means of 10 Alternatively, the dehydroiodination reaction may be con a suitable addition apparatus Such as a pump at the reaction ducted by contacting an aqueous solution of said basic Sub temperature. stance with a solution of the trihydroiodoperfluoroalkane in The ratio of perfluoroalkyl iodide to perfluoroalkyltrihy one or more organic solvents of lower polarity Such as an 15 alkane (e.g., hexane, heptane, or octane), aromatic hydrocar droolefin should be between about 1:1 to about 4:1, prefer bon (e.g., toluene), halogenated hydrocarbon (e.g., methyl ably from about 1.5:1 to 2.5:1. Ratios less than 1.5:1 tend to ene chloride, chloroform, carbon tetrachloride, or perchloro result in large amounts of the 2:1 adduct as reported by ethylene), or ether (e.g., diethyl ether, methyl tert-butyl ether, Jeanneaux, et. al. in Journal of Fluorine Chemistry, Vol. 4, tetrahydrofuran, 2-methyl tetrahydrofuran, dioxane, pages 261-270 (1974). dimethoxyethane, diglyme, or tetraglyme) in the presence of Preferred temperatures for contacting of said perfluoro a phase transfer catalyst. Suitable phase transfer catalysts alkyl iodide with said perfluoroalkyltrihydroolefin are pref include quaternary ammonium halides (e.g., tetrabutylam erably within therange of about 150° C. to 300° C., preferably monium bromide, tetrabutylammonium hydrosulfate, trieth from about 170° C. to about 250° C., and most preferably ylbenzylammonium chloride, dodecyltrimethylammonium from about 180° C. to about 230° C. 25 chloride, and tricaprylylmethylammonium chloride), quater Suitable contact times for the reaction of the perfluoroalkyl nary phosphonium halides (e.g., triphenylmethylphospho iodide with the perfluoroalkyltrihydroolefin are from about nium bromide and tetraphenylphosphonium chloride), or 0.5 hour to 18 hours, preferably from about 4 to about 12 cyclic polyether compounds known in the art as crown ethers hours. (e.g., 18-crown-6 and 15-crown-5). The trihydroiodoperfluoroalkane prepared by reaction of 30 Alternatively, the dehydroiodination reaction may be con ducted in the absence of solvent by adding the trihydroiodop the perfluoroalkyl iodide with the perfluoroalkyltrihydroole erfluoroalkane to a solid or liquid basic Substance. fin may be used directly in the dehydroiodination step or may Suitable reaction times for the dehydroiodination reactions preferably be recovered and purified by distillation prior to are from about 15 minutes to about six hours or more depend the dehydroiodination step. 35 ing on the solubility of the reactants. Typically the dehydroio The dehydroiodination step is carried out by contacting the dination reaction is rapid and requires about 30 minutes to trihydroiodoperfluoroalkane with a basic substance. Suitable about three hours for completion. basic Substances include alkali metal hydroxides (e.g., The compound of formula I may be recovered from the Sodium hydroxide or potassium hydroxide), alkali metal dehydroiodination reaction mixture by phase separation after oxide (for example, Sodium oxide), alkaline earth metal 40 addition of water, by distillation, or by a combination thereof. In another embodiment of the present invention, fluoroole hydroxides (e.g., calcium hydroxide), alkaline earth metal fins comprise cyclic fluoroolefins (cyclo-CX—CY oxides (e.g., calcium oxide), alkali metal alkoxides (e.g., (CZW), (Formula II), wherein X, Y, Z, and W are inde Sodium methoxide or Sodium ethoxide), aqueous ammonia, pendently selected from Hand F, and n is an integer from 2 to Sodium amide, or mixtures of basic Substances such as Soda 45 5). Representative cyclic fluoroolefins of Formula II are listed lime. Preferred basic substances are sodium hydroxide and in Table 2. potassium hydroxide. Said contacting of the trihydroiodoperfluoroalkane with a TABLE 2 basic Substance may take place in the liquid phase preferably 50 Cyclic in the presence of a solvent capable of dissolving at least a fluoroolefins Structure Chemical name portion of both reactants. Solvents suitable for the dehydroio FC-C13.16cc cyclo-CFCFCF-CF- 1,2,3,3,4,4- dination step include one or more polar organic solvents such hexafluoro as alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, cyclobutene 55 HFC-C1334cc. cyclo-CFCF-CH=CH- 3,3,4,4- n-butanol, isobutanol, and tertiary butanol), nitriles (e.g., tetrafluoro acetonitrile, propionitrile, butyronitrile, benzonitrile, or adi cyclobutene ponitrile), dimethyl sulfoxide, N,N-dimethylformamide, HFC-C1436 cyclo-CFCFCF-CH=CH- 3.34,4,5,5- hexafluoro N,N-dimethylacetamide, or sulfolane. The choice of solvent cyclopentene may depend on the boiling point product and the ease of FC-C1418y cyclo-CFCF–CFCFCF- 1,2,3,3,4,4,5,5- separation of traces of the solvent from the product during 60 octafluoro cyclopentene purification. Typically, ethanol or isopropanol are good sol FC-C151-10y cyclo-CFCF–CFCFCFCF- 1,2,3,3,4,4,5,5,6,6- vents for the reaction. decafluoro Typically, the dehydroiodination reaction may be carried cyclohexene out by addition of one of the reactants (either the basic sub 65 stance or the trihydroiodoperfluoroalkane) to the other reac In another embodiment, fluoroolefins may comprise those tant in a suitable reaction vessel. Said reaction may be fabri compounds listed in Table 3.

US 8,911,640 B2 17 18 TABLE 3-continued

Name Structure Chemical name HFC-1558ff CH2=C(CF)CH2C2Fs 4,4,5,5,5-pentafluoro-2- (trifluoromethyl)-1-pentene HFC-1567fts CFCFCF-C(CH)—CH 3.3.4.4.5.5.5-heptafluoro-2-methyl -entelle HFC-1567SZZ FCFCF-CH=CHCH 4,4,5,5,6,6,6-heptafluoro-2-hexene H=CHCHCFCFs 4,4,5,5,6,6,6-heptafluoro-1-hexene FCFCF-CFC-Hs sks ,2,2,3,4-heptafluoro-3-hexene H=CHCHCF(CF). 455,5-tetrafluoro-4- (tri fluoromethyl)-1-pentene HFC-1567myzZm FCF=CHCH(CF)(CH,) 1.1, .2.5.5.5-heptafluoro-4-methyl 2-pentene HFC-1567mmtyf (CF)2C=CFCHs s 1,3-tetrafluoro-2- (tri fluoromethyl)-2-pentene FC-161-14myy CFCF-CFCFCFCF sks 2,3,4,4,5,5,6,6,7,7,7- etradecafluoro-2-heptene FC-161-14mcyy CFCFCF-CFCF-C-Fs s ,1,2,2,3,4,5,5,6,6,7,7,7- etradecafluoro-2-heptene HFC-162-13mzy CFCH=CFCFCFCF ,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene HFC 162-13myz CFCF-CHCFCF-C-Fs ,1,1,2,4,4,5,5,6,6,7,7,7- tridecafluoro-2-heptene HFC-162-13mczy CFCF-CH=CFCFCF ,1,1,2,2,4,5,5,6,6,7,7,7- tridecafluoro-3-heptene HFC-162-13mcyz CFCF-CF=CHCFC-Fs ,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-heptene PEVE CF=CFOCFCF pentafluoroethyl trifluorovinyl ether PMVE CF–CFOCF, trifluoromethyl trifluorovinyl ether

The compounds listed in Table 2 and Table 3 are available 1.1.1.4.4.5.5.5-octafluoro-2-pentene may be prepared commercially or may be prepared by processes known in the from (CFCHICHCFCF) by reaction with KOH using a art or as described herein. 30 phase transfer catalyst at about 60° C. The synthesis of 1,1,1,4,4-pentafluoro-2-butene may be prepared from 1.1, 4-iodo-1.1.1.2.2.5.5.5-octafluoropentane may be carried out 1,2,4,4-hexafluorobutane (CHFCHCHFCF) by dehydrof by reaction of perfluoroethyliodide (CFCFI) and 3,3,3-tri luorination over solid KOH in the vapor phase at room tem fluoropropeneatabout 200°C. under autogenous pressure for perature. The synthesis of 1,1,1,2,4,4-hexafluorobutane is about 8 hours. described in U.S. Pat. No. 6,066,768, incorporated herein by 35 reference. 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene may be prepared 1.1.1.4.4.4-hexafluoro-2-butene may be prepared from from 1,1,1,2,2,5,5,6,6,6-decafluoro-3-iodohexane 1,1,14.4.4-hexafluoro-2-iodobutane (CFCHICHCF) by (CFCFCHICHCFCF) by reaction with KOH using a reaction with KOHusing a phase transfer catalyst at about 60° phase transfer catalyst at about 60° C. The synthesis of 1,1, C. The synthesis of 1,1,1,4,4,4-hexafluoro-2-iodobutane may 40 1.2.2.5.5,6,6,6-decafluoro-3-iodohexane may be carried out be carried out by reaction of perfluoromethyl iodide (CFI) by reaction of perfluoroethyliodide (CFCFI) and 3.3.4.4.4- and 3,3,3-trifluoropropene (CFCH=CH-) at about 200° C. pentafluoro-1-butene(CFCF-CH=CH-) at about 200° C. under autogenous pressure for about 8 hours. under autogenous pressure for about 8 hours. 3.4.4.5.5.5-hexafluoro-2-pentene may be prepared by 1,1,1,4,5,5.5-heptafluoro-4-(trifluoromethyl)-2-pentene dehydrofluorination of 1,1,1,2,2,3,3-heptafluoropentane 45 may be prepared by the dehydrofluorination of 1,1,1,2,5,5.5- (CFCFCFCHCH) using solid KOH or over a carbon heptafluoro-4-iodo-2-(trifluoromethyl)-pentane catalyst at 200-300° C. 1,1,1,2,2,3,3-heptafluoropentane may (CFCHICHCF(CF)) with KOH in isopropanol. be prepared by hydrogenation of 3.3.4.4.5.5.5-heptafluoro-1- CFCHICHCF (CF) is made from reaction of (CF)CFI pentene (CFCFCF-CH=CH-). with CFCH=CH at high temperature, such as about 200° 1,1,1,2,3,4-hexafluoro-2-butene may be prepared by dehy 50 C. drofluorination of 1,1,1,2,3,3,4-heptafluorobutane 1.1.1.4.4.5,5,6,6,6-decafluoro-2-hexene may be prepared (CHFCFCHFCF) using solid KOH. by the reaction of 1,1,1,4,4,4-hexafluoro-2-butene 1,1,1,2,4,4-hexafluoro-2-butene may be prepared by dehy (CFCH=CHCF) with tetrafluoroethylene (CF–CF) and drofluorination of 1,1,1,2,2,4,4-heptafluorobutane antimony pentafluoride (SbF). (CHFCHCFCF) using solid KOH. 55 2,3,3,4,4-pentafluoro-1-butene may be prepared by dehy 1,1,1,3,4,4-hexafluoro2-butene may be prepared by dehy drofluorination of 1,1,2,2,3,3-hexafluorobutane over fluo drofluorination of 1,1,1,3,3,4,4-heptafluorobutane rided alumina at elevated temperature. (CFCHCFCHF) using solid KOH. 2.3.3.4.4.5.5.5-ocatafluoro-1-pentene may be prepared by 1,1,1,2,4-pentafluoro-2-butene may be prepared by dehy dehydrofluorination of 2.2.3.3.4.4.5.5.5-nonafluoropentane drofluorination of 1,1,1,2,2,3-hexafluorobutane 60 over Solid KOH. (CHFCHCFCF) using solid KOH. 1,2,3,3,4,4,5,5-octafluoro-1-pentene may be prepared by 1,1,1,3,4-pentafluoro-2-butene may be prepared by dehy dehydrofluorination of 2.2.3.3.4.4.5.5.5-nonafluoropentane drofluorination of 1,1,1,3,3,4-hexafluorobutane over fluorided alumina at elevated temperature. (CFCHCFCHF) using solid KOH. The compositions of the present invention may comprise a 1,1,1,3-tetrafluoro-2-butene may be prepared by reacting 65 single compound of Formula I, Formula II, or Table 3 or may 1,1,1,3,3-pentafluorobutane (CFCHCFCH) with aqueous comprise a combination of said compounds. Additionally, KOH at 120° C. many of the compounds of Formula I, Formula II, and Table US 8,911,640 B2 19 20 3 may exist as different configurational isomers or stereoiso inaparticular weight percentage range, it may be necessary to mers. The present invention is intended to include all single add one or more of the components in a given amount in order configurational isomers, single stereoisomers or any combi to restore the composition to within the specification limits. nation thereof. For instance, 1,3,3,3-tetrafluoropropene The compositions of the present invention that are useful as (HFC-1234ze) is meant to represent the E-isomer, Z-isomer, refrigerants or heat transfer fluids comprise at least one fluo or any combination or mixture of both isomers in any ratio. roolefin selected from the group consisting of Another example is F12E, by which is represented the E-iso (i) fluoroolefins of the formula E- or Z R'CH=CHR, mer, Z-isomer, or any combination or mixture of both isomers wherein R' and Rare, independently, C, to Ce perfluo in any ratio. roalkyl groups, and wherein the total number of carbons Compositions of the present invention have Zero or low 10 in the compound is at least 5; oZone depletion potential and low global warming potential (ii) cyclic fluoroolefins of the formula cyclo-CX—CY (GWP). The fluoroolefins of the present invention or mixtures (CZW), , wherein X, Y, Z, and W, independently, are of fluoroolefins of this invention with other refrigerants will H or F, and n is an integer from 2 to 5; and have global warming potentials that are less than many (iii) fluoroolefins selected from the group consisting of hydrofluorocarbon refrigerants currently in use. One aspect 15 1,2,3,3,3-pentafluoro-1-propene?(CFCF–CHF); 1,1,3, of the present invention is to provide a refrigerant with a 3.3-pentafluoro-1-propene(CFCH=CF); 1.1.2.3, global warming potential of less than 1000, less than 500, less 3-pentafluoro-1-propene(CHFCF=CF); 1,2,3,3- than 150, less than 100, or less than 50. Another aspect of the tetrafluoro-1-propene (CHFCF=CHF): 2,3,3,3- present invention is to reduce the net GWP of refrigerant tetrafluoro-1-propene? CFCF–CH): 1,1,2,3- mixtures by adding fluoroolefins to said mixtures. tetrafluoro-1-propene?(CHFCF=CF); 1,1,3,3- The compositions of the present invention that are combi tetrafluoro-1-propene(CHFCH=CF); 2,3,3- nations or mixtures may be prepared by any convenient trifluoro-1-propene?(CHFCF=CH2): 3,3,3- method to combine the desired amounts of the individual trifluoro-1-propene(CFCH=CH-); 1,1,2-trifluoro components. A preferred method is to weigh the desired 1-propene (CHCF—CF); 1,2,3-trifluoro-1-propene component amounts and thereafter combine the components 25 (CHFCF–CF); 1,1,3-trifluoro-1-propene in an appropriate vessel. Agitation may be used, if desired. (CHFCH=CF); 1,3,3-trifluoro-1-propene An alternative means for making compositions of the (CHF.CH-CHF); 1.1.1.2.3.4.4.4-octafluoro-2- present invention comprises (i) reclaiming a Volume of one or butene (CFCF-CFCF); 1,1,2,3,3,4,4,4-oc more components of a refrigerant composition from at least tafluoro-1-butene (CFCFCF–CF); 1,1,1,2,4,4,4- one refrigerant container, (ii) removing impurities Suffi 30 heptafluoro-2-butene (CFCF-CHCF); 1.2.3.3.4.4, ciently to enable reuse of said one or more of the reclaimed 4-heptafluoro-1-butene (CHF=CFCFCF); 1,1,1,2, components, (iii) and optionally, combining all or part of said 3,4,4-heptafluoro-2-butene (CHFCF–CFCF); 1.3, reclaimed Volume of components with at least one additional 3,3-tetrafluoro-2-(trifluoromethyl)-1-propene refrigerant composition or component. ((CF)C=CHF); 1.1.3.3.4.4.4-heptafluoro-1- A refrigerant container may be any container in which is 35 butene (CF=CHCFCF); 1.1.2.3.4.4.4-hep stored a refrigerant blend composition that has been used in a tafluoro-1-butene (CF–CFCHFCF); 1,1,2,3,3,4,4- refrigeration apparatus, air-conditioning apparatus or heat heptafluoro-1-butene (CF=CFCFCHF); 2.3.3.4. pump apparatus. Said refrigerant container may be the refrig 4.4-hexafluoro-1-butene (CFCFCF–CH); 1.3.3. eration apparatus, air-conditioning apparatus or heat pump 4.4.4-hexafluoro-1-butene (CHF=CHCFCF); 1.2, apparatus in which the refrigerant blend was used. Addition 40 3.4.4.4-hexafluoro-1-butene (CHF=CFCHFCF): ally, the refrigerant container may be a storage container for 1,2,3,3,4,4-hexafluoro-1-butene collecting reclaimed refrigerant blend components, including (CHF CFCFCHF); 1,1,2,3,4,4-hexafluoro-2- but not limited to pressurized gas cylinders. butene (CHF.CF–CFCHF); 1,1,1,2,3,4- Residual refrigerant means any amount of refrigerant hexafluoro-2-butene (CHFCF=CFCF); 1,1,1,2,4, blend or refrigerant blend component that may be moved out 45 4-hexafluoro-2-butene (CHFCH=CFCF); 1,1,1,3, of the refrigerant container by any method known for trans 4.4-hexafluoro-2-butene (CFCH=CFCHF); 1.1.2, ferring refrigerant blends or refrigerant blend components. 3,3,4-hexafluoro-1-butene (CF–CFCFCHF); 1.1, Impurities may be any component that is in the refrigerant 2,3,4,4-hexafluoro-1-butene (CF–CFCHFCHF); blend or refrigerant blend component due to its use in a 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene refrigeration apparatus, air-conditioning apparatus or heat 50 (CH=C(CF)); 1,1,1,2,4-pentafluoro-2-butene pump apparatus. Such impurities include but are not limited (CHFCH=CFCF); 1,1,1,3,4-pentafluoro-2-butene to refrigeration lubricants, being those described earlier (CFCH=CFCHF); 3.3.4.4.4-pentafluoro-1-butene herein, particulates Such as metal or elastomer that may have (CFCF-CH=CH-); 1,1,1,4,4-pentafluoro-2-butene come out of the refrigeration apparatus, air-conditioning (CHF.CH=CHCF); 1,1,1,2,3-pentafluoro-2- apparatus or heat pump apparatus, and any other contami 55 butene (CHCF=CFCF); 2.3,3,4,4-pentafluoro-1- nants that may adversely effect the performance of the refrig butene (CH=CFCFCHF); 1,1,2,4,4-pentafluoro erant blend composition. 2-butene (CHF.CF–CHCHF); 1,1,2,3,3- Suchimpurities may be removed sufficiently to allow reuse pentafluoro-1-butene (CHCFCF–CF); 1,1,2,3,4- of the refrigerant blend or refrigerant blend component with pentafluoro-2-butene (CHFCF–CFCHF); 1,1,3,3, out adversely effecting the performance or equipment within 60 3-pentafluoro-2-methyl-1-propene (CF=C(CF) which the refrigerant blend or refrigerant blend component (CH)): 2-(difluoromethyl)-3,3,3-trifluoro-1-propene will be used. (CH=C(CHF) (CF)); 2.3.4.4.4-pentafluoro-1- It may be necessary to provide additional refrigerant blend butene (CH=CFCHFCF); 1.2.4.4.4-pentafluoro or refrigerant blend component to the residual refrigerant 1-butene (CHF=CFCHCF); 1.3.4.4.4-pen blend or refrigerant blend component in order to produce a 65 tafluoro-1-butene (CHF=CHCHFCF); 1,3,3,4,4- composition that meets the specifications required for a given pentafluoro-1-butene (CHF=CHCFCHF); 1,2,3,4, product. For instance, ifa refrigerant blend has 3 components 4-pentafluoro-1-butene (CHF=CFCHFCHF); 3.3,

