Fluorinated Alkenes

Abstract

A process for transferring heat comprising providing an article and contacting the article with a heat transfer medium, the heat transfer medium being a compound of formula (1), R f and a composition formed by the process of contacting CH═CHF with a fluorinated ethylene compound of formula (2), CX₁X₂═CX₃X₄, in the presence of a Lewis acid catalyst. f is C1~C 10 In the compound of formula (2), X1, X2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, and X4 is F. The resulting composition comprises a compound of formula (3), R f CF3(CX5X6CX7X8)nCH=CHCX9X 10 CX 11 X 12 In the compound of formula (3), X5, X6, X7, X8, X9, X 10 , X 11 and X 12 are each independently H, Cl, or F, and n is an integer of 0 or 1.

Description

[Technical field]

[0001] This application claims the benefit of U.S. Patent Application No. 62 / 835,703, filed April 18, 2019. The disclosure of U.S. Patent Application No. 62 / 835,703 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present invention is directed to the use of fluorinated alkene compounds as heat transfer materials. [Background technology]

[0003] There is interest in low temperature heat utilization (i.e., heat at temperatures below about 300°C). Such heat may be extracted from a variety of commercial, industrial, or natural sources. Increasing the temperature of available heat by a high temperature mechanical compression heat pump (HTHP) to meet heating requirements, and conversion of available heat to mechanical or electrical power via an organic Rankine cycle (ORC) are two promising approaches to low temperature heat utilization.

[0004] ORC and HTHP require the use of working fluids. Working fluids with high global warming potential (GWP) commonly used for HTHP and ORC (e.g., HFC-245fa) are being considered, and more environmentally sustainable working fluids for HTHP and ORC are needed. More specifically, there is a need for low GWP working fluids with boiling points higher than about 50°C (hereinafter, "°C") that are particularly suitable for converting heat available at temperatures approaching or above 200°C, and for heating at temperatures approaching 200°C from heat available at lower temperatures. Even more specifically, low GWP working fluids with boiling points close to that of ethanol (78.4°C) may be advantageous as replacements for ethanol in ORC systems, especially for heavy duty vehicles (e.g., trucks) in Europe. Such fluids can also be used as solvents and heat transfer fluids for various applications, including immersion cooling and phase change cooling (e.g., of electronics, including data center cooling).

[0005] Fluoroalkenes such as F23E (C2F5CH=CHC3F7) can be prepared from F-heptene-3 starting material using a four-step preparation involving a sequential hydrogenation / dehydrofluorination process. However, this process is lengthy and based on relatively expensive starting materials (F-heptene is produced using the reaction of hexafluoropropene (HFP) with two moles of tetrafluoroethene (TFE)).

[0006] WO 2008 / 057513 describes a process for the preparation of internal dihydrofluoroolefins of formula RCH=CHC2F5, which comprises reacting a fluorinated olefin of RCH=CHF, where R is selected from perfluoroalkyl groups having 1 to 10 carbon atoms, and the alkyl groups are either n-alkyl chains, sec-alkyl chains, or isoalkyl chains, with tetrafluoroethylene in the liquid phase in the presence of antimony pentafluoride (SbF5) catalyst, removing the Lewis acid catalyst, and isolating the dihydrofluoroolefin. The disclosure of WO 2008 / 057513 is incorporated herein by reference. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2008 / 057513 Summary of the Invention [Means for solving the problem]

[0008] The present invention is summarized by various embodiments. One embodiment of the present invention relates to a process for transferring heat, comprising: Providing the goods; contacting the article with a heat transfer medium; The heat transfer medium comprises a composition comprising a compound of formula (4), R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX11 X 12 F(4) In the formula, R f is C1~C 10 is a perfluorinated alkyl group, In the formula, X5, X6, X7, X8, X9, X 10 , X 11 and X 12 are each independently H, Cl, or F, and n is an integer of 0 or 1; X5, X6, X7, X8, X9, X 10 , X 11 and X 12 is at least 2, and optionally (E)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(Z)(epoxide),CFCH(-O-)CHCF 3), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF3)2) , (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E),HFO-1336ze(Z),HFC-245fa,HFC-245ea,HFC-365mfc,HFC-43-10mee, (E)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z),C HCl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, N-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000, CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA,C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3)), MPPE (HFX-75), Perfluorohept-2-ene / Perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), Perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-Bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-Bromo-1,1,1 ,3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoro-propene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture, (preferred mixture and Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent Publication No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoropropene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2,3,3-trifluoro The co-compound includes at least one of the following: perfluoro-1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3).

[0009] One embodiment of the present invention relates to any combination of the preceding embodiments, wherein the compound of formula (4) comprises 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5 (F23E).

[0010] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the co-compound comprises at least one of HFO-1336mzz(E), HFO-1336mzz(Z), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), or ethanol.

[0011] Another embodiment of the present invention is a process for transferring heat, comprising: Providing the goods; contacting the article with a heat transfer medium; The heat transfer medium is a compound of formula (1), R f CH=CHF(1) In the formula, R f is C1~C 10 is a perfluorinated alkyl group, A fluorinated ethylene compound of formula (2): CX1X2=CX3X4(2) In the formula, X1, X2, X3, and X4 are each independently H, Cl, or F; At least one of X1, X2, X3 or X4 is F; in a sufficient amount to form a composition comprising a compound of formula (3) in the presence of a Lewis acid catalyst; R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(3) In the formula, X5, X6, X7, X8, X9, X 10 , X 11 and X 12 are each independently H, Cl, or F, and n is an integer of 0 or 1; X5, X6, X7, X8, X9, X 10 , X 11 and X 12 is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2), and optionally (E)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(Z)(epoxide),CFCH(-O-)CHCF 3), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF3)2) , (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E),HFO-1336ze(Z),HFC-245fa,HFC-245ea,HFC-365mfc,HFC-43-10mee, (E)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z),C HCl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, N-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000, CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA,C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3)), MPPE (HFX-75), perfluorohept-2-ene / perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-bromo-1,1,1, 3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoropropene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture (preferred mixture) Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoropropene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2,3,3-trifluoro The co-compound includes at least one of the following: perfluoro-1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3).

[0012] One embodiment of the present invention relates to any combination of the preceding embodiments, wherein the compound of formula (3) comprises 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5 (F23E).

[0013] Another embodiment of the invention relates to any combination of the preceding embodiments, wherein the co-compound comprises at least one of HFO-1336mzz(E), HFO-1336mzz(Z), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), or ethanol.

[0014] Another embodiment of the present invention is a process for treating a surface, comprising the steps of: Providing a surface; contacting the surface with a treatment composition; the surface includes a treatable material deposited thereon; The treatment composition comprises a composition comprising 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5 (F23E), and optionally (E)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(Z)(epoxide),CFCH(-O-)CHCF 3), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF3)2) , (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E),HFO-1336ze(Z),HFC-245fa,HFC-245ea,HFC-365mfc,HFC-43-10mee, (E)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z),C HCl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, N-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000, CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA,C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3)), MPPE (HFX-75), perfluorohept-2-ene / perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-bromo-1,1,1, 3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoropropene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture (preferred mixture) Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoro-propene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2,3,3- At least one of trifluoro-1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3).

[0015] Another embodiment of the present invention comprises: An evaporator; A condenser; A compressor; An expansion device; a heat transfer medium; The heat transfer medium comprises a composition comprising C3F7CH=CHC2F5 (F23E), and optionally (E)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(Z)(epoxide),CFCH(-O-)CHCF 3), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF3)2) , (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E),HFO-1336ze(Z),HFC-245fa,HFC-245ea,HFC-365mfc,HFC-43-10mee, (E)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z),C HCl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, N-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000, CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA,C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3)), MPPE (HFX-75), perfluorohept-2-ene / perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-bromo-1,1,1, 3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoropropene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture (preferred mixture) Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoro-propene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2,3,3- At least one of trifluoro-1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3).