US 8,911,640 B2 25 26 7,7-tetradecafluoro-3-heptene TABLE 4-continued (CFCFCF–CFCFCF); 1,1,1,3,4,4,5,5,6,6,7,7, 7-tridecafluoro-2-heptene Prediction Experimental from (CFCH=CFCFCFCF); 1,1,1,2,4,4,5,5,6,6,7,7, Flammability flamma 7-tridecafluoro-2-heptene (LFL, vol% in bility (CFCF-CHCFCFCF); 1,1,1,2,2,4,5,5,6,6,7,7, Compound Formula #F #H F/(FH) air) factor 7-tridecafluoro-3-heptene Other (CFCF-CH=CFCFCF); 1,1,1,2,2,3,5,5,6,6,7,7, fluoroolefins 7-tridecafluoro-3-heptene 10 HFC-1243 CHF 3 3 O.15 l8 Flammable (CFCFCF-CHCFCF); CF–CFOCFCF FC-1318 CFs 8 O 1.O l8 Oil (PEVE) and CF, CFOCF. (PMVE). 1886 Of particular utility in compositions comprising at least HFC-1327 CHF, 7 1 O.88 l8 Oil 1886 one flammable refrigerant and at least one fluoroolefin are HFC-1336 C4H2Fs 6 2 0.75 l8 Oil those fluoroolefins that themselves are non-flammable. Flam 15 1886 mability of a fluoroolefinappears to be related to the numbers HFC-1345 CH3Fs 5 3 O.63 l8 1886 HFC-1354 CHF 4 4 OSO l8 1886 of fluorine atoms and the numbers of hydrogen atoms in the FC-141-10 CsFo 10 O 1.O l8 Oil molecule. The equation below provides a flammability factor 1886 that may be calculated as an indication of predicted flamma HFC-1429 CHFo 9 1 O.90 l8 Oil 1886 bility: HFC-1438 C5H2Fs 8 2 O.8O l8 Oil 1886 HFC-1447 C5HF7 7 3 O.70 l8 Oil 1886 flammability factor = (F+ H) HFC-1456 C5H4Fs 6 4. O6 l8 1886 FC-151-12 CF12 12 O 1.O l8 Oil 25 1886 HFC-152-11 CHF 11 1 O.92 l8 Oil wherein: 1886 F=the number of fluorine atoms; and HFC-153-10 CHF 10 2 O.83 l8 Oil H=the number of hydrogen atoms in a molecule. 1886 HFC-1549 C6H3Fo 9 3 0.75 l8 Oil As certain compounds have been experimentally deter 30 1886 mined to be flammable, the cut-off for non-flammable fluo HFC-1558 C6H4Fs 8 4 O.67 l8 1886 roolefin flammability factors has been determined. Fluo HFC-1567 CHSF7 7 5 O.S8 l8 1886 FC-161-14 C7F14 14 O 1.O l8 Oil roolefins may be determined to be flammable or non 1886 flammable by testing under conditions specified by ASHRAE HFC-162-13 C7HF 13 1 O.93 l8 Oil (American Society of Heating, Refrigerating and Air-Condi 35 1886 tioning Engineers, Inc.) Standard 34-2001, under ASTM HFC-163-12 CHF, 12 2 O.86 l8 Oil 1886 (American Society of Testing and Materials) E681-01, with HFC-164-11 CHF 11 3 0.79 l8 Oil an electronic ignition source. Such tests of flammability are 1886 conducted with the compound of interest at 101 kPa (14.7 HFC-165-10 CHF 10 4 O.71 l8 Oil 1886 psia) and a specified temperature (often 100° C. (212°F.)) at 40 various concentrations in air in order to determine the lower HFC-1669 C7H5F9 9 5 O.64 l8 1886 HFC-C1316 CF6 6 O 1.O l8 Oil flammability limit (LFL) and/or upper flammability limit 1886 (UFL) of the test compound in air. HFC-C1418 CSFs 8 O 1.O l8 Oil The flammability factors for several fluoroolefins are listed 1886 HFC-C151- C6Fo 10 O 1.O l8 Oil in Table 4 along with the experimental determination of flam 45 O 1886 mable or non-flammable. Therefore, it can be predicted for HFC-C1334 CH2F 4 2 O.67 l8 1886 the other fluoroolefins of the present disclosure, which will be HFC-C1436 C6H2Fs 6 2 0.75 l8 Oil most useful in combination with the flammable refrigerants flammable of the present disclosure as being in fact non-flammable fluo roolefins. 50 The fluoroolefins as listed in Table 4 may be determined to be flammable or non-flammable based upon the value of the TABLE 4 flammability factor. If the flammability factor is found to be Prediction equal to or greater than 0.70, then the fluoroolefin may be Experimental from expected to be non-flammable. If the flammability factor is Flammability flamma 55 (LFL, vol% in bility less than 0.70, then the fluoroolefin may be expected to be Compound Formula #F #H F/(FH) air) factor flammable. In another embodiment of the present invention, the fluo HFC- CHFs 5 1 O.83 Oil- Oil 1225ye flammable flammable roolefins for use in compositions with flammable refrigerants HFC-1234yf CHF 4 2 O.67 6.O flammable are those fluoroolefins selected from the group consisting of E-HFC- CHF 4 2 O.67 S.O flammable 60 1234ze (a) fluoroolefins of the formula E- or Z R'CH=CHR, HFC- C5HFo 9 1 O.90 Oil- Oil wherein R' and Rare, independently, C to C perfluo 1429myZim flammable flammable roalkyl groups; zy (mixture of isomers) (b) cyclic fluoroolefins of the formula cyclo-CX—CY F1 2E C6H2Fs 8 2 0.75 Oil- Oil 65 (CZW), , wherein X, Y, Z, and W, independently, are flammable flammable H or F, and n is an integer from 2 to 5, and wherein the flammability factor is greater than or equal to 0.70; and US 8,911,640 B2 27 28 (c) fluoroolefins selected from the group consisting of (trifluoromethyl)-1-butene(CHF=CHCH(CF)); 1,2,3,3,3-pentafluoro-1-propene(CFCF-CHF); 1,1,3, 1,1,14-tetrafluoro-2-(trifluoromethyl)-2-butene 3.3-pentafluoro-1-propene? CFCH=CF); 1.1.2.3, (CHFCH=C(CF)); 1,1,1,3-tetrafluoro-2-(trifluo 3-pentafluoro-1-propene(CHFCF=CF); 1,1,1,2,3, romethyl)-2-butene(CHCF=C(CF)); 1,1,2,3,3,4, 4.4.4-octafluoro-2-butene (CFCF–CFCF); 1.1.2, 4.5,5,6,6,6-dodecafluoro-1-hexene (CF (CF). 3.3.4.4.4-octafluoro-1-butene (CFCFCF–CF); CF=CF); 1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro-3- 1.1.1.2.4.4.4-heptafluoro-2-butene hexene(CFCFCF–CFCFCF); 1,1,1.4.4.4- (CFCF-CHCF); 1.2.3.3.4.4.4-heptafluoro-1- hexafluoro-2,3-bis(trifluoromethyl)-2-butene((CF) butene (CHF=CFCFCF); 1,1,1,2,3,4,4-hep C=C(CF)); 1,1,1,2,3,4,5,5.5-nonafluoro-4-(trif tafluoro-2-butene (CHFCF–CFCF); 1,3,3,3-tet 10 luoromethyl)-2-pentene((CF)CFCF–CFCF); rafluoro-2-(trifluoromethyl)-1-propene((CF) 1,1,144.5.5.5-octafluoro-2-(trifluoromethyl)-2- C–CHF); 1.1.3.3.4.4.4-heptafluoro-1-butene pentene ((CF)C=CHCFs); 1,1,1,3,4,5,5,5-oc (CF=CHCFCF); 1,1,2,3,4,4,4-heptafluoro-1- tafluoro-4-(trifluoromethyl)-2-pentene((CF). butene (CF=CFCHFCF); 1,1,2,3,3,4,4-hep CFCF–CHCF): 3,3,4,4,5,5,6,6,6-nonafluoro-1- tafluoro-1-butene (CF=CFCFCHF); 2.3.3.4.4.4- 15 hexene(CFCFCFCF-CH=CH-): 4,4,4-trifluoro hexafluoro-1-butene (CFCFCF-CH-); 1.3.3.4.4, 3.3-bis(trifluoromethyl)-1-butene(CH=CHC 4-hexafluoro-1-butene (CHF=CHCFCF); 1,2,3,4, (CF)); 1.1.1.4.4.4-hexafluoro-2-(trifluoromethyl)- 4.4-hexafluoro-1-butene (CHF=CFCHFCF); 1.2.3, 3-methyl-2-butene ((CF)C=C(CH)(CF)); 2.3.3. 3,4,4-hexafluoro-1-butene (CHF=CFCFCHF); 5.5.5-hexafluoro-4-(trifluoromethyl)-1-pentene 1,1,2,3,4,4-hexafluoro-2-butene (CH=CFCFCH(CF)); 1,1,1,2,4,4,5,5.5- (CHF.CF–CFCHF); 1,1,1,2,3,4-hexafluoro-2- nonafluoro-3-methyl-2-pentene(CFCF-C(CH) butene (CHFCF=CFCF); 1,1,1,2,4,4-hexafluoro CFCF): 1,1,1,5,5.5-hexafluoro-4- 2-butene (CHF.CH=CFCF); 1,1,1,3,4,4- (trifluoromethyl)-2-pentene(CFCH=CHCH hexafluoro-2-butene (CFCH=CFCHF); 1,1,1,2,3, (CF)); 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro 3,4-hexafluoro-1-butene (CF=CFCFCHF); 1.1.2, 25 2-heptene (CFCF–CFCFCFCFs); 1,1,1,2,2,3,4, 3,4,4-hexafluoro-1-butene (CF–CFCHFCHF); 5,5,6,6,7,7,7-tetradecafluoro-3-heptene 3,3,3-trifluoro-2-(trifluoromethyl)-1-propene (CFCFCF–CFCFCFs); 1,1,1,3,4,4,5,5,6,6,7,7, (CH=C(CF)); 1.1.1.2.3.4.4.5.5,5-decafluoro-2- 7-tridecafluoro-2-heptene pentene (CFCF–CFCFCF); 1,1,2,3,3,4,4,5,5.5- (CFCH=CFCFCFCFs); 1,1,1,2,4,4,5,5,6,6,7,7, decafluoro-1-pentene (CF–CFCFCFCF); 1,1,1, 30 7-tridecafluoro-2-heptene 4.4.4-hexafluoro-2-(trifluoromethyl)-2-butene (CFCF–CHCFCFCFs); 1,1,1,2,2,4,5,5,6,6,7,7, ((CF)C—CHCF); 1,1,1,2,4,4,5,5.5-nonafluoro-2- 7-tridecafluoro-3-heptene pentene (CFCF–CHCFCF); 1,1,1,3,4,4,5,5.5- (CFCF-CH=CFCFCF); and 1,1,1,2,2,3,5,5,6,6, nonafluoro-2-pentene (CFCH=CFCFCF); 1.2.3, 7,7,7-tridecafluoro-3-heptene 3.4.4.5.5.5-nonafluoro-1-pentene 35 (CFCFCF-CHCFCF). (CHF–CFCFCFCF); 1,1,3,3,4,4,5,5,5-non In yet another embodiment, the fluoroolefins of the present afluoro-1-pentene (CF=CHCFCFCF); 1,1,2,3,3, disclosure that may be particularly useful in combination 4.4.5.5-nonafluoro-1-pentene with flammable refrigerants, may be at least one fluoroolefin (CF–CFCFCFCHF); 1.1.2.3.4.4.5.5.5-non selected from the group consisting of: afluoro-2-pentene (CHFCF=CFCFCF); 1,1,1,2, 40 (a) fluoroolefins of the formula E- or Z R'CH=CHR, 3.4.4.5.5-nonafluoro-2-pentene wherein R' and Rare, independently, C, to Ce perfluo (CFCF–CFCFCHF); 1,1,1,2,3,4,5,5,5-non roalkyl groups, and wherein the flammability factor is afluoro-2-pentene (CFCF–CFCHFCF): 1,2,3,44, greater than or equal to 0.70; and 4-hexafluoro-3-(trifluoromethyl)-1-butene (b) cyclic fluoroolefins of the formula cyclo-CX—CY (CHF=CFCF (CF)); 1.1.2.4.4.4-hexafluoro-3- 45 (CZW), , wherein X, Y, Z, and W, independently, are (trifluoromethyl)-1-butene(CF=CFCH(CF)); H or F, and n is an integer from 2 to 5, and wherein the 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene flammability factor is greater than or equal to 0.70. (CFCH=C(CF)); 1.1.3.4.4.4-hexafluoro-3-(trif While the flammability factor provides a basis for predict luoromethyl)-1-butene (CF=CHCF(CF)); 2.3.3, ing flammability of certain fluoroolefin compounds, there 4.4.5.5.5-octafluoro-1-pentene 50 may be certain variables, such as position of the hydrogen (CH=CFCFCFCF); 1,2,3,3,4,4,5,5-octafluoro atoms on the molecule that would account for certain isomers 1-pentene (CHF=CFCFCFCHF); 3.3.4.4.4-pen with a given molecular formula being flammable while other tafluoro-2-(trifluoromethyl)-1-butene(CH=C(CF) isomers are non-flammable. Therefore, the flammability fac CFCF); 1,14.4.4-pentafluoro-3-(trifluoromethyl)- tor may only be used as a tool for predicting flammability 1-butene(CF–CHCH(CF)); 1.3.4.4.4- 55 characteristics. pentafluoro-3-(trifluoromethyl)-1-butene Flammable refrigerants of the present invention comprise (CHF=CHCF(CF)); 1, 1.4.4.4-pentafluoro-2- any compound, which may be demonstrated to propagate a (trifluoromethyl)-1-butene (CF=C(CF)CHCF); flame under specified conditions oftemperature, pressure and 3.4.4,4-tetrafluoro-3-(trifluoromethyl)-1-butene composition when mixed with air. Flammable refrigerants ((CF)CFCH=CH-); 3.3.4.4.5.5.5-heptafluoro-1- 60 may be identified by testing under conditions specified by pentene (CFCFCF-CH=CH-); 2.3.3.4.4.5.5-hep ASHRAE (American Society of Heating, Refrigerating and tafluoro-1-pentene (CH=CFCFCFCHF); 1,1,3, Air-Conditioning Engineers, Inc.) Standard 34-2001, under 3.5.5.5-heptafluoro-1-butene ASTM (American Society of Testing and Materials) E681 (CF=CHCFCHCF); 1,1,1,2,4,4,4-heptafluoro 01, with an electronic ignition Source. Such tests of flamma 3-methyl-2-butene(CFCF–C(CF)(CH)); 2.4.4.4- 65 bility are conducted with the refrigerant at 101 kPa (14.7 psia) tetrafluoro-3-(trifluoromethyl)-1-butene and a specified temperature (typically 100° C. (212° F.), or (CH=CFCH(CF)); 14,4,4-tetrafluoro-3- room temperature, that being about 23°C. (73°F) at various US 8,911,640 B2 29 30 concentrations in air in order to determine the lower flamma of HCFC-22/HFC-152a/HCFC-124 (known by the ASHRAE bility limit (LFL) and upper flammability limit (UFL) of the designations, R401 or R-401A, R-401B, and R-401C), HFC test compound in air. 125/HFC-143a/HFC-134a (known by the ASHRAE designa In practical terms, a refrigerant may be classified as flam tion, R-404 or R-404A), HFC-32/HFC-125/HFC-134a mable if upon leaking from a refrigeration apparatus or air (known by ASHRAE designations, R407 or R-407A, conditioning apparatus, and contacting an ignition Source a R-407B, and R-407C), HCFC-22/HFC-143a/HFC-125 fire may result. The compositions of the present invention, (known by the ASHRAE designation, R408 or R-408A), during such a leak, have a low probability of causing a fire. HCFC-22/HCFC-124/HCFC-142b (known by the ASHRAE Flammable refrigerants of the present invention include designation: R-409 or R-409A), HFC-32/HFC-125 (known hydrofluorocarbons (HFCs), fluoroolefins, fluoroethers, 10 by the ASHRAE designation R-410A), and HFC-125/HFC hydrocarbon ethers, hydrocarbons, ammonia (NH), and 143a (known by the ASHRAE designation: R-507 or R507A) combinations thereof. and carbon dioxide. Flammable HFC refrigerants include but are not limited to: Examples of mixtures of more than one flammable refrig difluoromethane (HFC-32), fluoromethane (HFC-41), 1,1,1- erant include propane?isobutane: HFC-152a/isobutane, R32/ trifluoroethane (HFC-143a), 1,1,2-trifluoroethane (HFC 15 propane, R32/isobutane; and HFC/carbon dioxide mixtures 143), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC such as HFC-152a/CO. 161), 1,1,1-trifluoropropane (HFC-263fb), 1,1,1,3,3- One aspect of the present invention is to provide a non pentafluoropropane (HFC-365mfc), and combinations flammable refrigerant with a global warming potential of less thereof. These flammable HFC refrigerants are commercial than 150, preferably less than 50. Another aspect of the products available from a number of sources such as chemical present invention is to reduce the flammability of flammable synthesis companies or may be prepared by synthetic pro refrigeration mixtures by adding non-flammable fluoroole cesses disclosed in the art. fins to said mixtures. Flammable refrigerants of the present invention further It may be demonstrated that while certain refrigerants are comprise fluoroolefins including but not limited to: 1,2,3,3- flammable, it is possible to produce a non-flammable refrig tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1- 25 erant composition by adding to the flammable refrigerant propene (HFC-1234ze); 2.3,3,3-tetrafluoro-1-propene another compound that is not flammable. Examples of Such (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC nonflammable refrigerant blends include R-410A (HFC-32 is 1234yc); 1,1,3,3-tetrafluoro-1-propene (HFC-1234zc); 2.3, a flammable refrigerant, while HFC-125 is non-flammable), 3-trifluoro-1-propene (HFC-1243yf): 3,3,3-trifluoro-1-pro and R-407C(HFC-32 is a flammable refrigerant, while HFC pene (HFC-1243Zf): 1,1,2-trifluoro-1-propene (HFC 30 125 and HFC-134a are not flammable). 1243yc); 1,1,3-trifluoro-1-propene (HFC-1243Zc); 1,2,3- The compositions of the present invention that are useful as trifluoro-1-propene (HFC-1243ye); and 1,3,3-trifluoro-1- refrigerants or heat transfer fluids comprising at least one propene (HFC-1243Ze). fluoroolefin and at least one flammable refrigerant may con Flammable refrigerants of the present invention further tain an effective amount of fluoroolefin to produce a compo comprise fluoroethers, compounds similar to hydrofluorocar 35 sition that is non-flammable based upon results of ASTM bons, which also contain at least one ether group oxygen E681-01. atom. Representative fluoroether refrigerants include but are The present inventive compositions comprising at least one not limited to CFOCHs available commercially. flammable refrigerant and at least one fluoroolefin may con Flammable refrigerants of the present invention further tain about 1 weight percent to about 99 weight percent fluo comprise hydrocarbon refrigerants. Representative hydrocar 40 roolefin and about 99 weight percent to about 1 weight per bon refrigerants include but are not limited to propane, pro cent flammable refrigerant. pylene, cyclopropane, n-butane, isobutane, n-pentane, 2-me In another embodiment, the compositions of the present thylbutane (isopentane), cyclobutane, cyclopentane, 2.2- invention may contain about 10 weight percent to about 80 dimethylpropane, 2,2-dimethylbutane, 2,3-dimethylbutane, weight percent fluoroolefin and about 90 weight percent to 2,3-dimethylpentane, 2-methylhexane, 3-methylhexane, 45 about 20 weight percent flammable refrigerant. In yet another 2-methylpentane, 3-ethylpentane, 3-methylpentane, cyclo embodiment, the compositions of the present invention may hexane, n-heptane, methylcyclopentane, and n-hexane. contain about 20 weight percent to about 70 weight percent Flammable hydrocarbon refrigerants are readily available fluoroolefin and about 80 weight percent to about 30 weight from multiple commercial sources. percent flammable refrigerant. Flammable refrigerants of the present invention further 50 Of particular interest is an embodiment of the present dis comprise hydrocarbon ethers, such as dimethyl ether (DME, closure wherein the fluoroolefin comprises HFC-1225ye and CH3OCH3) and methyl t-butyl ether (MTBE, (CH3) the flammable refrigerant comprises HFC-32 (difluo 3COCH3), both available from multiple commercial sources. romethane). It has been determined that compositions com Flammable refrigerants of the present invention further prising up to 37 weight percent HFC-32 are non-flammable, comprise ammonia (NH3), a commercially available com 55 while compositions comprising 38 weight percent HFC-32 or pound. greater are flammable as determined by ASTM 681-01. The Flammable refrigerants of the present invention may fur present disclosure provides non-flammable compositions ther comprise mixtures of more than one refrigerant Such as a comprising about 1.0 weight percent to about 37.0 weight mixture of two or more flammable refrigerants (eg. two HFCs percent HFC-32 and about 99.0 weight percent to about 63 or an HFC and a hydrocarbon) or a mixture comprising a 60 weight percent HFC-1225ye. flammable refrigerant and a non-flammable refrigerant, Such Also, of particular interest is an embodiment of the present that the overall mixture is still considered to be a flammable disclosure wherein the composition comprises HFC-1225ye, refrigerant, identified under the ASTM conditions described HFC-32 and HFC-125. This composition of the present herein, or in practical terms. invention comprises about 20 weight percent to about 95 Examples of non-flammable refrigerants that may be com 65 weight percent HFC-1225ye, about 1.0 weight percent to bined with other refrigerants of the present invention include about 65 weight percent HFC-32, and about 1.0 weight per R-134a, R-134, R-23, R125, R-236fa, R-245fa, and mixtures cent to about 40 weight percent HFC-125. In another embodi US 8,911,640 B2 31 32 ment, the composition comprises about 30 weight percent to (UOP LLC, Des Plaines, Ill.). For refrigerants with small about 90 weight percent HFC-1225ye, about 5.0 weight per molecular size such as HFC-32, XH-11 desiccant is pre cent to about 55 weight percent HFC-32, and about 1.0 weight ferred. percent to about 35 weight percent HFC-125. In yet another The compositions of the present invention may further embodiment, the composition comprises about 40 weight comprise at least one lubricant. Lubricants of the present percent to about 85 weight percent HFC-1225ye, about 10 invention comprise those suitable for use with refrigeration or weight percent to about 45 weight percent HFC-32 and about air-conditioning apparatus. Among these lubricants are those 1.0 weight percent to about 28 weight percent HFC-125. conventionally used in compression refrigeration apparatus Those compositions containing less than about 40 weight utilizing chlorofluorocarbon refrigerants. Such lubricants and 10 their properties are discussed in the 1990 ASHRAE Hand percent HFC-32 are expected to be non-flammable composi book, Refrigeration Systems and Applications, chapter 8, tions. This flammability limit will vary from less than about titled “Lubricants in Refrigeration Systems, pages 8.1 45 weight percent HFC-32 to less than about 37 weight per through 8.21, herein incorporated by reference. Lubricants of cent HFC-32 depending on the relative ratios of HFC-1225ye the present invention may comprise those commonly known and HFC-125 present in the composition. 15 as “mineral oils” in the field of compression refrigeration In another embodiment of particular interest, the flam lubrication. Mineral oils comprise paraffins (i.e. straight mable refrigerant comprises HFC-1243Zf and a non-flam chain and branched-carbon-chain, Saturated hydrocarbons), mable fluoroolefin intended to reduce the flammability of the naphthenes (i.e. cyclic paraffins) and aromatics (i.e. unsatur overall composition. The composition may comprise about ated, cyclic hydrocarbons containing one or more rings char 1.0 weight percent to about 99 weight percent HFC-1243Zf acterized by alternating double bonds). Lubricants of the and about 99 weight percent to about 1.0 weight percent present invention further comprise those commonly known as HFC-1225ye. Alternatively, the composition may comprise “synthetic oils” in the field of compression refrigeration about 40 weight percent to about 70 weight percent HFC lubrication. Synthetic oils comprise alkylaryls (i.e. linear and 1243Zf and about 60 weight percent to about 30 weight per branched alkyl alkylbenzenes), synthetic paraffins and naph cent HFC-1225ye. 25 thenes, and poly(alphaolefins). Representative conventional In another embodiment of particular interest, the compo lubricants of the present invention are the commercially avail sition comprises about 1.0 weight percent to about 98 weight able BVM 100 N (paraffinic mineral oil sold by BVA Oils), percent HFC-1243Zf about 1.0 weight percent to about 98 Suniso(R) 3GS and Suniso(R) 5GS (naphthenic mineral oil sold weight percent HFC-1225ye; and about 1.0 weight percent to by Crompton Co.), Sontex.R. 372LT (naphthenic mineral oil about 50 weight percent HFC-125. Alternatively, the compo 30 sold by Pennzoil), Calumet(R) RO-30 (naphthenic mineral oil sition comprises about 40 weight percent to about 70 weight sold by Calumet Lubricants), Zero1R 75, Zero1R 150 and percent HFC-1243Zf about 20 weight percent to about 60 ZerolR 500 (linear alkylbenzenes sold by Shrieve Chemicals) weight percent HFC-1225ye; and about 1.0 weight percent to and HAB 22 (branched alkylbenzene sold by Nippon Oil). about 10 weight percent HFC-125. Lubricants of the present invention further comprise those, In another embodiment of particular interest the composi 35 which have been designed for use with hydrofluorocarbon tion comprises about 1.0 weight percent to about 98 weight refrigerants and are miscible with refrigerants of the present percent HFC-1243Zf about 1.0 weight percent to about 98 invention under compression refrigeration and air-condition weight percent HFC-1225ye; and about 1.0 weight percent to ingapparatus operating conditions. Such lubricants and their about 50 weight percent HFC-32. Alternatively, the compo properties are discussed in “Synthetic Lubricants and High sition comprises about 40 weight percent to about 70 weight 40 Performance Fluids'. R. L. Shubkin, editor, Marcel Dekker, percent HFC-1243Zf about 20 weight percent to about 60 1993. Such lubricants include, but are not limited to, polyol weight percent HFC-1225ye; and about 1.0 weight percent to esters (POEs) such as Castrol (R) 100 (Castrol, United King about 10 weight percent HFC-32. dom), polyalkylene glycols (PAGs) such as RL-488A from In yet another embodiment of particular interest, the com Dow (Dow Chemical, Midland, Mich.), and polyvinyl ethers position comprises about 1.0 weight percent to about 97 45 (PVEs). weight percent HFC-1243Zf about 1.0 weight percent to Lubricants of the present invention are selected by consid about 97 weight percent HFC-1225ye; about 1.0 weight per ering a given compressor's requirements and the environment cent to about 50 weight percent HFC-125; and about 1.0 to which the lubricant will be exposed. weight percent to about 50 weight percent HFC-32. Commonly used refrigeration system additives may Alternatively, the composition comprises about 40 weight 50 optionally be added, as desired, to compositions of the percent to about 70 weight percent HFC-1243Zf about 20 present invention in order to enhance lubricity and system weight percent to about 60 weight percent HFC-1225ye; and stability. These additives are generally known within the field about 1.0 weight percent to about 10 weight percent HFC of refrigeration compressor lubrication, and include antiwear 125; and about 1.0 weight percent to about 10 weight percent agents, extreme pressure lubricants, corrosion and oxidation HFC-32. 55 inhibitors, metal Surface deactivators, foaming and antifoam The present invention further relates to a method for reduc control agents, leak detectants and the like. In general, these ing the flammability of a flammable refrigerant said method additives are present only in Small amounts relative to the comprising combining the flammable refrigerant with at least overall lubricant composition. They are typically used at con one fluoroolefin. The amount offluoroolefinadded must bean centrations of from less than about 0.1% to as much as about effective amount to produce a non-flammable compositions 60 3% of each additive. These additives are selected on the basis as determined by ASTM 681-01. of the individual system requirements. Some typical Compositions of the present invention may be used in examples of Such additives may include, but are not limited combination with a desiccantina refrigeration, air-condition to, lubrication enhancing additives, such as alkyl oraryl esters ing, or heat pump system to aid in removal of moisture. of phosphoric acid and of thiophosphates. Additionally, the Desiccants may be composed of acitivated alumina, silica gel. 65 metal dialkyl dithiophosphates (e.g. Zinc dialkyl dithiophos or zeolite based molecular sieves. Representative molecular phate or ZDDP, Lubrizol 1375) and other members of this sieves include MOLSIV XH-7, XH-6, XH-9 and XH-11 family of chemicals may be used in compositions of the US 8,911,640 B2 33 34 present invention. Other antiwear additives include natural no. 99-82-1); oleanane (CAS reg. no. 471-67-0); ophiobo product oils and assymetrical polyhydroxyl lubrication addi lane (CAS reg. no. 20098-65-1); picrasane (CAS reg. no. tives such as Synergol TMS (International Lubricants). Simi 35732-97-9); pimarane (CAS reg. no. 30257-03-5]); larly, stabilizers such as antioxidants, free radical scavengers, pinane (CAS reg. no.473-55-2); podocarpane (CAS reg. no. and water scavengers (drying compounds) may be employed. 471-78-3); protostane (CAS reg. no. 70050-78-1); rosane Such additives include but are not limited to, nitromethane, (CAS reg. no. 6812-82-4I); taxane (CAS reg. no. 1605-68 hindered phenols (such as butylated hydroxy toluene, or 1); thujane (CAS reg. no. 471-12-5); trichothecane (CAS BHT), hydroxylamines, thiols, phosphites, epoxides or lac reg. no.24706-08-9); and ursane (CAS reg. no. 464-93-7). tones. Water scavengers include but are not limited to ortho The terpenoids of the present invention are commercially esters such as trimethyl-, triethyl-, or tripropylortho formate. 10 Single additives or combinations may be used. available or may be prepared by methods known in the art or In one embodiment, the present invention provides com may be isolated from the naturally occurring source. positions comprising at least one fluoroolefin and at least one In one embodiment, the terpene or terpenoid stabilizers stabilizer selected from the group consisting of thiophos may be combined with at least one epoxide. Representative phates, butylated triphenylphosphorothionates, organo phos 15 epoxides include 1,2-propylene oxide (CAS reg. no. 75-56 phates, dialkylthiophosphate esters, terpenes, terpenoids, 9); 1.2-butylene oxide (CAS reg. no. 106-88-7); or mix fullerenes, functionalized perfluoropolyethers, polyoxyalky tures thereof. lated aromatics, epoxides, fluorinated epoxides, oxetanes, In another embodiment, the terpene or terpenoid stabilizers ascorbic acid, thiols, lactones, thioethers, nitromethanes, of the present invention may be combined with at least one alkylsilanes, benzophenone derivatives, arylsulfide, divinyl fluorinated epoxide. The fluorinated epoxides of the present terephthalate, diphenyl terephthalate, alkylamines, hindered invention may be depicted by Formula 3, wherein each of R amine antioxidants, and phenols, The alkylamines can through R is H, alkyl of 1-6 carbon atoms or fluoroalkyl of include triethylamine, tributylamine, diisopropylamine, tri 1-6 carbon atoms with the proviso that at least one of R isopropylamine, triisobutylamine, and other members of this through R is a fluoroalkyl group. family of alkylamine compounds. 25 In another embodiment, the stabilizers of the present inven tion may comprise specific combinations of stabilizers. One Formula 3 combination of Stabilizers of particular interest comprises at least one terpene or terpenoid. These terpenes or terpenoids may be combined with at least one compound selected from 30 SA R4 epoxides, fluorinated epoxides, and oxetanes. Terpenes are hydrocarbon compounds characterized by structures containing more than one repeating isoprene Representative fluorinated epoxide stabilizers include but (2-methyl-1,3-butadiene) unit. Terpenes may be acyclic or are not limited to trifluoromethyloxirane and 1,1-bis(trifluo cyclic. Representative terpenes include but are not limited to 35 romethyl)oxirane. Such compounds may be prepared by myrcene (2-methyl-6-methyl-eneocta-1,7-diene), allo methods known in the art, for instance by methods described cimene, beta-ocimene, terebene, limonene (or d-limonene), in, Journal of Fluorine Chemistry, volume 24, pages 93-104 retinal, pinene (or alpha-pinene), menthol, geraniol, farnesol, (1984), Journal of Organic Chemistry, volume 56, pages phytol, Vitamin A, terpinene, delta-3-carene, terpinolene, 3.187 to 3189 (1991), and Journal of Fluorine Chemistry, phellandrene, fenchene and mixtures thereof. Terpene stabi 40 volume 125, pages 99-105 (2004). lizers are commercially available or may be prepared by In another embodiment, the terpene or terpenoid stabilizers methods known in the art or isolated from natural Sources. of the present invention may be combined with at least one Terpenoids are natural products and related compounds oxetane. The oxetane stabilizers of the present invention may characterized by structures containing more than one repeat be compounds with one or more oxetane groups and is rep ing isoprene unit and optionally contain oxygen. Represen 45 resented by Formula 4, wherein R-R are the same or differ tative terpenoids include carotenoids, such as lycopene (CAS ent and can be selected from hydrogen, alkyl or Substituted reg. no. 502-65-8), betacarotene (CAS reg. no. 7235-40 alkyl, aryl or substituted aryl. 7), and Xanthophylls, i.e. zeaxanthin (CAS reg. no. 144-68 3); retinoids, such as hepaxanthin (CAS reg. no. 512-39-0), and isotretinoin (CAS reg. no. 4759-48-21); abietane (CAS 50 Formula 4 reg. no. 640-43-7); ambrosane (CAS reg. no. 24749-18 6); aristolane (CAS reg. no. 29788-49-6); atisane (CAS reg. no. 24379-83-7); beyerane (CAS reg. no. 2359-83-3), bisabolane (CAS reg. no. 29799-19-7); bornane (CAS reg. no. 464-15-3); caryophyllane (CAS reg. no. 20479-00-9); 55 cedrane (CAS reg. no. 13567-54-9); dammarane (CAS reg. no. 545-22-2); drimane (CAS reg. no. 5951-58-6); eremo Representative oxetane stabilizers include but are not lim philane (CAS reg. no. 3242-05-5); eudesmane (CAS reg. ited to 3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 no. 473-11-0); fenchane (CAS reg. no. 6248-88-0); gam (Toagosei Co., Ltd), 3-ethyl-3-((phenoxy)methyl)-oxetane, macerane (CAS reg. no. 559-65-9); germacrane (CAS reg. 60 such as OXT-211 (Toagosei Co., Ltd); and 3-ethyl-3-((2- no. 645-10-3); gibbane (CAS reg. no. 6902-95-0); gray ethyl-hexyloxy)methyl)-oxetane, such as OXT-212 (Toag anotoxane (CAS reg. no. 39907-73-8); guaiane (CAS reg. osei Co., Ltd). no. 489-80-5); himachalane (CAS reg. no. 20479-45-2); Another embodiment of particular interest is a combina hopane (CAS reg. no. 471-62-5); humulane (CAS reg. no. tion of stabilizers comprising fullerenes. The fullerene stabi 430-19-3); kaurane (CAS reg. no. 1573-40-6); labdane 65 lizers may be combined with at least one compound selected (CAS reg. no. 561-90-0); lanostane (CAS reg. no. 474-20 from the group consisting of epoxides, fluorinated epoxides, 4); lupane (CAS reg. no. 464-99-3); p-menthane (CAS reg. and oxetanes. The epoxides, fluorinated epoxides, and oxet US 8,911,640 B2 35 36 anes for combination with fullerenes have been previously In one embodiment of the present invention, these combi described herein as for combination with terpenes or terpe nations of stabilizers comprising terpenes or terpenoids, or noids. fullerenes or phenols with at least one compound selected Another embodiment of particular interest is a combina from the group consisting of epoxides, fluorinated epoxides, and oxetanes, may further comprise an additional stabilizer tion of stabilizers comprising phenols. The fullerene stabiliz compound selected from the group consisting of ers may be combined with at least one compound selected areoxalyl bis(benzylidene)hydrazide (CAS reg. no. 6629 from the group consisting of epoxides, fluorinated epoxides, 10-3): and oxetanes. The epoxides, fluorinated epoxides, and oxet N,N'-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhy anes for combination with phenols have been previously drazine) (CAS reg. no. 32687-78-8); described herein as for combination with terpenes or terpe 10 2,2'-oxamidobis-ethyl-(3,5-d-tert-butyl-4-hydroxyhy noids. drorcinnamate) (CAS reg. no. 70331-94-1); Phenol stabilizers comprise any substituted or unsubsti N,N'-(disalicyclidene)-1,2-propanediamine (CAS reg. no. tuted phenol compound including phenols comprising one or 94-91-1); and more Substituted or unsubstituted cyclic, straight chain, or ethyenediaminetetraacetic acid (CAS reg. no. 60-00-4) and branched aliphatic Substituent group. Such as, alkylated 15 salts thereof. monophenols including 2,6-di-tert-butyl-4-methylphenol; In another embodiment of the present invention, these 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6-tertbu combinations of stabilizers comprising terpenes or terpe tylphenol; tocopherol; and the like, hydroquinone and alky noids, or fullerenes or phenols with at least one compound lated hydroquinones including t-butyl hydroquinone, other selected from the group consisting of epoxides, fluorinated derivatives of hydroquinone; and the like, hydroxylated thio epoxides, and oxetanes, may further comprise at least one diphenyl ethers, including 4,4'-thio-bis(2-methyl-6-tert-bu alkylamine selected from the group consisting of triethy tylphenol): 4,4'-thiobis(3-methyl-6-tertbutylphenol); 2,2'- lamine; tributylamine; triisopropylamine; diisobutylamine; thiobis(4-methyl-6-tert-butylphenol); and the like, triisopropylamine; triisobutylamine; and hindered amine alkylidene-bisphenols including: 4,4'-methylenebis(2,6-di antioxidants. tert-butylphenol); 4,4'-bis(2,6-di-tert-butylphenol); deriva- 25 The compositions of the present invention may further tives of 2,2'- or 4.4-biphenoldiols; 2,2'-methylenebis(4-ethyl comprise a compound or composition that is a tracer and is 6-tertbutylphenol): 2,2'-methylenebis(4-methyl-6- selected from the group consisting of hydrofluorocarbon tertbutylphenol); 4,4-butylidenebis(3-methyl-6-tert (HFCs), deuterated hydrocarbon, deuterated hydrofluorocar butylphenol): 4.4-isopropylidenebis(2,6-di-tert- 30 bon, perfluorocarbons, fluoroether, brominated compound, butylphenol); 2,2'-methylenebis(4-methyl-6-nonylphenol): iodated compound, alcohol, aldehyde, ketones, nitrous oxide 2,2'-isobutylidenebis(4,6-dimethylphenol; 2,2'-methyl (NO) and combinations thereof. The tracer used in the enebis(4-methyl-6-cyclohexylphenol, 2.2- or 4.4-biphenyl present invention are different compositions from those used diols including 2,2'-methylenebis(4-ethyl-6-tert-butylphe as refrigerant or heat transfer fluids, are added to the refrig nol); butylated hydroxyl toluene (BHT), bisphenols erant and heat transfer compositions in previously deter comprising heteroatoms including 2,6-di-tert-alpha-dim 35 mined quantities to allow detection of any dilution, contami ethylamino-p-cresol, 4.4-thiobis(6-tert-butyl-m-cresol); and nation or other alteration of the composition, as described in the like; acylaminophenols; 2,6-di-tert-butyl-4(N,N'-dim U.S. patent application Ser. No. 11/062,044, filed Feb. 18, ethylaminomethylphenol); sulfides including: bis(3-methyl 2005. 4-hydroxy-5-tert-butylbenzyl)sulfide; bis(3,5-di-tert-butyl Typical tracer compounds for use in the present composi 4-hydroxybenzyl)sulfide; and the like. tions are listed in Table 5. TABLE 5 Compound Structure Deuterated hydrocarbons and hydrofluorocarbons Ethane-d6 CDCD Propane-d8 CDCD-CD HFC-32-2 CDF HFC-134a-d2 CDFCF HFC-143a-d3 CDCF HFC-125-d CDFCF HFC-227 ea-d CFCDFCF HFC-227 ca-d CFCF-CDF HFC-134-d2 CDF-CDF HFC-236fa-d2 CFCDCF HFC-24Scb-3 CFCF-CD HFC-263fb-d2 CFCDCH HFC-263fb-d3 CFCH-CD Fluoroethers