[0016] One embodiment of the present invention relates to any combination of the preceding embodiments, wherein the condenser operates at a temperature above 100°C.

[0017] Another embodiment of the present invention comprises: a heat pipe having a working fluid therein; The working fluid comprises a composition comprising C3F7CH=CHC2F5 (F23E), and optionally (E)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(Z)(epoxide),CFCH(-O-)CHCF 3), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF3)2) , (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E),HFO-1336ze(Z),HFC-245fa,HFC-245ea,HFC-365mfc,HFC-43-10mee, (E)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z),C HCl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, N-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000, CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA,C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3)), MPPE (HFX-75), perfluorohept-2-ene / perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-bromo-1,1,1, 3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoropropene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture (preferred mixture) Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoro-propene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2,3,3- At least one of trifluoro-1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3).

[0018] Another embodiment of the present invention relates to a process for recovering heat from a heat source and generating mechanical energy, the process comprising: (a) passing a first working fluid in a liquid phase through a heat exchanger or evaporator, the heat exchanger or evaporator being in communication with a heat source that provides heat; (b) removing at least a portion of the first working fluid in a vapor phase from the heat exchanger or the evaporator; (c) passing said at least a portion of the first working fluid in a vapor phase through an expander, wherein at least a portion of the heat is converted to mechanical energy; and (d) passing at least a portion of the first working fluid in a vapor phase from the expander to a condenser, wherein the at least a portion of the first working fluid in the vapor phase is condensed to a second working fluid in a liquid phase; (e) optionally compressing and mixing the second working fluid in liquid phase with the first working fluid in step (a); (f) optionally repeating steps (a)-(e) at least once; At least one of the first working fluid or the second working fluid comprises a composition comprising a compound of formula (4), R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(4) In the formula, R f is C1~C 10 is a perfluorinated alkyl group, In the formula, X5, X6, X7, X8, X9, X 10 , X 11 and X 12 are each independently H, Cl, or F, and n is an integer of 0 or 1; X5, X6, X7, X8, X9, X 10 , X 11 and X 12 is at least 2, and optionally (E)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(Z)(epoxide),CFCH(-O-)CHCF 3), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF3)2) , (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E),HFO-1336ze(Z),HFC-245fa,HFC-245ea,HFC-365mfc,HFC-43-10mee, (E)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z),C HCl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, N-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000, CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA,C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3)), MPPE (HFX-75), Perfluorohept-2-ene / Perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), Perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-Bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-Bromo-1,1,1 ,3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoro-propene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture, (preferred mixture and Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent Publication No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoropropene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2,3,3-trifluoro The co-compound includes at least one of the following: perfluoro-1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3).

[0019] In another embodiment of the invention, an apparatus includes (a) a first heat exchanger through which a working fluid flows and is heated; (b) a compressor in fluid communication with the first heat exchanger that compresses the heated working fluid to a higher pressure; (c) a second heat exchanger in fluid communication with the compressor through which the high pressure working fluid flows and is cooled; and (d) a pressure reduction device in fluid communication with the second heat exchanger that reduces the pressure of the cooled working fluid, the pressure reduction device being further in fluid communication with an evaporator such that the working fluid is subsequently repeatedly flowed through components (a), (b), (c) and (d) in a repeating cycle.

[0020] An embodiment of the present invention relates to any combination of the preceding embodiments, wherein at least one of the first working fluid or the second working fluid comprises a composition comprising a compound of formula (4), R f CF3(CX5X6CX7X8) nCH=CHCX9X 10 CX 11 X 12 F(4) In the formula, R f is C1~C 10 is a perfluorinated alkyl group, In the formula, X5, X6, X7, X8, X9, X 10 , X 11 and X 12 are each independently H, Cl, or F, and n is an integer of 0 or 1; X5, X6, X7, X8, X9, X 10 , X 11 and X 12 is at least 2, and optionally (E)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-Hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-Bis(trifluoromethyl)oxirane, (HFO-1336mzz(Z)(epoxide),CFCH(-O-)CHCF3 ), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF3)2), (Z)-1,3,4,4,4-Pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E),HFO-1336ze(Z),HFC-245fa,HFC-245ea,HFC-365mfc,HFC-43-10mee, (E)-1-Chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)-1-Chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z),CH Cl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, N-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000, CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA,C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3)), MPPE (HFX-75), Perfluorohept-2-ene / Perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), Perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-Bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-Bromo-1,1,1 ,3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoro-propene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture, (preferred mixture and Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent Publication No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoropropene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2,3,3-trifluoro The co-compound includes at least one of the following: perfluoro-1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3).