HFOC-12SE CHFOCF, HFOC-134a CHFOCF HFOC-143aE CHOCF HFOC-227 ea. CFOCHF F, HFOC-236faE CFOCHCF HFOC-245faERY or CHFOCHCF HFOC-245faEC.f3 (or CHF.CHOCF) HFOC-245cbEpsy or CHOCFCF HFOC-245.cbc.f3 (or CHCFOCF)

US 8,911,640 B2 39 40 TABLE 5-continued Compound Structure Perfluoromethyldecalin CF2 (see structure below) (cis or trans and all additional possible CF F F isomers) 3 F F F

F F F F Brominated compounds Bromomethane CHBr Bromofluoromethane CHFBr Bromodifluoromethane CHFBr Dibromofluoromethane CHFBr. Tribromomethane CHBr, Bromoethane CHCH-Br Bromoethene CH=CHBr 2-dibromoethane CH-BrCH-Br -bromo-1,2- CFBr-CHF difluoroethene Iodated compounds odotrifluoromethane CFI Difluoroiodomethane CHFI Fluoroiodomethane CHFI ,1,2-trifluoro-1- CFICHF iodoethane ,1,2,2-tetrafluoro-1- CFICHF iodoethane ,1,2,2-tetrafluoro-1,2- CFICFI diiodoethane odopentafluorobenzene CFSI Alcohols

Ethanol CHCH-OH n-propanol CHCHCH-OH Sopropanol CHCH(OH)CH Aldehydes and Ketones Acetone (2-propanone) CHC(O)CH n-propanal CHCH-CHO n-butanal CHCHCHCHO Methyl ethyl ketone (2- CHC(O)CHCH butanone) Other

Nitrous oxide NO

45 The compounds listed in Table 5 are available commer million by weight (ppm) to about 1000 ppm. Preferably, the cially (from chemical Supply houses) or may be prepared by tracer compound or tracer blend is present at a total concen processes known in the art. tration of about 50 ppm to about 500 ppm and most prefer Single tracer compounds may be used in combination with ably, the tracer compound or tracer blend is present at a total arefrigeration/heating fluid in the compositions of the present 50 concentration of about 100 ppm to about 300 ppm. invention or multiple tracer compounds may be combined in The compositions of the present invention may further any proportion to serve as a tracer blend. The tracer blend may comprise an ultra-violet (UV) dye and optionally a solubiliz contain multiple tracer compounds from the same class of ing agent. The UV dye is a useful component for detecting compounds or multiple tracer compounds from different leaks of the refrigerant composition or heat transfer fluids by classes of compounds. For example, a tracer blend may con 55 tain 2 or more deuterated hydrofluorocarbons, or one deuter permitting one to observe the fluorescence of the dye in the ated hydrofluorocarbon in combination with one or more refrigerant or heat transfer fluid composition at or in the perfluorocarbons. vicinity of a leak point in said apparatus in the refrigeration, Additionally, some of the compounds in Table 4 exist as air-conditioning, heat pump apparatus. One may observe the multiple isomers, structural or optical. Single isomers or mul 60 fluorescence of the dye under an ultra-violet light. Solubiliz tiple isomers of the same compound may be used in any ing agents may be needed due to poor solubility of such UV proportion to prepare the tracer compound. Further, single or dyes in some refrigerants and heat transfer fluids. multiple isomers of a given compound may be combined in By “ultra-violet dye is meant a UV fluorescent composi any proportion with any number of other compounds to serve tion that absorbs light in the ultra-violet or “near ultra-violet as a tracer blend. 65 region of the electromagnetic spectrum. The fluorescence The tracer compound or tracer blend may be present in the produced by the UV fluorescent dye under illumination by a compositions at a total concentration of about 50 parts per UV light that emits radiation with wavelength anywhere from US 8,911,640 B2 41 42 10 nanometer to 750 nanometer may be detected. Therefore, molecule may contain different Roxyalkylene groups. The if refrigerant or heat transfer fluid containing such a UV present polyoxyalkylene glycol ether solubilizing agents fluorescent dye is leaking from a given point in a refrigera preferably comprise at least one oxypropylene radical. Where tion, air-conditioning, or heat pump apparatus, the fluores R" is an aliphatic oralicyclic hydrocarbon radical having 1 to cence can be detected at the leak point, or in the vicinity of the 6 carbonatoms and y bonding sites, the radical may be linear, leak point. Such UV fluorescent dyes include but are not branched or cyclic. Representative R' aliphatic hydrocarbon limited to naphthalimides, perylenes, coumarins, radicals having two bonding sites include, for example, an anthracenes, phenanthracenes, Xanthenes, thioxanthenes, ethylene radical, a propylene radical, a butylene radical, a naphthoxanthenes, fluoresceins, and derivatives of said dye pentylene radical, a hexylene radical, a cyclopentylene radi or combinations thereof. Solubilizing agents of the present 10 cal and a cyclohexylene radical. Representative R' aliphatic invention comprise at least one compound selected from the hydrocarbon radicals having three or four bonding sites group consisting of hydrocarbons, hydrocarbon ethers, poly include residues derived from polyalcohols, such as trimethy oxyalkylene glycol ethers, amides, nitriles, ketones, chloro lolpropane, glycerin, pentaerythritol. 1,2,3-trihydroxycyclo carbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1- hexane and 1.3.5-trihydroxycyclohexane, by removing their trifluoroalkanes. 15 hydroxyl radicals. Hydrocarbon solubilizing agents of the present invention Representative polyoxyalkylene glycol ether solubilizing comprise hydrocarbons including straight chained, branched agents include but are not limited to: CHOCH2CH(CH) chain or cyclic alkanes or alkenes containing 16 or fewer O(H or CH) (propylene glycol methyl (or dimethyl)ether), carbon atoms and only hydrogen with no other functional CHOCH2CH(CH)O(H or CH) (dipropylene glycol groups. Representative hydrocarbon Solubilizing agents methyl (or dimethyl)ether), CHOICHCH(CH)O(H or comprise propane, propylene, cyclopropane, n-butane, isobu CH) (tripropylene glycol methyl (or dimethyl)ether), tane, n-pentane, octane, decane, and hexadecane. It should be CHOCH2CHCCH)O(H or CHs) (propylene glycol ethyl noted that if the refrigerant is a hydrocarbon, then the solu (or diethyl)ether), CHOICHCH(CH)O(H or CH) bilizing agent may not be the same hydrocarbon. (dipropylene glycol ethyl (or diethyl) ether), CHOICHCH Hydrocarbon ether solubilizing agents of the present 25 (CH)O(H or CH) (tripropylene glycol ethyl (or diethyl) invention comprise ethers containing only carbon, hydrogen ether), CH,OCH2CHCCH)O(H or CH 7) (propylene glycol and oxygen, such as dimethyl ether (DME). n-propyl (or di-n-propyl)ether), CH,OICH-CH(CH)O(H Polyoxyalkylene glycol ether solubilizing agents of the or CH 7) (dipropylene glycoln-propyl (or di-n-propyl)ether), present invention are represented by the formula R' (OR), CH,OCH2CH(CH)O(H or CH 7) (tripropylene glycol OR l, wherein: X is an integer from 1-3; y is an integer from 30 n-propyl (or di-n-propyl)ether), CHOCHCHCCH)OH 1-4; R' is selected from hydrogen and aliphatic hydrocarbon (propylene glycol n-butyl ether), CHOICH-CH(CH)O radicals having 1 to 6 carbonatoms and y bonding sites; R is (H or CH) (dipropylene glycol n-butyl (or di-n-butyl)ether), selected from aliphatic hydrocarbylene radicals having from CHOICHCH(CH)O(H or CH) (tripropylene glycol 2 to 4 carbon atoms; R is selected from hydrogen and ali n-butyl (or di-n-butyl)ether), (CH) COCHCH(CH)OH phatic and alicyclic hydrocarbon radicals having from 1 to 6 35 (propylene glycol t-butyl ether), (CH),COICHCHCCH) carbon atoms; at least one of R' and R is said hydrocarbon O(H or (CH)) (dipropylene glycol t-butyl (or di-t-butyl) radical; and wherein said polyoxyalkylene glycol ethers have ether), (CH) COCH2CH(CH)O(H or (CH)) (tripropy a molecular weight of from about 100 to about 300 atomic lene glycol t-butyl (or di-t-butyl)ether), CHOCHCH mass units. As used herein, bonding sites mean radical sites (CH)OH (propylene glycol n-pentyl ether), CHOCHCH available to form covalent bonds with other radicals. Hydro 40 (CH)OH (butylene glycol n-butyl ether), CHOICHCH carbylene radicals mean divalent hydrocarbon radicals. In the (CH)OH (dibutylene glycol n-butyl ether), present invention, preferred polyoxyalkylene glycol ether trimethylolpropane tri-n-butyl ether (CHC(CHO(CHO). solubilizing agents are represented by R" (OR), OR: X is CH)) and trimethylolpropane di-n-butyl ether (CHC preferably 1-2; y is preferably 1: R' and R are preferably (CHOC(CH2)CH) CH-OH). independently selected from hydrogen and aliphatic hydro 45 Amide solubilizing agents of the present invention com carbon radicals having 1 to 4 carbon atoms; R is preferably prise those represented by the formulae RC(O)NR'R'' and selected from aliphatic hydrocarbylene radicals having from cyclo-IRC(O)N(R), wherein R', R, R and Rare inde 2 or 3 carbon atoms, most preferably 3 carbon atoms; the pendently selected from aliphatic and alicyclic hydrocarbon polyoxyalkylene glycol ether molecular weight is preferably radicals having from 1 to 12 carbonatoms; R is selected from from about 100 to about 250 atomic mass units, most prefer 50 aliphatic hydrocarbylene radicals having from 3 to 12 carbon ably from about 125 to about 250 atomic mass units. The R' atoms; and wherein said amides have a molecular weight of and Rhydrocarbon radicals having 1 to 6 carbon atoms may from about 100 to about 300 atomic mass units. The molecu belinear, branched orcyclic. Representative R' and Rhydro lar weight of said amides is preferably from about 160 to carbon radicals include methyl, ethyl, propyl, isopropyl. about 250 atomic mass units. R. R. RandR may option butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neo 55 ally include substituted hydrocarbon radicals, that is, radicals pentyl, tert-pentyl, cyclopentyl, and cyclohexyl. Where free containing non-hydrocarbon Substituents selected from halo hydroxyl radicals on the present polyoxyalkylene glycol gens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). ether solubilizing agents may be incompatible with certain R", R. RandR may optionally include heteroatom-substi compression refrigeration apparatus materials of construc tuted hydrocarbon radicals, that is, radicals, which contain the tion (e.g. MylarR), R' and Rare preferably aliphatic hydro 60 atoms nitrogen (aza-), oxygen (oxa-) or Sulfur (thia-) in a carbon radicals having 1 to 4 carbonatoms, most preferably 1 radical chain otherwise composed of carbon atoms. In gen carbon atom. The Raliphatic hydrocarbylene radicals hav eral, no more than three non-hydrocarbon Substituents and ing from 2 to 4 carbon atoms form repeating oxyalkylene heteroatoms, and preferably no more than one, will be present radicals—(OR), that include oxyethylene radicals, for each 10 carbonatoms in R', and the presence of any such oxypropylene radicals, and oxybutylene radicals. The oxy 65 non-hydrocarbon Substituents and heteroatoms must be con alkylene radical comprising R in one polyoxyalkylene gly sidered in applying the aforementioned molecular weight col ether solubilizing agent molecule may be the same, or one limitations. Preferred amide solubilizing agents consist of US 8,911,640 B2 43 44 carbon, hydrogen, nitrogen and oxygen. Representative R', tanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, R, R and Raliphatic and alicyclic hydrocarbon radicals 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohex include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec anone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl ketone. dodecyl and their configurational isomers. A preferred Nitrile solubilizing agents of the present invention com embodiment of amide solubilizing agents are those wherein prise nitriles represented by the formula RCN, wherein R' is R" in the aforementioned formula cyclo-IRC(O)N(R)- selected from aliphatic, alicyclic orarylhydrocarbon radicals may be represented by the hydrocarbylene radical (CRR), having from 5 to 12 carbon atoms, and wherein said nitriles in other words, the formula: cyclo-I(CRR),C(O)N(R)- 10 have a molecular weight of from about 90 to about 200 atomic wherein: the previously-stated values for molecular weight mass units. R' in said nitrile solubilizing agents is preferably apply; n is an integer from 3 to 5; R is a saturated hydrocar selected from aliphatic and alicyclic hydrocarbon radicals bon radical containing 1 to 12 carbon atoms; R and Rare having 8 to 10 carbon atoms. The molecular weight of said independently selected (for each n) by the rules previously nitrile solubilizing agents is preferably from about 120 to offered defining R'. In the lactams represented by the for 15 about 140 atomic mass units. R' may optionally include sub mula: cyclo-I(CRR),C(O)N(R)-1, all Rand R7 are pref stituted hydrocarbon radicals, that is, radicals containing non erably hydrogen, or contain a single Saturated hydrocarbon hydrocarbon Substituents selected from halogens (e.g., fluo radical among the n methylene units, and R is a saturated rine, chlorine) and alkoxides (e.g. methoxy). R' may hydrocarbon radical containing 3 to 12 carbon atoms. For optionally include heteroatom-substituted hydrocarbon radi example, 1-(saturated hydrocarbon radical)-5-methylpyrroli cals, that is, radicals, which contain the atoms nitrogen (aza-), din-2-ones. oxygen (keto-, oxa-) or Sulfur (thia-) in a radical chain other Representative amide solubilizing agents include but are wise composed of carbon atoms. In general, no more than not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2- three non-hydrocarbon Substituents and heteroatoms, and one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, preferably no more than one, will be present for each 10 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2- 25 carbon atoms in R', and the presence of any such non-hydro one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, carbon Substituents and heteroatoms must be considered in 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpip applying the aforementioned molecular weight limitations. erid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolac Representative R' aliphatic, alicyclic and aryl hydrocarbon tam, 1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, radicals in the general formula RCN include pentyl, isopen 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, 30 tyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, N,N-dibutylformamide and N,N-diisopropylacetamide. octyl, nonyl, decyl, undecyl, dodecyl and their configura Ketone solubilizing agents of the present invention com tional isomers, as well as phenyl, benzyl, cumenyl, mesityl, prise ketones represented by the formula RC(O)R’, wherein tolyl, xylyl and phenethyl. RandR are independently selected from aliphatic, alicyclic Representative nitrile solubilizing agents include but are and aryl hydrocarbon radicals having from 1 to 12 carbon 35 not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopen atoms, and wherein said ketones have a molecular weight of tane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cya from about 70 to about 300 atomic mass units. R' and R in nooctane, 1-cyanononane, 1-cyanodecane, 2-cyanodecane, said ketones are preferably independently selected from ali 1-cyanoundecane and 1-cyanododecane. phatic and alicyclic hydrocarbon radicals having 1 to 9 carbon Chlorocarbon Solubilizing agents of the present invention atoms. The molecular weight of said ketones is preferably 40 comprise chlorocarbons represented by the formula RCl, from about 100 to 200 atomic mass units. R' and R may wherein; X is selected from the integers 1 or 2: R is selected together form a hydrocarbylene radical connected and form from aliphatic and alicyclic hydrocarbon radicals having 1 to ing a five, six, or seven-membered ring cyclic ketone, for 12 carbon atoms; and wherein said chlorocarbons have a example, cyclopentanone, cyclohexanone, and cyclohep molecular weight of from about 100 to about 200 atomic mass tanone. R' and R may optionally include substituted hydro 45 units. The molecular weight of said chlorocarbon solubilizing carbon radicals, that is, radicals containing non-hydrocarbon agents is preferably from about 120 to 150 atomic mass units. Substituents selected from halogens (e.g., fluorine, chlorine) Representative Raliphatic and alicyclic hydrocarbon radicals and alkoxides (e.g. methoxy). R' and R may optionally in the general formula RC1 include methyl, ethyl, propyl. include heteroatom-Substituted hydrocarbon radicals, that is, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso radicals, which contain the atoms nitrogen (aza-), oxygen 50 pentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, hep (keto-, oxa-) or Sulfur (thia-) in a radical chain otherwise tyl, octyl, nonyl, decyl, undecyl, dodecyl and their configu composed of carbon atoms. In general, no more than three rational isomers. non-hydrocarbon Substituents and heteroatoms, and prefer Representative chlorocarbon Solubilizing agents include ably no more than one, will be present for each 10 carbon but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3- atoms in RandR, and the presence of any such non-hydro 55 methylpentane, 1-chlorohexane, 1,6-dichlorohexane, 1-chlo carbon Substituents and heteroatoms must be considered in roheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, applying the aforementioned molecular weight limitations. and 1,1,1-trichlorodecane. Representative R' and Raliphatic, alicyclic and aryl hydro Ester solubilizing agents of the present invention comprise carbon radicals in the general formula RC(O)R’ include esters represented by the general formula R'COR, wherein methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, 60 R" and Rare independently selected from linear and cyclic, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopen saturated and unsaturated, alkyl and aryl radicals. Preferred tyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl esters consist essentially of the elements C, H and O, have a and their configurational isomers, as well as phenyl, benzyl, molecular weight of from about 80 to about 550 atomic mass cumenyl, mesityl, tolyl, Xylyl and phenethyl. units. Representative ketone solubilizing agents include but are 65 Representative esters include but are not limited to: not limited to: 2-butanone, 2-pentanone, acetophenone, buty (CH) CHCHOOC(CH), OCOCH-CH(CH), (di rophenone, hexanophenone, cyclohexanone, cyclohep isobutyl dibasic ester), ethyl hexanoate, ethyl hep US 8,911,640 B2 45 46 tanoate, n-butyl propionate, n-propyl propionate, ethyl -continued

benzoate, di-n-propyl phthalate, benzoic acid ethoxy ethyl ester, dipropyl carbonate, “Exxate 700' (a com mercial C, alkyl acetate), “Exxate 800 (a commercial Cs alkyl acetate), dibutyl phthalate, and tert-butyl acetate. Lactone solubilizing agents of the present invention com prise lactones represented by structures A, B, and C: 10 These lactones contain the functional group —CO - in a ring of six (A), or preferably five atoms (B), wherein for structures A and B. R through Rs are independently selected from hydrogen or linear, branched, cyclic, bicyclic, 15 saturated and unsaturated hydrocarbyl radicals. Each R through Rs may be connected forming a ring with another R through Rs. The lactone may have an exocyclic alkylidene group as in structure C, wherein R through R are indepen dently selected from hydrogen or linear, branched, cyclic, bicyclic, Saturated and unsaturated hydrocarbyl radicals. Each R though Re may be connected forming a ring with another R through R. The lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass 25 units. Representative lactone solubilizing agents include but are not limited to the compounds listed in Table 6. TABLE 6

Molecular Molecular Weight Additive Molecular Structure Formula (amu) (E,Z)-3-ethylidene-5- O O C7H10O2 126 methyl-dihydro-furan 2-one N

(E,Z)-3-propylidene-5- O O CsFH12O2 140 methyl-dihydro-furan 2-one N N

(E,Z)-3-butylidene-5- O O CoH4O2 154 methyl-dihydro-furan 2-one N N-1

(E,Z)-3-pentylidene-5- O O CoH16O2. 168 methyl-dihydro-furan 2-one S N-1N

(E,Z)-3-Hexylidene-5- O O CH18O2 182 methyl-dihydro-furan 2-one S N1\1

(E,Z)-3-Heptylidene-5- O O C12H2O2 196 methyl-dihydro-furan 2-one Sri Y-1N1 S.

(E,Z)-3-octylidene-5- O O CH22O2. 210 methyl-dihydro-furan 2-one N N-1N1\1

US 8,911,640 B2 51 TABLE 6-continued

Molecular Molecular Weight Additive Molecular Structure Formula (amu)

5-methyl-5-octyl C13H2O2 212 dihydro-furan-2-one

Hexahydro C8H12O2 140 isobenzofuran-1-one

delta-decalactone C10H18O2 170

delta-undecalactone C11H2OO2 184

delta-dodecalactone C12H22O2 198

mixture of 4-hexyl C10H18O2 170 dihydrofuran-2-one and 3-hexyl-dihydro-furan 2-one

Lactone solubilizing agents generally have a kinematic 45 limited to: methyl phenyl ether (anisole), 1,3-dimethyoxy viscosity of less than about 7 centistokes at 40° C. For benzene, ethyl phenyl ether and butyl phenyl ether. instance, gamma-undecalactone has kinematic viscosity of Fluoroether solubilizing agents of the present invention 5.4 centistokes and cis-(3-hexyl-5-methyl)dihydrofuran-2- comprise those represented by the general formula one has viscosity of 4.5 centistokes both at 40° C. Lactone 50 ROCFCF-H, wherein R' is selected from aliphatic, alicy solubilizing agents may be available commercially or pre clic, and aromatic hydrocarbon radicals having from about 5 pared by methods as described in U.S. patent application Ser. to about 15 carbon atoms, preferably primary, linear, Satu No. 10/910,495, filed Aug. 3, 2004, incorporated herein by rated, alkyl radicals. Representative fluoroether solubilizing reference. agents include but are not limited to: CH-OCFCFH and Aryl ether solubilizing agents of the present invention fur 55 CHOCFCFH. It should be noted that if the refrigerant is ther comprise aryl ethers represented by the formula ROR, a fluoroether, then the solubilizing agent may not be the same wherein: R' is selected from arylhydrocarbon radicals having fluoroether. from 6 to 12 carbon atoms; R is selected from aliphatic Fluoroether solubilizing agents may further comprise hydrocarbon radicals having from 1 to 4 carbon atoms; and ethers derived from fluoroolefins and polyols. The fluoroole wherein said aryl ethers have a molecular weight of from 60 fins may be of the type CF=CXY, wherein X is hydrogen, about 100 to about 150 atomic mass units. Representative R' chlorine or fluorine, and Y is chlorine, fluorine, CF, or OR aryl radicals in the general formula R'OR include phenyl, wherein R, is CF, CFs, or CF, Representative fluoroole biphenyl, cumenyl, mesityl, tolyl. Xylyl, naphthyl and fins are tetrafluoroethylene, chlorotrifluoroethylene, pyridyl. Representative Raliphatic hydrocarbon radicals in hexafluoropropylene, and perfluoromethylvinyl ether. The the general formula R'OR include methyl, ethyl, propyl, 65 polyols may be linear or branched. Linear polyols may be of isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Represen the type HOCH.(CHOH), (CRR), CHOH, wherein RandR tative aromatic ether solubilizing agents include but are not are hydrogen, or CH, or CHs and wherein X is an integer US 8,911,640 B2 53 54 from 0-4, and y is an integer from 0-4. Branched polyols may ing agent or fragrance. Typical examples of odor masking be of the type C(OH),(R)(CHOH)(CH), CHOH), agents or fragrances may include Evergreen, Fresh Lemon, wherein R may be hydrogen, CH or CHs m may be an Cherry, Cinnamon, Peppermint, Floral or Orange Peel, all of integer from 0 to 3, tandu may be 0 or 1, V and w are integers which are commercially available, as well as d-limonene and from 0 to 4, and also wherein t+u+V+w=4. Representative 5 pinene. Such odor masking agents may be used at concentra polyols are trimethylol propane, pentaerythritol, butanediol. tions of from about 0.001% to as much as about 15% by and ethylene glycol. weight based on the combined weight of odor masking agent 1,1,1-Trifluoroalkane solubilizing agents of the present and solubilizing agent. invention comprise 1,1,1-trifluoroalkanes represented by the The present invention further relates to a method of using general formula CFR', wherein R' is selected from aliphatic 10 and alicyclic hydrocarbon radicals having from about 5 to the refrigerant or heat transfer fluid compositions comprising about 15 carbon atoms, preferably primary, linear, Saturated, ultraviolet fluorescent dye to detect leaks in refrigeration alkyl radicals. Representative 1,1,1-trifluoroalkane solubiliz apparatus, air-conditioning apparatus, or heat pump appara ing agents include but are not limited to: 1,1,1-trifluorohex tus. The presence of the dye in the compositions allows for ane and 1,1,1-trifluorododecane. 15 detection of leaking refrigerant in the refrigeration, air-con Solubilizing agents of the present invention may be present ditioning, or heat pump apparatus. Leak detection helps to as a single compound, or may be present as a mixture of more one to address, resolve and/or prevent inefficient operation of than one solubilizing agent. Mixtures of solubilizing agents the apparatus or system or equipment failure. Leak detection may contain two solubilizing agents from the same class of also helps one contain chemicals used in the operation of the compounds, say two lactones, or two solubilizing agents from apparatus. two different classes, such as a lactone and a polyoxyalkylene The method comprises providing the composition com glycol ether. prising refrigerant, ultra-violet fluorescent dye or comprising In the present compositions comprising refrigerant and UV heat transfer fluid and UV fluorescent dye, as described fluorescent dye, or comprising heat transfer fluid and UV herein, and optionally, a solubilizing agent as described fluorescent dye, from about 0.001 weight percent to about 1.0 25 herein, to refrigeration, air-conditioning, or heat pump appa weight percent of the composition is UV dye, preferably from ratus and employing a suitable means for detecting the UV about 0.005 weight percent to about 0.5 weight percent, and fluorescent dye-containing refrigerant. Suitable means for most preferably from 0.01 weight percent to about 0.25 detecting the dye include, but are not limited to, ultra-violet weight percent. lamps, often referred to as a “black light” or “blue light'. Such Solubility of these UV fluorescent dyes in refrigerant and 30 ultra-violet lamps are commercially available from numerous heat transfer compositions may be poor. Therefore, methods Sources specifically designed for detecting UV fluorescent for introducing these dyes into the refrigeration, air-condi dye. Once the ultra-violet fluorescent dye containing compo tioning, or heat pump apparatus have been awkward, costly sition has been introduced to the refrigeration, air-condition and time consuming. U.S. Pat. No. RE 36,951, incorporated ing, or heat pump apparatus and has been allowed to circulate herein by reference, describes a method, which utilizes a dye 35 throughout the system, a leak point or the vicinity of the leak powder, solid pellet or slurry of dye that may be inserted into point can be located by shining said ultra-violet lamp on the a component of the refrigeration or air-conditioning appara apparatus and observing the fluorescence of the dye in the tus. As refrigerant and lubricant are circulated through the vicinity of any leak point. apparatus, the dye is dissolved or dispersed and carried Mechanical refrigeration is primarily an application of throughout the apparatus. Numerous other methods for intro 40 thermodynamics wherein a cooling medium, Such as a refrig ducing dye into a refrigeration or air-conditioning apparatus erant, goes through a cycle so that it can be recovered for are described in the literature. reuse. Commonly used cycles include vapor-compression, Ideally, the UV fluorescent dye could be dissolved in the absorption, Steam-jet or steam-ejector, and air. refrigerant thereby not requiring any specialized method for Vapor-compression refrigeration systems include an introduction to the refrigeration, air-conditioning, or heat 45 evaporator, a compressor, a condenser, and an expansion pump apparatus. The present invention relates to composi device. A vapor-compression cycle re-uses refrigerant in mul tions including UV fluorescent dye, which may be introduced tiple steps producing a cooling effect in one step and a heating into the system dissolved in the refrigerant in combination effect in a different step. The cycle can be described simply as with a solubilizing agent. The inventive compositions will follows. Liquid refrigerant enters an evaporator through an allow the storage and transport of dye-containing refrigerant 50 expansion device, and the liquid refrigerant boils in the and heat transfer fluid even at low temperatures while main evaporator at a low temperature to form a gas and produce taining the dye in solution. cooling. The low-pressure gas enters a compressor where the In the present compositions comprising refrigerant, UV gas is compressed to raise its pressure and temperature. The fluorescent dye and solubilizing agent, or comprising heat higher-pressure (compressed) gaseous refrigerant then enters transfer fluid and UV fluorescent dye and solubilizing agent, 55 the condenser in which the refrigerant condenses and dis from about 1 to about 50 weight percent, preferably from charges its heat to the environment. The refrigerant returns to about 2 to about 25 weight percent, and most preferably from the expansion device through which the liquid expands from about 5 to about 15 weight percent of the combined compo the higher-pressure level in the condenser to the low-pressure sition is solubilizing agent in the refrigerant or heat transfer level in the evaporator, thus repeating the cycle. fluid. In the compositions of the present invention the UV 60 There are various types of compressors that may be used in fluorescent dye is present in a concentration from about 0.001 refrigeration applications. Compressors can be generally weight percent to about 1.0 weight percent in the refrigerant classified as reciprocating, rotary, jet, centrifugal, Scroll, or heat transfer fluid, preferably from 0.005 weight percent to screw or axial-flow, depending on the mechanical means to about 0.5 weight percent, and most preferably from 0.01 compress the fluid, or as positive-displacement (e.g., recip weight percent to about 0.25 weight percent. 65 rocating, scroll or screw) or dynamic (e.g., centrifugal orjet), Solubilizing agents such as ketones may have an objection depending on how the mechanical elements act on the fluid to able odor, which can be masked by addition of an odor mask be compressed. US 8,911,640 B2 55 56 The compositions of the present invention comprising ratio of about 4 to 1; that is, the absolute discharge pressure fluoroolefins may be useful in any of the compressor types can be four times the absolute suction pressure. Several mentioned above. The choice of refrigerant for any given examples of two-stage centrifugal compressor systems, par compressor will depend on many factors including for ticularly for automotive applications, are described in U.S. instance, boiling point and vapor pressure requirements. 5 Pat. No. 5,065,990 and U.S. Pat. No. 5,363,674, both incor Either positive displacement or dynamic compressors may porated herein by reference. be used in the present inventive processes. A centrifugal type The present disclosure further relates to a method for pro compressor is one preferred type of equipment for certain of ducing heating or cooling in a refrigeration, air-conditioning, the refrigerant compositions comprising at least one fluo or heat pump apparatus, said method comprising introducing roolefin. 10 a refrigerant or heat transfer fluid composition into said appa A centrifugal compressor uses rotating elements to accel ratus having (a) a centrifugal compressor, (b) a multi-stage erate the refrigerant radially, and typically includes an impel centrifugal compressor, or (c) a single slab? single pass heat ler and diffuser housed in a casing. Centrifugal compressors exchanger, wherein said refrigerant or heat transfer fluid usually take fluid in at an impeller eye, or central inlet of a composition comprises at least one fluoroolefin selected from circulating impeller, and accelerate it radially outward. Some 15 the group consisting of static pressure rise occurs in the impeller, but most of the (i) fluoroolefins of the formula E- or Z R'CH=CHR, pressure rise occurs in the diffuser section of the casing, wherein R' and Rare, independently, C, to Ce perfluo where velocity is converted to static pressure. Each impeller roalkyl groups; diffuser set is a stage of the compressor. Centrifugal compres (ii) cyclic fluoroolefins of the formula cyclo-CX—CY sors are built with from 1 to 12 or more stages, depending on (CZW), , wherein X, Y, Z, and W, independently, are the final pressure desired and the volume of refrigerant to be H or F, and n is an integer from 2 to 5; or handled. (iii) fluoroolefins selected from the group consisting of The pressure ratio, or compression ratio, of a compressoris 1,2,3,3,3-pentafluoro-1-propene(CFCF-CHF); 1,1,3, the ratio of absolute discharge pressure to the absolute inlet 3.3-pentafluoro-1-propene?(CFCH=CF); 1.1.2.3, pressure. Pressure delivered by a centrifugal compressor is 25 3-pentafluoro-1-propene(CHFCF=CF); 1,2,3,3- practically constant over a relatively wide range of capacities. tetrafluoro-1-propene (CHFCF=CHF): 2,3,3,3- Positive displacement compressors draw vapor into a tetrafluoro-1-propene? CFCF–CH): 1,3,3,3- chamber, and the chamber decreases in Volume to compress tetrafluoro-1-propene(CFCH=CHF); 1,1,2,3- the vapor. After being compressed, the vapor is forced from tetrafluoro-1-propene?(CHFCF=CF); 1,1,3,3- the chamber by further decreasing the volume of the chamber 30 tetrafluoro-1-propene (CHFCH=CF); 2.3.3- to Zero or nearly Zero. A positive displacement compressor trifluoro-1-propene?(CHFCF=CH2): 3,3,3- can buildup a pressure, which is limited only by the volumet trifluoro-1-propene(CFCH=CH-): 1,1,2-trifluoro ric efficiency and the strength of the parts to withstand the 1-propene (CHCF=CF); 1,1,3-trifluoro-1-propene pressure. (CHFCH=CF); 1,2,3-trifluoro-1-propene Unlike a positive displacement compressor, a centrifugal 35 (CHFCF–CHF); 1,3,3-trifluoro-1-propene compressor depends entirely on the centrifugal force of the (CHF.CH-CHF); 1.1.1.2.3.4.4.4-octafluoro-2- high-speed impeller to compress the vapor passing through butene(CFCF–CFCF); 1,1,2,3,3,4,4,4-octafluoro the impeller. There is no positive displacement, but rather 1-butene (CFCFCF–CF); 1,1,1,2,4,4,4-hep what is called dynamic-compression. tafluoro-2-butene (CFCF–CHCF); 1.2.3.3.4.4.4- The pressure a centrifugal compressor can develop 40 heptafluoro-1-butene (CHF=CFCFCF); 1,1,1,2,3, depends on the tip speed of the impeller. Tip speed is the speed 4.4-heptafluoro-2-butene (CHFCF–CFCF); 1,3,3, of the impeller measured at its tip and is related to the diam 3-tetrafluoro-2-(trifluoromethyl)-1-propene((CF), eter of the impeller and its revolutions perminute. The capac C–CHF); 1.1.3.3.4.4.4-heptafluoro-1-butene ity of the centrifugal compressor is determined by the size of (CF=CHCFCF); 1,1,2,3,4,4,4-heptafluoro-1- the passages through the impeller. This makes the size of the 45 butene (CF–CFCHFCF); 1,1,2,3,3,4,4-hep compressor more dependent on the pressure required than the tafluoro-1-butene (CF=CFCFCHF); 2.3.3.4.4.4- capacity. hexafluoro-1-butene (CFCFCF-CH); 1.3.3.4.4, Because of its high-speed operation, a centrifugal com 4-hexafluoro-1-butene (CHF=CHCFCF); 1,2,3,4, pressor is fundamentally a high Volume, low-pressure 4.4-hexafluoro-1-butene (CHF=CFCHFCF); 1.2.3, machine. A centrifugal compressor works best with a low- 50 3,4,4-hexafluoro-1-butene (CHF=CFCFCHF); pressure refrigerant, such as trichlorofluoromethane (CFC 1,1,2,3,4,4-hexafluoro-2-butene 11) or 1.2.2-trichlorotrifluoroethane (CFC-113). Some of the (CHF.CF–CFCHF); 1,1,1,2,3,4-hexafluoro-2- low pressure refrigerant fluids of the present invention may be butene (CHFCF=CFCF); 1,1,1,2,4,4-hexafluoro suitable as drop-in replacements for CFC-113 in existing 2-butene (CHF.CH=CFCF); 1,1,1,3,4,4- centrifugal equipment. 55 hexafluoro-2-butene (CFCH=CFCHF); 1,1,2,3,3, Large centrifugal compressors typically operate at 3000 to 4-hexafluoro-1-butene (CF–CFCFCHF); 1.1.2.3, 7000 revolutions per minute (rpm). Small turbine centrifugal 4.4-hexafluoro-1-butene (CF–CFCHFCHF); 3.3, compressors (mini-centrifugal compressors) are designed for 3-trifluoro-2-(trifluoromethyl)-1-propene (CH=C high speeds, from about 40,000 to about 70,000 (rpm), and (CF)); 1,1,1,2,4-pentafluoro-2-butene have small impeller sizes, typically less than 0.15 meters 60 (CHFCH=CFCF); 1,1,1,3,4-pentafluoro-2-butene (about 6 inches). (CFCH=CFCHF); 3.3.4.4.4-pentafluoro-1-butene A multi-stage impeller may be used in a centrifugal com (CFCF-CH=CH-); 1,1,1,4,4-pentafluoro-2-butene pressor to improve compressor efficiency thus requiring less (CHF.CH=CHCF); 1,1,1,2,3-pentafluoro-2- power in use. For a two-stage system, in operation, the dis butene (CHCF=CFCF); 2.3,3,4,4-pentafluoro-1- charge of the first stage impeller goes to the Suction intake of 65 butene (CH=CFCFCHF); 1,1,2,4,4-pentafluoro a second impeller. Both impellers may operate by use of a 2-butene (CHF.CF–CHCHF); 1,1,2,3,3- single shaft (or axle). Each stage can build up a compression pentafluoro-1-butene (CHCFCF–CF); 1,1,2,3,4-

US 8,911,640 B2 59 60 result in high flow velocities and high frictional losses in all The present invention further relates to a process to pro components. In these cases, the evaporator design may be duce cooling comprising compressing a composition of the modified. Rather than several microchannel slabs connected present invention, in a mini-centrifugal compressor powered in series (with respect to the refrigerant path) a single slab? by a ratioed gear drive assembly with a ratioed belt drive; single pass heat exchanger arrangement may be used. There condensing said composition; and thereafter evaporating said fore, a preferred heat exchanger for the refrigerant or heat composition in the vicinity of a body to be cooled. transfer fluid compositions of the present invention is a single The present invention relates to a process to produce cool slab? single pass heat exchanger. ing in a refrigeration apparatus, air-conditioning apparatus, or The present invention further relates to a process for pro heat pump apparatus, wherein said apparatus comprises at 10 least one single slab? single pass heat exchanger, said process ducing cooling comprising evaporating the fluoroolefin com comprising compressing a composition of the present inven positions of the present invention in the vicinity of a body to tion, in a centrifugal compressor, condensing said composi be cooled, and thereafter condensing said compositions. tion, and thereafter evaporating said composition in the vicin The present invention further relates to a process for pro ity of a body to be cooled. ducing heat comprising condensing the fluoroolefin compo 15 The present invention further relates to a method for sitions of the present invention in the vicinity of a body to be replacing or substituting for a refrigerant composition having heated, and thereafter evaporating said compositions. a GWP of about 150 or more, or a high GWP refrigerant, with The present invention further relates to a process to pro a composition having a lower GWP. One method comprises duce cooling comprising compressing a composition com providing a composition comprising at least one fluoroolefin prising at least one fluoroolefin in a centrifugal compressor, of the present invention as the replacement. In another condensing said composition, and thereafter evaporating said embodiment of the present invention the refrigerant or heat composition in the vicinity of a body to be cooled. Addition transfer fluid composition of the present invention, having a ally, the centrifugal compressor of the inventive method may lower GWP than the composition being replaced or substi be a multi-stage centrifugal compressor and preferably a tuted is introduced into the refrigeration, air conditioning or 2-stage centrifugal compressor. 25 heat pump apparatus. In some cases, the high GWP refriger The present invention further relates to a process to pro ant present in the apparatus will need to be removed from the duce cooling in a refrigeration apparatus, air-conditioning apparatus before introduction of the lower GWP composi apparatus, or heat pump apparatus, wherein said apparatus tions. In other cases, the fluoroolefin compositions of the comprises at least one single slab? single pass heat exchanger, present invention may be introduced into the apparatus while said process comprising condensing a composition of the 30 the high GWP refrigerant is present. present invention, and thereafter evaporating said composi Global warming potentials (GWPs) are an index for esti tion in the vicinity of a body to be cooled. mating relative global warming contribution due to atmo The compositions of the present invention are particularly spheric emission of a kilogram of a particular greenhouse gas useful in Small turbine centrifugal compressors (mini-cen compared to emission of a kilogram of carbon dioxide. GWP trifugal compressors), which can be used in auto and window 35 can be calculated for different time horizons showing the air-conditioning, heat pumps, or transport refrigeration, as effect of atmospheric lifetime for a given gas. The GWP for well as other applications. These high efficiency mini-cen the 100 year time horizon is commonly the value referenced. trifugal compressors may be driven by an electric motor and A high GWP refrigerant would be any compound capable can therefore be operated independently of the engine speed. of functioning as a refrigerant or heat transfer fluid having a A constant compressor speed allows the system to provide a 40 GWP at the 100 year time horizon of about 1000 or greater, relatively constant cooling capacity at all engine speeds. This alternatively 500 or greater, 150 or greater, 100 or greater, or provides an opportunity for efficiency improvements espe 50 or greater. Refrigerants and heat transfer fluids that are in cially at higher engine speeds as compared to a conventional need of replacement, based upon GWP calculations pub R-134a automobile air-conditioning system. When the lished by the Intergovernmental Panel on Climate Change cycling operation of conventional systems at high driving 45 (IPCC), include but are not limited to HFC-134a (1,1,1,2- speeds is taken into account, the advantage of these low tetrafluoroethane). pressure systems becomes even greater. The present invention will provide compositions that have Alternatively, rather than use electrical power, the mini Zero or low oZone depletion potential and low global warming centrifugal compressor may be powered by an engine exhaust potential (GWP). The fluoroolefins of the present invention or gas driven turbine or a ratioed gear drive assembly with 50 mixtures of fluoroolefins of this invention with other refrig ratioed belt drive. The electrical power available in current erants will have global warming potentials that are less than automobile design is about 14 volts, but the new mini-cen many hydrofluorocarbon refrigerants currently in use. Typi trifugal compressor requires electrical power of about 50 cally, the fluoroolefins of the present invention are expected to volts. Therefore, use of an alternative power source would be have GWP of less than about 25. One aspect of the present advantageous. A refrigeration apparatus or air-conditioning 55 invention is to provide a refrigerant with a global warming apparatus powered by an engine exhaust gas driven turbine is potential of less than 1000, less than 500, less than 150, less described in detail in U.S. patent application Ser. No. 1 1/367, than 100, or less than 50. Another aspect of the present inven 517, filed Mar. 3, 2006. A refrigeration apparatus or air tion is to reduce the net GWP of refrigerant mixtures by conditioning apparatus powered by a ratioed gear drive adding fluoroolefins to said mixtures. assembly is described in detail in U.S. patent application Ser. 60 The present invention further relates to a method for low No. 1 1/378,832, filed Mar. 17, 2006. ering the GWP of a refrigerant or heat transfer fluid, said The present invention further relates to a process to pro method comprising combining said refrigerant or heat trans duce cooling comprising compressing a composition of the fer fluid with at least one fluoroolefin of the present invention. present invention, in a mini-centrifugal compressor powered In another embodiment, the method for lowering the global by an engine exhaust gas driven turbine; condensing said 65 warming potential comprises combining said first composi composition; and thereafter evaporating said composition in tion with a composition comprising at least one fluorolefin, to the vicinity of a body to be cooled. produce a second composition Suitable for use as a refrigerant US 8,911,640 B2 61 62 or heat transfer fluid, and wherein said second composition Hydrofluorocarbon refrigerants of the present invention has a lower global warming potential than said first compo may further comprise the azeotropic, azeotrope-like and non sition. It may be determined that the GWP of a mixture or azeotropic compositions, including HFC-125/HFC-143a/ combination of compounds may be calculated as a weighted HFC-134a (known by the ASHRAE designation, R404 or average of the GWP for each of the pure compounds. R404A), HFC-32/HFC-125/HFC-134a (known by ASHRAE The present invention further relates to a method of using designations, R407 or R407A, R407B, or R407C), HFC-32/ the composition of the present invention comprising at least HFC-125 (R410 or R410A), and HFC-125/HFC-143a one fluoroolefin to lower global warming potential of an (known by the ASHRAE designation: R507 or R507A), original refrigerant or heat transfer fluid composition, said R413A (a blend of R134a/R218/isobutane), R423A (a blend 10 of R134a/R227ea), R507A (a blend of R125/R143a), and method comprising combining said original refrigerant or others. heat transfer fluid composition with the composition of the Chlorofluorocarbon refrigerants of the present invention present invention comprising at least one fluoroolefin, to pro which may need replacing include R22 (CHF,Cl), R123 duce a second refrigerant or heat transfer fluid composition (CHCICF), R124 (CHCIFCF), R502 (being a blend of wherein said second refrigerant or heat transfer fluid compo 15 CFC-115 (CCIFCF) and R22), R503 (being a blend of sition has a lower global warming potential than said original R23/R13 (CCIF)), and others. refrigerant or heat transfer fluid composition. Hydrochlorofluorocarbons of the present invention which The present invention further relates to a method for reduc may need replacing include R12 (CF2Cl2). R11 (CCIF), ing the GWP of an original refrigerant or heat transfer fluid R113 (CC1FCCIF). R114 (CFCICFCI), R401A or R401B composition in a refrigeration, air-conditioning or heat pump (being blends of R22/R152a/R124), R408A (a blend of R22/ apparatus, wherein said original refrigerant or heat transfer R125/R143a), and others, fluid has a GWP of about 150 or higher; said method com The fluoroether refrigerants of the present invention which prising introducing a second, lower GWP refrigerant or heat may need replacing may comprise compounds similar to transfer fluid composition of the present invention into said hydrofluorocarbons, which also contain at least one ether refrigeration, air-conditioning or heat pump apparatus. 25 group oxygen atom. The fluoroether refrigerants include but The present method for reducing the GWP of an original are not limited to CFOCH, and CFOCHs (both avail refrigerant may further comprise removing the original able commercially). refrigerantorheat transfer fluid composition from said refrig The original refrigerant or heat transfer fluid compositions eration, air-conditioning or heat pump apparatus before the of the present invention which may need replacement may second, lower GWP refrigerant or heat transfer fluid is intro 30 optionally further comprise combinations of refrigerants that duced. contain up to 10 weight percent of dimethyl ether, or at least The present invention further relates to a method for one C to Cs hydrocarbon, e.g., propane, propylene, cyclo replacing an original refrigerant or heat transfer fluid compo propane, n-butane, isobutane, n-pentane, cyclopentane and sition with a second refrigerant or heat transfer fluid compo neopentane (2,2-dimethylpropane). Examples of refrigerants sition comprising providing a composition of the present 35 containing such C to Cs hydrocarbons are azeotrope-like invention as the second refrigerant or heat transfer fluid com compositions of HCFC-22/HFC-125/propane (known by the position. An original refrigerant may be any refrigerant being ASHRAE designation, R402 or R402A and R402B), HCFC used in a refrigeration, air-conditioning or heat pump appa 22/octafluoropropane/propane (known by the ASHRAE des ratus in need of replacement ignation, R403 or R403 A and R403B), octafluoropropane/ The original refrigerant or heat transfer fluid needing 40 HFC-134a/isobutane (known by the ASHRAE designation, replacement may be any of hydrofluorocarbon refrigerants, R413 or R413A), HCFC-22/HCFC-124/HCFC-142b/isobu chlorofluorocarbon refrigerants, hydrochlorofluorocarbon, tane (known by the ASHRAE designation, R414 or R414A refrigerants, fluoroether refrigerants, or blends of refrigerant and R414B), HFC-134a/HCFC-124/n-butane (known by the compounds. ASHRAE designation, R416 or R416A), HFC-125/HFC The hydrofluorocarbon refrigerants of the present inven 45 134a/n-butane (known by the ASHRAE designation, R417 or tion which may need replacing include but are not limited to: R417A), HFC-125/HFC-134a/dimethyl ether (known by the CHF (HFC-23), CHF (HFC-32), CHF (HFC-41), ASHRAE designation, R419 or R419A), and HFC-125/ CHFCF (HFC-125), CHF CHF (HFC-134), CHFCF HFC-134a/isobutane (known by ASHRAE designation, (HFC-134a), CHF,CHF (HFC143), CFCH. (HFC-143a), R422, R422A, R422B, R422c, R422D). CHFCH (HFC-152a), CHFCH (HFC-161), 50 The present invention further relates to a method for CHF.CFCF (HFC-227ca), CFCFHCF. (HFC-227ea), replacing an original refrigerant or heat transfer fluid compo CHF.CFCHF (HFC-236ca), CHFCFCF (HFC-236cb), sition, said original composition being R134a (HFC-134a, CHFCHFCF (HFC-236ea), CFCHCF. (HFC-236fa), 1,1,1,2-tetrafluoroethane, CFCHF) in refrigeration appara CHFCFCHF (HFC-245ca), CHCFCF. (HFC-245cb), tus, air-conditioning apparatus, or heat pump apparatus, CHF CHFCHF (HFC-245ea), CHFCHFCF. (HFC 55 wherein said method comprises substituting R134a with a 245eb), CHF.CHCF. (HFC-245fa), CHFCFCHF (HFC second refrigerant or heat transfer fluid composition compris 254ca), CHCFCHF (HFC-254cb), CHFCHFCHF ing at least one compound selected from the group consisting (HFC-254ea), CHCHFCF (HFC-254eb), CHF CHCHF, of trifluoromethyl trifluorovinyl ether (PMVE). (HFC-254 fa), CHFCHCF. (HFC-254fb), CFCHCH The present invention further relates to a method for (HFC-263fb), CHCFCHF (HFC-263ca), CHCFCH 60 replacing an original refrigerant or heat transfer fluid compo (HFC-272ca), CHCHFCHF (HFC-272ea), sition, said original composition being R152a (HFC-152a, CHFCHCHF (HFC-272fa), CHCHCFH(HFC-272fb), 1,1-difluoroethane, CHFCH) in refrigeration apparatus, CHCHFCH, (HFC-281ea), CHCHCHF (HFC-281 fa), air-conditioning apparatus, or heat pump apparatus, wherein CHF.CFCFCF-H(HFC-338 pcc), CFCHCFCH (HFC said method comprises Substituting R152a with a second 365mfc), CFCHFCHFCFCF (HFC-43-10mee). These 65 refrigerant or heat transfer fluid composition comprising at hydrofluorocarbon refrigerants are available commercially or least one compound selected from the group consisting of may be prepared by methods known in the art. E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3- US 8,911,640 B2 63 64 pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropro pentene (HFC-152-11mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dode pene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), cafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2- and trifluoromethyl trifluorovinyl ether (PMVE). butene (HFC-1354mzy); 1,1,14.4.4-hexafluoro-2,3-bis The present invention further relates to a method for (trifluoromethyl)-2-butene (HFC-151-12mmitt); 1.2.3.3.4.4, replacing R227ea (HFC-227ea, 1,1,1,2,3,3,3-heptafluoro 5 5,5,6,6-decafluorocyclohexene (FC-C151-10y); 3.3.4.4.5.5, propane, CFCHFCF) in refrigeration apparatus, air-condi 5-heptafluoro-2-methyl-1-pentene (HFC-1567fts); 3.3.4.4.5, tioning apparatus, or heat pump apparatus, wherein said 5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6- method comprises providing as a Substitute a composition heptafluoro-2-hexene (HFC-1567szZ); 1,1,1,4,4,5,5,6,6,6- comprising at least one compound selected from the group decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5.5-nonafluoro-4- consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze). 10 (trifluoromethyl)-2-pentene (HFC-151-12mmzZ); and 1,1,1, 1,2,3,3,3-pentafluoropropene (HFC-1225ye), 2,3,3,3-tet 2.2.5.5,6,6,6-decafluoro-3-hexene (F22E). rafluoropropene (HFC-1234yf), 3,3,3-trifluoropropene The present invention further relates to a method for (HFC-1243Zlf), and trifluoromethyl trifluorovinyl ether replacing an original refrigerant or heat transfer fluid compo (PMVE). sition, said original composition being R365mfc (HFC The present invention further relates to a method for 15 365mfc. 1,1,1,3,3-pentafluorobutane, CFCHCFCH) in replacing an original refrigerant or heat transfer fluid compo refrigeration apparatus, air-conditioning apparatus, or heat sition, said original composition being R113 (CFC-113, 1.1, pump apparatus, wherein said method comprises Substituting 2-trichloro-1,2,2-trifluoroethane, CFCICFCI) in refrigera a second refrigerant or heat transfer fluid composition com tion apparatus, air-conditioning apparatus, or heat pump prising at least one compound selected from the group con apparatus, wherein said method comprises Substituting a sec sisting of 1,1,1,3,4,5,5.5-octafluoro-4-(trifluoromethyl)-2- ond refrigerant or heat transfer fluid composition comprising butene (HFC-152-11 mmyyz); 1,1,144.5.5.5-octafluoro-2- at least one compound selected from the group consisting of (trifluoromethyl)-2-pentene (HFC-152-11mmtz); 1,1,1,2,2, 1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-butene 3,4,5,5,6,6,6-dodecafluoro-3-hexene (HFC-151-12mcy): (HFC-152-11 mmyyZ); 1,1,144.5.5.5-octafluoro-2-(trifluo 1,1,1,3-tetrafluoro-2-butene (HFC-1354mzy); 1,1,1.4.4.4- romethyl)-2-pentene (HFC-152-11mmtz); 1,1,1,2,2,3,4,5.5, 25 hexafluoro-2,3-bis(trifluoromethyl)-2-butene (HFC-151 6,6,6-dodecafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tet 12mmitt); 1.2.3.3.4.4.5,5,6,6-decafluorocyclohexene (FC rafluoro-2-butene (HFC-1354mzy); 1,1,1,4,4,4-hexafluoro C151-10y); 3.3.4.4.5.5.5-heptafluoro-2-methyl-1-pentene 2,3-bis(trifluoromethyl)-2-butene (HFC-151-12mmitt); 1.2.3, (HFC-1567fts): 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene 3.4.4.5,5,6,6-decafluorocyclohexene (FC-C151-10y); 3.3.4. (PFBE): 4,4,5,5,6,6,6-heptafluoro-2-hexene (HFC-1567szZ); 4.5.5.5-heptafluoro-2-methyl-1-pentene (HFC-1567fts); 3.3, 30 1,1,144.5,5,6,6,6-decafluoro-2-hexene (F13E); 1,1,1,2,3,4, 4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE): 4,4,5,5,6,6,6- 5.5.5-nonafluoro-4-(trifluoromethyl)-2-pentene (HFC-151 heptafluoro-2-hexene (HFC-1567szZ); 1,1,1,4,4,5,5,6,6,6- 12mmzz); and 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5.5-nonafluoro-4- (F22E). (trifluoromethyl)-2-pentene (HFC-151-12mmzZ); and 1,1,1, The present invention further relates to a method for 2.2.5.5,6,6,6-decafluoro-3-hexene (F22E). 35 replacing an original refrigerant or heat transfer fluid compo The present invention further relates to a method for sition, said original composition being R11 (CFC-11, trichlo replacing an original refrigerant or heat transfer fluid compo rofluoromethane, CFCI) in refrigeration apparatus, air-con sition, said original composition being R43-10mee (HFC-43 ditioning apparatus, or heat pump apparatus, wherein said 10mee), 1.1.1.2.3.4.4.5.5.5-decafluoropentane, method comprises Substituting a second refrigerant or heat CFCHFCHFCFCF) in refrigeration apparatus, air-condi 40 transfer fluid composition comprising at least one compound tioning apparatus, or heat pump apparatus, wherein said selected from the group consisting of 1.2.3.3.4.4.5.5-oc method comprises Substituting a second refrigerant or heat tafluorocyclopentene (FC-C 1418y); 1,1,1,2,3,4,4,5,5,5-de transfer fluid composition comprising at least one compound cafluoro-2-pentene (FC-141-10myy); 1,1,1,2,4,4,5,5.5-non selected from the group consisting of 1.1.1.3.4.5.5.5-oc afluoro-2-pentene (HFC-1429myZ); 1,1,1,3,4,4,5,5.5- tafluoro-4-(trifluoromethyl)-2-butene (HFC-152-11 45 nonafluoro-2-pentene (HFC-1429mzy); 3.3.4.4.5.5.5- mmyy Z); 1,1,1,4,4,5,5.5-octafluoro-2-(trifluoromethyl)-2- heptafluoro-1-pentene (HFC-1447f7); 1,1,1.4.4.4- pentene (HFC-152-11 mmtz); 1,1,1,2,2,3,4,5,5,6,6,6-dode hexafluoro-2-butene (F11E); 1,1,1,4,4,4-hexafluoro-2- cafluoro-3-hexene (HFC-151-12mcy); 1,1,1,3-tetrafluoro-2- (trifluoromethyl)-2-butene (HFC-1429mzt); and 1,1,144.5, butene (HFC-1354mzy); 1,1,14.4.4-hexafluoro-2,3-bis 5.5-octafluoro-2-pentene (F12E). (trifluoromethyl)-2-butene (HFC-151-12mmitt); 1.2.3.3.4.4, 50 The present invention further relates to a method for 5,5,6,6-decafluorocyclohexene (FC-C151-10y); 3.3.4.4.5.5, replacing an original refrigerant or heat transfer fluid compo 5-heptafluoro-2-methyl-1-pentene (HFC-1567fts); 3.3.4.4.5, sition, said original composition being R123 (HCFC-123, 5,6,6,6-nonafluoro-1-hexene (PFBE); 4,4,5,5,6,6,6- 2,2-dichloro-1,1,1-trifluoroethane, CFCHCl) in refrigera heptafluoro-2-hexene (HFC-1567szZ); 1,1,1,4,4,5,5,6,6,6- tion apparatus, air-conditioning apparatus, or heat pump decafluoro-2-hexene (F13E); 1,1,1,2,3,4,5,5.5-nonafluoro-4- 55 apparatus, wherein said method comprises Substituting a sec (trifluoromethyl)-2-pentene (HFC-151-12mmzZ); and 1,1,1, ond refrigerant or heat transfer fluid composition comprising 2.2.5.5,6,6,6-decafluoro-3-hexene (F22E). at least one compound selected from the group consisting of The present invention further relates to a method for 1.2.3.3.4.4.5.5-octafluorocyclopentene (FC-C 1418y); 1,1,1, replacing an original refrigerant or heat transfer fluid compo 2.3.4.4.5.5,5-decafluoro-2-pentene (FC-141-10myy); 1,1,1, sition, said original composition being CFOCH (perfluo 60 2.4.4.5.5.5-nonafluoro-2-pentene (HFC-1429myZ); 1,1,1,3, robutyl methyl ether) in refrigeration apparatus, air-condi 4.4.5.5.5-nonafluoro-2-pentene (HFC-1429mzy); 3.3.4.4.5, tioning apparatus, or heat pump apparatus, wherein said 5.5-heptafluoro-1-pentene (HFC-1447fz); 1,1,1.4.4.4- method comprises Substituting a second refrigerant or heat hexafluoro-2-butene (F11E); 1,1,1,4,4,4-hexafluoro-2- transfer fluid composition comprising at least one compound (trifluoromethyl)-2-butene (HFC-1429mzt); and 1,1,144.5, selected from the group consisting of 1.1.1.3.4.5.5.5-oc 65 5.5-octafluoro-2-pentene (F12E). tafluoro-4-(trifluoromethyl)-2-butene (HFC-152-11 The present invention further relates to a method for mmyy Z); 1,1,1,4,4,5,5.5-octafluoro-2-(trifluoromethyl)-2- replacing an original refrigerant or heat transfer fluid compo US 8,911,640 B2 65 66 sition, said original composition being R245fa (HFC-245fa, The present invention further relates to a method for 1,1,1,3,3-pentafluoropropane, CFCHCHF) in refrigera replacing an original refrigerant or heat transfer fluid compo tion apparatus, air-conditioning apparatus, or heat pump sition, said original composition being R409A in refrigera apparatus, wherein said method comprises Substituting a sec tion apparatus, air-conditioning apparatus, or heat pump ond refrigerant or heat transfer fluid composition comprising 5 apparatus, wherein said method comprises Substituting a sec at least one compound selected from the group consisting of ond refrigerant or heat transfer fluid composition comprising 2,3,3-trifluoropropene (HFC-1243yf); 1,1,1.4.4.4- at least one compound selected from the group consisting of hexafluoro-2-butene (F11E); 1,3,3,3-tetrafluoropropene E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3- (HFC-1234ze); 1,1,1,2,4,4,4-heptafluoro-2-butene (HFC pentafluoropropene (HFC-1225ye): 2,3,3,3-tetrafluoropro 1327my); 1,2,3,3-tetrafluoropropene (HFC-1234ye); and 10 pentafluoroethyl trifluorovinyl ether (PEVE). pene (HFC-1234yf): 3,3,3-trifluoropropene (HFC-1243zf); The present invention further relates to a method for and trifluoromethyl trifluorovinyl ether (PMVE). R409A is replacing an original refrigerant or heat transfer fluid compo the ASHRAE designation for a refrigerant blend containing sition, said original composition being R114 (CFC-114, 1.2- about 60 weight percent HCFC-22 (chlorodifluoromethane, dichloro-1,1,2,2-tetrafluoroethane, CFCCFCI) in refrig 15 CHF,Cl), about 25 weight percent HCFC-124 (2-chloro-1,1, eration apparatus, air-conditioning apparatus, or heat pump 1,2-tetrafluoroethane, CFCHCIF), and about 15 weight per apparatus, wherein said method comprises Substituting a sec cent HCFC-142b (1-chloro-1,1-difluoroethane, CFCICH). ond refrigerant or heat transfer fluid composition comprising The present invention further relates to a method for at least one compound selected from the group consisting of replacing an original refrigerant or heat transfer fluid compo 1,1,1,2,3,4,4,4-octafluoro-2-butene (FC-1318my); 1.2.3,3,4, sition, said original composition being R409B in refrigera 4-hexafluorocyclobutene (FC-C1316 cc); 2.3.3.4.4.4- tion apparatus, air-conditioning apparatus, or heat pump hexafluoro-1-butene (HFC-1336yf); and 3.3.4.4.4-pen apparatus, wherein said method comprises Substituting a sec tafluoro-1-butene (HFC-1345fz). ond refrigerant or heat transfer fluid composition comprising The present invention further relates to a method for at least one compound selected from the group consisting of replacing an original refrigerant or heat transfer fluid compo 25 E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3- sition, said original composition being R236fa (HFC-236fa, pentafluoropropene (HFC-1225ye): 2,3,3,3-tetrafluoropro 1,1,1,3,3,3-hexafluoropropane, CFCHCF) in refrigeration pene (HFC-1234yf): 3,3,3-trifluoropropene (HFC-1243zf); apparatus, air-conditioning apparatus, or heat pump appara and trifluoromethyl trifluorovinyl ether (PMVE). R409B is tus, wherein said method comprises Substituting a second the ASHRAE designation for a refrigerant blend containing refrigerant or heat transfer fluid composition comprising at 30 about 65 weight percent HCFC-22 (chlorodifluoromethane, least one compound selected from the group consisting of CHF,Cl), about 25 weight percent HCFC-124 (2-chloro-1,1, 1,1,1,2,3,4,4,4-octafluoro-2-butene (FC-1318my); 1.2.3.3.4. 1,2-tetrafluoroethane, CFCHCIF), and about 10 weight per 4-hexafluorocyclobutene (FC-C1316 cc); 2.3.3.4.4.4- cent HCFC-142b (1-chloro-1,1-difluoroethane, CFCICH). hexafluoro-1-butene (HFC-1336yf); and 3.3.4.4.4-pen The present invention further relates to a method for tafluoro-1-butene (HFC-1345fz). 35 replacing an original refrigerant or heat transfer fluid compo The present invention relates to a method for replacing an sition, said original composition being R414B in refrigera original refrigerant or heat transfer fluid composition, said tion apparatus, air-conditioning apparatus, or heat pump original composition being R401A in refrigeration apparatus, apparatus, wherein said method comprises Substituting a sec air-conditioning apparatus, or heat pump apparatus, wherein ond refrigerant or heat transfer fluid composition comprising said method comprises Substituting a second refrigerant or 40 at least one compound selected from the group consisting of heat transfer fluid composition comprising at least one com E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze), 1,2,3,3,3- pound selected from the group consisting of E-1,3,3,3-tet pentafluoropropene (HFC-1225ye), 2,3,3,3-tetrafluoropro rafluoropropene (E-HFC-1234ze); 1,2,3,3,3-pentafluoropro pene (HFC-1234yf), 3,3,3-trifluoropropene (HFC-1243zf), pene (HFC-1225ye); 2.3,3,3-tetrafluoropropene (HFC and trifluoromethyl trifluorovinyl ether (PMVE). R414B is 1234yf): 3,3,3-trifluoropropene (HFC-1243zf); and 45 the ASHRAE designation for a refrigerant blend containing trifluoromethyl trifluorovinyl ether (PMVE). R401A is the about 50 weight percent HCFC-22 (chlorodifluoromethane, ASHRAE designation for a refrigerant blend containing CHF,Cl), about 39 weight percent HCFC-124 (2-chloro-1,1, about 53 weight percent HCFC-22 (chlorodifluoromethane, 1,2-tetrafluoroethane, CFCHCIF), about 1.5 weight percent CHF,Cl), about 13 weight percent HFC-152a (1,1-difluoro isobutane (R600a, CHCH(CH)CH) and about 9.5 weight ethane, CHFCH), and about 34 weight percent HCFC-124 50 percent HCFC-142b (1-chloro-1,1-difluoroethane, (2-chloro-1,1,1,2-tetrafluoroethane, CFCHCIF). CFCICH). The present invention further relates to a method for The present invention further relates to a method for replacing an original refrigerant or heat transfer fluid compo replacing an original refrigerant or heat transfer fluid compo sition, said original composition being R401B in refrigera sition, said original composition being R416A in refrigera tion apparatus, air-conditioning apparatus, or heat pump 55 tion apparatus, air-conditioning apparatus, or heat pump apparatus, wherein said method comprises Substituting a sec apparatus, wherein said method comprises Substituting a sec ond refrigerant or heat transfer fluid composition comprising ond refrigerant or heat transfer fluid composition comprising at least one compound selected from the group consisting of at least one compound selected from the group consisting of E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze): 1,2,3,3,3- E-1,3,3,3-tetrafluoropropene (E-HFC-1234ze); 1,2,3,3,3- pentafluoropropene (HFC-1225ye): 2,3,3,3-tetrafluoropro 60 pentafluoropropene (HFC-1225ye): 2,3,3,3-tetrafluoropro pene (HFC-1234yf): 3,3,3-trifluoropropene (HFC-1243zf); pene (HFC-1234yf): 3,3,3-trifluoropropene (HFC-1243zf); and trifluoromethyl trifluorovinyl ether (PMVE). R401B is and trifluoromethyl trifluorovinyl ether (PMVE). R416A is the ASHRAE designation for a refrigerant blend containing the ASHRAE designation for a refrigerant blend containing about 61 weight percent HCFC-22 (chlorodifluoromethane, about 59 weight percent HFC-134a (1,1,1,2-tetrafluoroet CHF,Cl), about 11 weight percent HFC-152a (1,1-difluoro 65 hane, CFCHF)), about 39.5 weight percent HCFC-124 ethane, CHFCH), and about 28 weight percent HCFC-124 (2-chloro-1,1,1,2-tetrafluoroethane, CFCHCIF), and about (2-chloro-1,1,1,2-tetrafluoroethane, CFCHCIF). 1.5 weight percent n-butane (CHCH2CH2CH). US 8,911,640 B2 67 68 The present invention further relates to a method for about 45 weight percent HFC-32 and about 1.0 weight per replacing an original refrigerant or heat transfer fluid compo cent to about 28 weight percent HFC-125. sition, said original composition being R12 (CFC-12, dichlo The present invention relates to a method for replacing an rodifluoromethane, CF2Cl2) in refrigeration apparatus, air original refrigerantorheat transfer fluid composition wherein conditioning apparatus, or heat pump apparatus, wherein said the original refrigerant or heat transfer fluid composition is method comprises Substituting a second refrigerant or heat R134a or R12 and wherein said R134a or R12 is substituted transfer fluid composition comprising at least one compound by a second refrigerant or heat transfer fluid composition selected from the group consisting of 1.2.3.3.3-pentafluoro comprising: propene (HFC-1225ye); 2.3,3,3-tetrafluoropropene (HFC HFC-1243Zf and HFC-1225ye; 1234yf); 3,3,3-trifluoropropene (HFC-1243Zf); and trifluo 10 HFC-1243zf, HFC-1225ye, and HFC-125; romethyl trifluorovinyl ether (PMVE). HFC-1243zf, HFC-1225ye, and HFC-32; or The present invention further relates to a method for HFC-1243zf, HFC-1225ye, HFC-125, and HFC-32. replacing an original refrigerant or heat transfer fluid compo In all the previously described methods for replacing sition, said original composition being R500 in refrigeration refrigerants, the fluoroolefins may be used to replace refrig apparatus, air-conditioning apparatus, or heat pump appara 15 erant in existing equipment. Additionally, the fluoroolefins tus, wherein said method comprises Substituting a second may be used to replace refrigerant in existing equipment refrigerant or heat transfer fluid composition comprising at designed for use of said refrigerant. Additionally, the fluo least one compound selected from the group consisting of roolefins may be used to replace refrigerant in existing equip 1,2,3,3,3-pentafluoropropene (HFC-1225ye); 2.3,3,3-tet ment without the need to change or replace the lubricant. rafluoropropene (HFC-1234yf); 3,3,3-trifluoropropene The present invention relates to a method for reducing the (HFC-1243Zlf); and trifluoromethyl trifluorovinyl ether fire hazard in refrigeration apparatus, air-conditioning appa (PMVE). R500 is the ASHRAE designation for an azeotropic ratus, or heat pump apparatus, said method comprising intro refrigerant blend containing about 73.8 weight percent R12 ducing a composition of the present invention into said refrig ((CFC-12, dichlorodifluoromethane, CFC1) and about 26.2 erant apparatus or air-conditioning apparatus. weight percent R152a (HFC-152a, 1,1-difluoroethane, 25 Refrigerant that may leak from a refrigeration apparatus, CHFCH). air-conditioning apparatus, or heat pump apparatus, is a The present invention relates to a method for replacing an major concern when considering flammability. Should a leak original refrigerantorheat transfer fluid composition wherein occur in a refrigeration apparatus or air-conditioning appara the original refrigerant or heat transfer fluid composition is tus, refrigerant and potentially a small amount of lubricant R134a or R12 and wherein said R134a or R12 is substituted 30 may be released from the system. If this leaking material by a second refrigerant or heat transfer fluid composition comes in contact with an ignition Source, a fire may result. By comprising about 1.0 weight percent to about 37 weight per fire hazard is meant the probability that afire may occur either cent HFC-32 and about 99 weight percent to about 63 weight within or in the vicinity of a refrigeration apparatus, air percent HFC-1225ye. In another embodiment, the second conditioning apparatus, or heat pump apparatus. Reducing refrigerant or heat transfer fluid composition may comprise 35 the fire hazard in a refrigeration apparatus, air-conditioning about 1.0 weight percent to about 10 weight percent HFC-32 apparatus, or heat pump apparatus may be accomplished by and about 99 weight percent to about 90 weight percent using a refrigerant or heat transfer fluid that is not considered HFC-1225ye. flammable as determined and defined by the methods and The present invention relates to a method for replacing an standards described previously herein. Additionally, the non original refrigerantorheat transfer fluid composition wherein 40 flammable fluoroolefins of the present invention may be the original refrigerantorheat transfer fluid composition R22, added to a flammable refrigerant or heat transfer fluid, either R404A, or R410A and wherein said R22, R404A or R410A is in the apparatus already or prior to adding to the apparatus. substituted by a second refrigerant or heat transfer fluid com The non-flammable fluoroolefins of the present invention position comprising about 1.0 weight percent to about 37 reduce the probability of a fire in the event of a leak and/or weight percent HFC-32 and about 99 weight percent to about 45 reduce the degree of fire hazard by reducing the temperature 63 weight percent HFC-1225ye. In another embodiment, the or size of any flame produced. second refrigerant or heat transfer fluid composition may The present invention further relates to a method for reduc comprise about 20 weight percent to about 37 weight percent ing fire hazard in or in the vicinity of a refrigeration apparatus, HFC-32 and about 80 weight percent to about 63 weight air-conditioning apparatus, or heat pump apparatus, said percent HFC-1225ye. 50 method comprising combining at least one non-flammable The present invention further relates to a method for fluoroolefin with a flammable refrigerant and introducing the replacing an original refrigerant or heat transfer fluid compo combination into a refrigeration apparatus, air-conditioning sition wherein the original refrigerant or heat transfer fluid apparatus, or heat pump apparatus. composition is R22, R404A, or R410A and wherein said R22, The present invention further relates to a method for reduc R404A or R410A is substituted by a second refrigerant or 55 ing fire hazard in or in the vicinity of a refrigeration apparatus, heat transfer fluid composition comprising about 20 weight air-conditioning apparatus, or heat pump apparatus, said percent to about 95 weight percent HFC-1225ye, about 1.0 method comprising combining at least one non-flammable weight percent to about 65 weight percent HFC-32, and about fluoroolefin with a lubricant and introducing the combination 1.0 weight percent to about 40 weight percent HFC-125. In into the refrigeration apparatus, air-conditioning apparatus, another embodiment, the second refrigerant or heat transfer 60 or heat pump apparatus comprising flammable refrigerant. fluid composition comprises about 30 weight percent to about The present invention further relates to a method for reduc 90 weight percent HFC-1225ye, about 5.0 weight percent to ing fire hazard in or in the vicinity of a refrigeration apparatus, about 55 weight percent HFC-32, and about 1.0 weight per air-conditioning apparatus, or heat pump apparatus, said cent to about 35 weight percent HFC-125. In yet another method comprising introducing at least one fluoroolefin into embodiment, the second refrigerant or heat transfer fluid 65 said apparatus. composition comprises about 40 weight percent to about 85 The present invention further relates to a method of using a weight percent HFC-1225ye, about 10 weight percent to flammable refrigerant in refrigeration apparatus, air-condi US 8,911,640 B2 69 70 tioning apparatus, or heat pump apparatus, said method com erator or freezer cases in a Supermarket, building spaces prising combining said flammable refrigerant with at least requiring air-conditioning, or the passenger compartment of one fluoroolefin. an automobile requiring air-conditioning. A heat sink may be The present invention further relates to a method for reduc defined as any space, location, object or body capable of ing flammability of a flammable refrigerant or heat transfer 5 absorbing heat. A vapor compression refrigeration system is fluid, said method comprising combining the flammable one example of such a heat sink. refrigerant with at least one fluoroolefin. The present invention further relates to a process for trans EXAMPLES fer of heat from a heat source to a heat sink wherein the compositions of the present invention serve as heat transfer 10 Example 1 fluids. Said process for heat transfer comprises transporting the compositions of the present invention from a heat Source Performance Data to a heat sink. Heat transfer fluids are utilized to transfer, move or remove Table 7 shows refrigeration performance, as pressure in the heat from one space, location, object or body to a different 15 evaporator (Evap) and condenser (Cond), discharge tempera space, location, object or body by radiation, conduction, or ture (Disch T), energy efficiency (COP), and capacity (Cap), convection. A heat transfer fluid may function as a secondary for compounds of the present invention as compared to CFC coolant by providing means of transfer for cooling (or heat 113, HFC-43-10mee, CFOCH, and HFC-365mfc. The ing) from a remote refrigeration (or heating) system. In some data are based on the following conditions. systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or con dense). Alternatively, evaporative cooling processes may uti Evaporator temperature 40.0° F (4.4° C.) lize heat transfer fluids as well. Condenser temperature 110.0° F (43.3° C.) Subcool temperature 10.0° F. (5.5° C) Aheat Source may be defined as any space, location, object Return gas temperature 75.0° F (23.8° C.) or body from which it is desirable to transfer, move or remove 25 Compressor efficiency is 70% heat. Examples of heat Sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrig TABLE 7 Comp Comp Evap Evap Cond Cond Disch Disch Pres Pres Pres Pres T T Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F) (C.) COP (Btu/min) (kW) CFC-113 2.7 8.6 12.8 88.3 156.3 69.1 4.18 4.8 O.26 HFC-43-1Omee 2.0 3.4 10.4 71.9 1328 56.O 394 2.2 O.21 CFOCH 1.5 O.1 8.3 57.0 131.3 SS.2, 3.93 9.5 O.17 HFC-36Smfc. 3.6 25.1 6.3 112.1. 146.3 63.5 4.11 21.4 O.38 ,1,1,3,4,5,55-octafluoro-4- 2.1 4.4 10.7 71.9 127.1 52.8 3.83 2.3 O.24 (trifluoromethyl)-2-butene ((HFC-152-11mmyyZ) 1,144.55,5-octafluoro-2- 2.0 3.4 10.4 71.9 127.3 52.9 3.83 1.8 O.23 (trifluoromethyl)-2-pentene (HFC-152-11mmtz) ,1,1,2,2,3,4,5,5,6,6,6- 2.5 7.3 12.3 85.1 121.8 49.9 3.69 3.8 O.24 dodecafluoro-3-hexene (FC-151-12mcy) 1,3-tetrafluoro-2-butene 2.5 7.4 11.6 80.1 162.O 72.2 4.25 5.9 O.28 (HFC-1354mzy) 1,144.4-hexafluoro-2,3- 2.0 3.S 10.O 69.2 122.7 SO4 3.73 1.2 O.2O bis(trifluoromethyl)-2-butene (FC-151-12mmitt) 2,3,3,4,4,5,5,6,6- 2.1 4.4 10.6 72.9 126.7 52.6 3.84 2.3 O.22 decafluorocyclohexene (FC-C151-10y) 3,3,4,4,5,5,5-heptafluoro-2- 2.0 4.1 9.9 68.5 13.O.O 54.4 3.92 2.0 O.21 methyl-1-pentene (HFC-1567fts) 3.34,4,5,5,6,6,6-nonafluoro-1- 1.6 1.O 8.6 59.4 130.7 54.8 3.92 O.O O.18 hexene (PFBE) 4,4,5,5,6,6,6-heptafluoro-2- 1.3 9.2 7.4 S13 137.8 S8.8 4.04 8.9 O16 hexene (HFC-1567szz) 1,1,144,5,5,6,6,6-decafluoro 2.0 3.7 10.7 73.8 1311 SS.1 3.90 2.4 O.22 2-hexene (F13E) 1,1,1,2,3,4,5,55-nonafluoro 2.5 7.3 12.3 85.1 121.8 49.9 3.69 3.8 O.24 4-(trifluoromethyl)-2- pentene (FC-151-12 mmZZ) 1,1,1,2,2,5,5,6,6,6- 2.4 6.6 12.6 86.7 1280 53.3 3.83 4.4 O.25 decafluoro-3-hexene (F22E) US 8,911,640 B2 71 72 Example 2 ture (Disch T), energy efficiency (COP), and capacity (Cap), Performance Data for compounds of the present invention as compared to HFC Table 8 shows refrigeration performance, as pressure in the 245fa. The data are based on the following conditions. evaporator (Evap) and condenser (Cond), discharge tempera ture (Disch T), energy efficiency (COP), and capacity (Cap), 5 for compounds of the present invention as compared to CFC 11 and HCFC-123. The data are based on the following con ditions. Evaporator temperature 40.0° F (4.4° C.) 10 Condenser temperature 110.0° F (43.3° C.) Evaporator temperature 40.0° F (4.4° C.) Subcool temperature 10.0° F. (5.5° C) Condenser temperature 110.0° F (43.3° C.) Subcool temperature 10.0° F (5.5° C.) Return gas temperature 75.0° F (23.8° C.) Return gas temperature 75.0° F (23.8° C.) Compressor efficiency is 70% Compressor efficiency is 70%

TABLE 8 Comp Comp Evap Evap Cond Cond Disch Disch Pres Pres Pres Pres T T Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F) (C.) COP (Btu/min) (kW) CFC-11 7.1 49.0 28.0 1928, 190.5 88.1 4.29 41.1 0.72 HCFC-123 5.8 40.3 25.0 1724 174.2 79.0 4.25 35.2 O.62 1,2,3,3,445.5- 6.0 41.6 25.3 1746 131.7 SS.4 3.87 31.6 0.55 octafluorocyclopentene (FC-C1418y) 1,1,1,2,3,4,4,5,5,5- 7.5 S1.8 3O.O 206.6 124.9 S1.6 3.66 35.3 O.62 decafluoro-2-pentene (FC-141-10myy) 1,1,1,2,4,4,5,5,5- S.S. 37.9 23.7 163.1 132.0 SS6 3.85 29.0 O.S1 nonafluoro-2-pentene (HFC-1429myz) 1,1,1,3,4,4,5,5,5- 5.5 37.9 23.7 163.1 132.O 55.6 3.85 29.0 O.51 nonafluoro-2-pentene (HFC-1429mzy) 3,3,4,4,5,55- 5.4 37.O 23.1 1593 135.3 S74 3.92 29.0 O.S1 heptafluoro-1-pentene (HFC-1447fz) 1,1,1,444-hexafluoro-2- 4.7 32.3 20.8 1434 150.1 65.6 4.11 27.5 O.48 butene (F11E) 1,1,1,444-hexafluoro-2- 4.8 330 21.O 1449 132.6 55.9 3.88 25.9 O.45 (trifluoromethyl)-2- butene (HFC-1429mzt) 1,1,1,44.55.5- S.S. 37.9 244 168.O 137.O 58.3 3.93 30.6 O.S4 octafluoro-2-pentene (F12E)

Example 3 45

Performance Data

Table 9 shows refrigeration performance, as pressure in the 50 evaporator (Evap) and condenser (Cond), discharge tempera TABLE 9 Comp Comp Evap Evap Cond Cond Disch Disch Pres Pres Pres Pres T T Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F) (C.) COP (Btu/min) (kW) HFC- 245fa 1.O.O 68.8 38.9 268.S 156.7 69.3 4.10 53.3 O.93 2,3,3-trifluoropropene 12.6 87.1 45.4 313.O 172.8 78.2 4.19 65.6 1.15 (HFC-1243yf) 1,1,144.4-hexafluoro-2- 12.S 85.9 47.5 327.4 148.8 64.9 3.99 62.8 1.10 butene (F11E) 1,3,3,3-tetrafluoropropene 12.1. 83.4 45.8 315.6 1788 81.6 4.19 65.6 1.15 (HFC-1234ze) 1,1,1,2,4,4,4-heptafluoro- 1O.S. 72.5 39.9 27SO 142.3 61.3 3.94 S2.O O.91 2-butene (HFC-1327my) US 8,911,640 B2 74 TABLE 9-continued Comp Comp Evap Evap Cond Cond Disch Disch Pres Pres Pres Pres T T Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F) (C.) COP (Btu/min) (kW) 1,2,3,3-tetrafluoropropene 9.6 66.3 36.9 254.6 176.9 8O.S 4.21 53.0 (HFC-1234ye) pentafluoroethyl 13.1 90.4 49.3 339.8 130.7 548 3.69 59.3 1.04 trifluorovinyl ether (PEVE)

Example 4 perature (Disch T), energy efficiency (COP), and capacity Performance Data (Cap), for compounds of the present invention as compared to Table 10 shows refrigeration performance, as pressure in 15 HFC-134a, HFC-152a, and HFC-227ea. The data are based the evaporator (Evap) and condenser (Cond), discharge tem perature (Disch T), energy efficiency (COP), and capacity on the following conditions. (Cap), for compounds of the present invention as compared to CFC-114 and HFC-236fa. The data are based on the follow ing conditions. 2O Evaporator temperature 40.0° F (4.4° C.) Condenser temperature 110.0° F (43.3° C.) Evaporator temperature 40.0° F (4.4° C.) Subcool temperature Condenser temperature 110.0° F (43.3° C.) 10.0° F. (5.5° C) Subcool temperature 10.0° F (5.5° C.) Return gas temperature 75.0° F (23.8° C.) Return gas temperature 75.0° F (23.8° C.) Compressor efficiency is 70% Compressor efficiency is 70% 25

TABLE 10 Comp Comp Evap Evap Cond Cond Disch Disch Pres Pres Pres Pres T T Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F) (C.) COP (Btu/min) (kW) CFC-114 15.4 106.5 54.3 374.2 147.2 64.O 3.97 72.9 1.28 HFC-236fa 18.2 1258 64.2 442.6 142.8 61.6 3.86 82.9 1.45 1,1,1,2,3,444-octafluoro-2- 17.2 118.8 59.1 407.4 131.8 55.4 3.68 72.1 1.26 butene (FC-1318my) 1,2,3,3,4,4- 16.5 113.5 58.8 405-4 141.1 60.6 3.90 76.6 1.34 hexafluorocyclobutene (FC C1316cc) 2,3,3,444-hexafluoro-1- 14.2 98.2 SO.2 346.3 139.4 59.7 3.88 65.3 1.14 butene (HFC-1336yf) 3.3.4.4.4-pentafluoro-1- 14.8 101.8 S3.S. 368.S 145.5 63.1 3.95 70.7 1.24 butene (HFC-1345fz)

Example 5 45

Performance Data Table 11 shows refrigeration performance, as pressure in 50 the evaporator (Evap) and condenser (Cond), discharge tem TABLE 11 Comp Comp Evap Evap Cond Cond Disch Disch Pres Pres Pres Pres T T Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F) (C.) COP (Btu/min) (kW) HFC-134a 49.6 3416 1612 1111.4 168.9 76.1 3.86 213.3 3.73 HFC-152a. 46.2 318.8 146.5 1009.9 2001 93.4 4.02 209.4 3.67 HFC-227ea 32.3 222.7 105.5 727.4 142.9 61.6 3.67 129.3 2.26 2,3,3,3-tetrafluoropropene 47.4 326.7 1396 962.2 154.8 68.2 3.79 18O.S 3.16 (HFC-1234yf) 3,3,3-trifluoropropene (HFC- 39.0 268.8 122.0 841.O 1662 74.6 3.95 166.3 2.91 1243zf) 1,2,3,3,3-pentafluoropropene 36.1 248.9 112.9 778.4 157.8 69.9 3.86 148.9 2.61 (HFC-1225ye) US 8,911,640 B2 76 TABLE 1 1-continued Comp Comp Evap Evap Cond Cond Disch Disch Pres Pres Pres Pres T T Cap Cap Compound (Psia) (kPa) (Psia) (kPa) (F) (C.) COP (Btu/min) (kW) E-1,3,3,3-tetrafluoropropene 35.5 245.0 115.1 793.9 162.4 72.4 3.90 153.8 2.69 (E-HFC-1234ze) trifluoromethyl trifluorovinyl 39.3 271.1 124.0 855.2 140.9 60.5 3.57 147.6 2.58 ether (PMVE)

Example 6 V tangential Velocity of refrigerant entering impeller, meters/sec Flammability 15 r—radius of inlet of impeller, meters Assuming the refrigerant enters the impeller in an essen Flammable compounds may be identified by testing under tially axial direction, the tangential component of the Velocity ASTM (American Society of Testing and Materials) E681 v=0, therefore 01, with an electronic ignition Source. Such tests of flamma bility were conducted on compositions of the present disclo T=m *y-, *r, Equation 2 sure at 101 kPa (14.7 psia), 50 percent relative humidity, and The power required at the shaft is the product of the torque the temperature indicated, at various concentrations in air in and the rotative speed order to determine if flammable and if so, find the lower flammability limit (LFL). The results are given in Table 12. P=To Equation 3 25 where TABLE 12 P-power, W () angular Velocity, radians/s Temperature Composition (° C.) LFL (vol% in air) therefore,

HFC-1225ye 100 Non-flammable 30 HFC-1234yf 100 S.O E-HFC-1234ze 100 6.O At low refrigerant flow rates, the tip speed of the impeller HFC-1429myz/mzy 23 Non-flammable and the tangential velocity of the refrigerant are nearly iden F1 2E 23 Non-flammable tical; therefore HFC-1225ye/HFC- 60 Non-flammable 32 (6.5/35 wt %) ro)=y. Equation 5 HFC-1225ye/HFC- 60 Non-flammable 35 32 (63/37 wt.%) and HFC-1225ye/HFC- 60 13.0 32 (62/38 wt %) P=m *y-, *y, Equation 6 HFC-1225ye/HFC- 60 13.0 32 (60/40 wt %) Another expression for ideal power is the product of the 40 mass rate of flow and the isentropic work of compression, The results indicate that HFC-1234yf and E-HFC-1234ze are flammable, while HFC-1225ye, HFC-1429myZ/mzy, and P=m*H*(1000 J/kJ) Equation 7 F12E are non-flammable. For mixtures of HFC-1225ye and where H=Difference in enthalpy of the refrigerant from a satu HFC-32 (which is known to be flammable in the pure state) it 45 has been determined that 37 weight percent HFC-32 is the rated vapor at the evaporating conditions to Saturated con highest amount that can be present to maintain the non-flam densing conditions, kJ/kg. mable characteristic. Those compositions comprising fluo Combining the two expressions Equation 6 and 7 produces, roolefins that are non-flammable are more acceptable candi dates as refrigerant or heat transfer fluid compositions. v, *y-1000*H, Equation 8 50 Although Equation 8 is based on Some fundamental Example 7 assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip Tip Speed to Develop Pressure speeds of refrigerants. Table 13 below shows theoretical tip speeds that are calcu Tip speed can be estimated by making some fundamental 55 lated for 1.2.2-trichlorotrifluoroethane (CFC-113) and com relationships for refrigeration equipment that use centrifugal positions of the present invention. The conditions assumed compressors. The torque an impeller ideally imparts to a gas for this comparison are: is defined as 60 T=m (v*r-v *r) Equation 1 Evaporator temperature 40.0° F (4.4° C.) Condenser temperature 110.0° F (43.3° C.) where Liquid Subcool temperature 10.0°F. (5.5° C.) T-torque, Newton-meters Return gas temperature 75.0° F (23.8° C.) m mass rate of flow, kg/sec Compressor efficiency is 70% V tangential Velocity of refrigerant leaving impeller (tip 65 speed), meters/sec These are typical conditions under which small turbine re-radius of exit impeller, meters centrifugal compressors perform. US 8,911,640 B2 77 78 TABLE 13 compressor design changes. Most preferred compositions have tip speeds within about 10 percent of CFC-113. Tip speed Tip speed H H*O.7 H8O.7 (V2) relative Example 8 Compound Btu/lb Btu/lb KJ/Kg mis to CFC-113 Refrigeration Performance Data CFC-113 10.92 7.6 17.8 33.3 na HFC-152-11mmyyZ 11.56 8.1 18.8 37.2 1.03% Table 14 shows the performance of various refrigerant FC-151-12mcy 11.86 8.3 19.3 39.0 10496 compositions of the present invention as compared to HFC HFC-1354mzy 13.96 9.8 22.7 SO.8 11.3% FC-151-12mmitt 11.93 8.4 19.4 39.4 105% 134a. In Table 14, Evap Pres is evaporator pressure, Cond FC-C151-10y 1248 8.7 20.3 42.5 107% 10 Pres is condenser pressure, Comp Disch T is compressor HFC-1567 fin 14.21 9.9 23.1 52.1 114% discharge temperature, COP is energy efficiency, and CAP is PFBE 12.8 9.0 20.8 44.4 1.08% capacity. The data are based on the following conditions. HFC-1567SZZ 1342 9.4 21.9 47.8 11.1% HFC-1438mzz 11.73 8.2 19.1 38.2 10496 FC-151-12mmzz 11.86 8.3 19.3 39.0 10496 15 Evaporator temperature 40.0° F (4.4° C.) HFC-153-1Omczz 12.23 8.6 19.9 41.1 106% Condenser temperature 130.0° F (54.4° C.) Subcoolamount 10.0° F. (5.5° C) Return gas temperature 60.0° F (15.6° C.) The example shows that compounds of the present inven Compressor efficiency is 100% tion have tip speeds within about 15 percent of CFC-113 and would be effective replacements for CFC-113 with minimal Note that the Superheat is included in cooling capacity. TABLE 1.4 Comp Comp Evap Evap Cond Cond Disch Disch Cap Pres Pres Pres Pres T T (Btu? Cap Composition (wt %) (Psia) (kPa) (Psia) (kPa) (F) (C.) min) (kW) COP HFC-134a S.O.3 346 214 1476 1S6 68.9 213 3.73 4.41 HFC-1225ye 37.6 259 165 138. 146 633 162 2.84 4.41 HFC-1225ye/HFC-152a (85/15) 39.8. 274 173 193 151 66.1 173 3.03 4.45 HFC-1225ye/HFC-32 43.1 297 184 1269 149 6SO 186 3.26 4...SO (97/3) HFC-1225ye/HFC-32 (964) 44.2 3OS 189 1303 150 65.6 191 3.35 4.51 HFC-1225ye/HFC-32 46.S 321 197 1358 151 66.1 200 3.SO 4.53 (95/5) HFC-1225ye/HFC-32 (94/6) 47.3 326 200 1379 153 67.2 203 3.56 4.52 HFC-1225ye/HFC-32 (93/7) 48.8 336 20S 1413 154 67.8 210 3.68 4.53 HFC-1225ye/HFC-32 (90/10) S3.0 36S 222 1531 57 69.4 227 3.98 4.52 HFC-1243zf HFC-1225ye 40.8. 281 72 1186 148 644 170 2.97 4.39 (40/60) HFC-1243zf HFC-1225ye 41.8 288 74 1200 149 6SO 172 3.02 4.37 (50/50) HFC-1243zf HFC-1225ye 42.9 296 77 1220 149 65.O. 175 3.07 4.36 (60/40) HFC-1243zf HFC-1225ye 44.1 304 8O 1241 SO 65.6 178 3.12 4.35 (70/30) HFC-1243zf HFC-1225ye/HFC- 42.7 294 79 1234 148 644 176 3.09 4.38 25 (4.0/56/4) HFC-1243zf HFC-1225ye/HFC- 43.7 301 81 1248. 149 6S.O 179 3.13 4.37 25 (50/46/4) HFC-1243zf HFC-1225ye/HFC- 44.8 309 84 1269 149 65.O 182 3.18 4.36 25 (60/36/4) HFC-1243zf HFC-1225ye/HFC- 49.9 344 201 1386 153 67.2 202 3.54 4.40 25 (70/26/4) HFC-1243zf HFC-1225ye/HFC- 48.4 334 99 1372 153 67.2 202 3.54 4.47 32 (40/55/5) HFC-1243zf HFC-1225ye/HFC- 45.6 314 89 1303 151 66.1 190 3.33 4.44 32 (42/55/3) HFC-1243zf HFC-1225ye/HFC- 50.3 347 203 1400 154 67.8. 206 3.60 4.43 32 (60/35/5) HFC-1243zf HFC-1225ye/HFC- 47.7 329 94 1338 152 66.7 195 3.41 4.41 32 (62/35/3) HFC-1243zf HFC-1225ye/HFC- 44.2 305 84 1269 149 6S.O 183 3.21 4.41 25/HFC-32 (40/55/4/1) HFC-1243zf HFC-1225ye/HFC- 45.3 312 88 1296 1SO 65.6 188 3.29 4.42 25/HFC-32 (40/55/3/2) HFC-1243zf HFC-1225ye/HFC- 46.3 319 89 1303 150 65.6 188 3.29 4.37 25/HFC-32 (60/35/4/1) HFC-1243zf HFC-1225ye/HFC- 47.3 326 93 1331 S1 66.1 192 3.37 4.39 25/HFC-32 (60/35/3/2) US 8,911,640 B2 79 80 Several com TABLE 15-continued positions have even higher energy efficiency (COP) than Existing Evap Cond P Compr HFC-134a while maintaining lower or equivalent discharge Refrigeran Press Press Disch T CAP pressures and temperatures. Capacity for the compositions Product wt % (kPa)) (kPa) (C.) (kJ/m3) EER listed in Table 14 is also similar to R134a indicating these HFC-32.H 30, 15,55 276 2046 710 4.76 compositions could be replacement refrigerants for R134a in 25 HFC refrigeration and air-conditioning, and in mobile air-condi 225ye tioning applications in particular. Results also show cooling HFC-32.H 30, 19 S1 278 2056 24.8 724 4.75 capacity of HFC-1225ye can be improved with addition of 25 HFC 10 225ye other compounds such as HFC-32. HFC-32.H 3O2OSO 287 2102 24.0 757 4.73 25 HFC Example 9 225ye HFC-32.H 3O3O40 311 2218 24.0 855 4.68 Refrigeration Performance Data 25 HFC 15 225ye HFC-32.H 30,35/35 324 2271 23.0 906 4.66 Table 15 shows the performance of various refrigerant 25 HFC compositions of the present invention as compared to R404A 225ye HFC-32.H 31 20.49 285 2090 25.5 7S6 4.74 and R422A. In Table 15, Evap Pres is evaporator pressure, 25 H Cond Presis condenser pressure, Comp Disch T is compres 225ye sor discharge temperature, EER is energy efficiency, and CAP HFC-32.H 33.22.45 298 2157 27.0 820 4.72 is capacity. The data are based on the following conditions. 25 H 225ye HFC-32.H 35/15/50 296 2157 29.0 820 4.72 25 H Evaporator temperature -17.8° C. 225ye Condenser temperature 46.1° C. 25 HFC-32.H 3S2O45 3O8 2212 29.0 868 4.70 Subcoolamount 5.5oC. 25 H Return gas temperature 15.6°C. 225ye Compressor efficiency is 70% HFC-32.H 35/30/35 332 2321 27.0 968 4.66 25 H 225ye Note that the Superheat is included in cooling capacity. 30 HFC-32.H 3S4O2S 357 2424 26.0 2O68 4.64 25 HFC TABLE 1.5 225ye HFC-32.H SO3O2O 390 2S84 38.0 2277 4.54 Existing Evap Cond P Compr 25 H Refrigerant Press Press Disch T CAP 225ye Product wt % (kPa)) (kPa) (C.) (kJ/m3) EER 35 HFC-32.H 40.30.30 353 2418 31.0 2O77 4.66 25 H R22 267 1774 144 697 4.99 225ye R404A 330 2103 101.1 769 4.64 HFC-32.H 40.35,25 364 246S 31.0 2124 4.64 RSO7A 342 2151 100.3 8O1 4.61 25 H R422A 324 2124 95.0 699 4.54 225ye Candidate HFC-32.H 45, 30.25 372 2505 3S.O 2180 4.66 Replacement 40 25 HFC 225ye HFC-32, 20.80 200 62O 17 331 4.91 HFC-1225ye HFC-32, 30, 70 246 879 26 S87 4.85 Several compositions have energy efficiency (EER) com HFC-1225ye parable top R404A and R422A. Discharge temperatures are HFC-32, 40.60 284 2101 34 788 4.74 45 HFC-1225ye also lower than R404A and R507A. Capacity for the compo HFC-32, 35.65 256 948 3O.S 652 485 sitions listed in Table 15 is also similar to R404A, R507A, and HFC-1225ye R422A indicating these compositions could be replacement HFC-32, 37,63 264 991 32.2 694 4.81 refrigerants for R404A, R507A, or R422A in refrigeration HFC-1225ye and air-conditioning. HFC-32, 10.10.80 173 435 O7.O 159 4.97 50 HFC-125 HFC Example 10 225ye HFC-32 HFC- 15.5.5, 79.5 184 509 11.9 235 4.97 Refrigeration Performance Data 25 HFC 225ye Table 16 shows the performance of various refrigerant HFC-32, HFC- 24f13.7.62.3 242 851 19.7 544 4.85 55 compositions of the present invention as compared to HCFC 25 HFC 225ye 22 and R410A. In Table 16, Evap Presis evaporator pressure, HFC-32, HFC- 2S,2SFSO 276 2041 2O.O 689 4.73 Cond Pres is condenser pressure, Comp Disch T is compres 25 HFC sor discharge temperature, EER is energy efficiency, and CAP 225ye is capacity. The data are based on the following conditions. HFC-32, HFC- 25,40,35 314 2217 19.0 840 4.66 25 HFC 60 225ye Evaporator temperature 4° C. HFC-32 HFC- 27.5/17.5/55 264 1980 22.8 653 4.78 Condenser temperature 43° C. 25 HFC Subcoolamount 6° C. 225ye Return gas temperature 18° C. HFC-32, HFC- 30.10,60 26S 1990 2S.O 664 4.78 Compressor efficiency is 70% 25 HFC 65 225ye US 8,911,640 B2 81 82 Note that the Superheat is included in cooling capacity. Evaporator temperature 4.4° C. Condenser temperature S4.4° C. TABLE 16 Subcoolamount 5.5oC. Return gas temperature 15.6°C. Compr Compressor efficiency is 100% Evap Cond Disch Press Press Temp CAP (kPa) (kPa) (C.) (kJ/m3) EER Note that the Superheat is included in cooling capacity. Existing refrigerant product TABLE 17 R22 S6S 1648 90.9 3808 9.97 10 R410A 900 2571 88.1 S488 9.27 Evap Cond Compr Candidate replacement product Existing Refrigerant Press Press Disch T CAP (Composition wt %) Product wt % (kPa)) (kPa) (C.) (kJ/m) EER HFC-32/HFC-1225ye (40/60) 630 1948 86.7 4242 9.S6 R22 573. 2149 88.6 3494. 14.73 HFC-32/HFC-1225ye (45/55) 666 2041 88.9 4445 949 15 R410A 911 3343 89.1 4787 13.07 HFC-32/HFC-1225ye (50/50) 701. 2127 91.0 4640 9.45 R407C 567 2309 80.0 3397 14:06 HFC-32/HFC-1225ye (30/70) 536 1700 82.1 3729 9.73 R417A 494 1979 67.8 2768 13.78 HFC-32/HFC-1225ye (35/65) 575 1805 84.5 3956 9.66 Candidate Replacement HFC-32/HFC-1225ye (37/63) S90 1845 85.5 4043 9.64 HFC-32/HFC-125/HFC-1225ye 784 2323 94.6 5087 942 HFC-32 HFC-12SHFC- 30.40, 732 2823 81.1 3937 13:20 (60/5/35) 1225ye 30 HFC-32/HFC-125/HFC-1225ye 8O3 236S 94.2 5173 942 HFC-32 HFC-12SHFC- 23:25, 598 2429 78.0 3409 13.54 (60/10/30) 1225ye 52 HFC-32/HFC-125/HFC-1225ye 822 24O7 93.9 5256 9.39 (60/15/25) HFC-32/HFC-125/HFC-1225ye 742 2220 90.3 482O 942 Compositions have energy efficiency (EER) comparable to (50/10/40) HFC-32/HFC-125/HFC-1225ye 721 2173 90.7 4730 9.45 25 R22, R407C, R417A, and R410A while maintaining low (50/5/45) discharge temperatures. Capacity for the compositions listed HFC-32/HFC-125/HFC-1225ye 762 2266 90.0 4911 942 in Table 17 is also similar to R22, R407c and R417A indicat (50/15/35) ing these compositions could be replacement refrigerants for HFC-32/HFC-125/HFC-1225ye 692 2097 85.9 4518 9.45 (40/15/45) R22, R407C or R417A in refrigeration and air-conditioning. HFC-32/HFC-125/HFC-1225ye 671. 2047 86.2 4.425 949 30 What is claimed is: (40/10/50) 1. A method for producing heating or cooling in a refrig HFC-32/HFC-125/HFC-1225ye 654 2001 83.8 4304 9.49 eration, air-conditioning, or heat pump apparatus, said (35/15/50) HFC-32/HFC-125/HFC-1225ye 643 1976 85.2 4287 9.54 method comprising introducing a refrigerant or heat transfer (37.5/11.5/51) fluid composition into said apparatus having a centrifugal HFC-32/HFC-125/HFC-1225ye 593 1848 83.8 4028 9.62 35 compressor; wherein said refrigerant or heat transfer fluid (34/6/60) composition consists of E-1,3,3,3-tetrafluoro-1-propene or HFC-32/HFC-125/HFC-1225ye 548 1732 82.O 3788 9.70 (30/3/67) Z-1,3,3,3-tetrafluoro-1-propene and optionally an additive HFC-32/HFC-125/HFC-1225ye 590 1837 81.7 398O 96.O selected from the group consisting of lubricants, tracers, UV (30/12.7/57.3) dyes, solubilizing agents, and stabilizers; and wherein said HFC-32/HFC-125/HFC-1225ye 544 1715 78.7 3713 9.66 40 apparatus is used as designed for HFC-134a or HFC-245fa. (24/13.7/62.3) HFC-32/HFC-125/HFC-1225ye 471 1522 76.9 3329 9.82 2. The method of claim 1 comprising producing cooling by (20/5/75) evaporating the refrigerant or heat transfer fluid composition HFC-32/HFC-125/HFC-1225ye 427 1398 74.1 3061 9.89 in the vicinity of a body to be cooled, and thereafter condens (15/5.5/79.5) ing said composition. 45 3. The method of claim 1 comprising producing heating by Compositions have energy efficiency (EER) comparable to condensing the refrigerant or heat transfer fluid composition R22 and R410A while maintaining reasonable discharge tem in the vicinity of a body to be heated and thereafter evaporat peratures. Capacity for certain compositions listed in Table ing said composition. 16 is also similar to R22 indicating these compositions could 4. The method of claim 1 wherein the centrifugal compres be replacement refrigerants for R22 in refrigeration and air 50 sor is a multi-stage centrifugal compressor. conditioning. Additionally, there are compositions listed in 5. The method of claim 1, wherein the refrigeration, air Table 16 with capacity approaching or equivalent to that for conditioning or heat pump apparatus is designed for using R410A indicating that those compositions could be replace HFC-134a. ment refrigerants for R410A in refrigeration and air-condi 6. The method of claim 5, wherein the refrigerant or heat tioning. 55 transfer fluid composition comprises E-1,3,3,3-tetrafluoro-1- propene. Example 11 7. The method of claim 1, wherein the refrigeration, air conditioning or heat pump apparatus is designed for use of Refrigeration Performance Data HFC-245fa. 60 8. The method of claim 7, wherein the refrigerant or heat Table 17 shows the performance of various refrigerant transfer fluid composition comprises Z-1,3,3,3-tetrafluoro-1- compositions of the present invention as compared to HCFC propene. 22, R410A, R407C, and R417A. In Table 17, Evap Presis 9. The method of claim 1, wherein said refrigerant or heat evaporator pressure, Cond Presis condenser pressure, Comp transfer fluid composition consists of E-1,3,3,3-tetrafluoro Disch T is compressor discharge temperature, EER is energy 65 1-propene or Z-1,3,3,3-tetrafluoro-1-propene and an additive efficiency, and CAP is capacity. The data are based on the selected from the group consisting of lubricants, tracers, UV following conditions. dyes, solubilizing agents, and stabilizers. US 8,911,640 B2 83 84 10. The method of claim 1, wherein the centrifugal com pressor comprises at least 2 stages. 11. The method of claim 1, wherein the refrigeration, air conditioning or heat pump apparatus is a chiller. 12. The method of claim 1, wherein the refrigeration, air- 5 conditioning or heat pump apparatus is a heat pump. k k k k k