[0021] In one embodiment, a process for transferring heat includes providing an article and contacting the article with a heat transfer medium. The heat transfer medium is a compound of formula (4), R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 In the compound of formula (4), R f is C1~C 10 Perfluorinated alkyl groups are X5, X6, X7, X8, X9, and X 10 , X 11 and X 12 are each independently H, Cl, or F, n is an integer of 0 or 1, and X5, X6, X7, X8, X9, and X 10 , X 11 and X 12 The total number of F's represented by is at least 2.

[0022] The heat transfer medium may further include one or more co-compounds.

[0023] In another embodiment, a process for transferring heat includes providing an article and contacting the article with a heat transfer medium. The heat transfer medium is a compound of formula (1), R f The present invention includes a composition formed by the process of contacting CH=CHF with a fluorinated ethylene compound of formula (2), CX1X2=CX3X4. f is C1~C 10 In the compound of formula (2), X1, X2, X3 and X4 are each independently H, Cl or F, and at least one of X1, X2, X3 or X4 is F. The contact is represented by formula (3), R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 The reaction is carried out in the presence of a Lewis acid catalyst in an amount sufficient to form a composition comprising a compound of formula (3), wherein X5, X6, X7, X8, X9, X 10 , X 11 and X 12 are each independently H, Cl, or F; X5, X6, X7, X8, X9, and X 10 , X 11 and X 12 is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2).

[0024] The heat transfer medium may further include one or more co-compounds.

[0025] In another embodiment, a process for treating a surface includes providing a surface and contacting the surface with a treatment composition. The surface includes a treatable material deposited thereon. The treatment composition includes a composition including 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5 (F23E).

[0026] The treatment composition may further include one or more co-compounds.

[0027] In another embodiment, a refrigerant system includes an evaporator, a condenser, a compressor, an expansion device, and a heat transfer medium. The heat transfer medium includes a composition comprising 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5 (F23E).

[0028] The treatment composition may further include one or more co-compounds.

[0029] In another embodiment, a heat pipe system includes a heat pipe having a working fluid therein, the working fluid comprising a composition including 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5 (F23E).

[0030] The working fluid may further include one or more co-compounds.

[0031] In another embodiment, a process for transferring heat includes providing an article and contacting the article with a heat transfer medium. The heat transfer medium is a compound of formula (4), R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(4). In the compound of formula (4), R f is C1~C 10 Perfluorinated alkyl groups are X5, X6, X7, X8, X9, and X 10 , X 11 and X12 are each independently H, Cl, or F, n is an integer of 0 or 1, and X5, X6, X7, X8, X9, and X 10 , X 11 and X 12 The total number of F's represented by is at least 2.

[0032] The heat transfer medium may further include one or more co-compounds.

[0033] Suitable co-compounds useful with the above working fluids, process compounds, and heat transfer media include (E)-1,1,1,4,4,4-hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-bis(trifluoromethyl)oxirane, , (HFO-1336mzz(Z)(epoxide), CFCH(-O-)CHCF3), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl) (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF3)2), (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E),HFO-1336ze(Z),HFC-245fa, HFC-245ea, HFC-365mfc, HFC-43-10mee, (E)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)- 1-Chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z), CHCl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, n-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000,CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA, C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3)), MPPE (HFX-75), perfluorohept-2-ene / perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-bromo-1,1,1, 3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoropropene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture (preferred mixture) Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoro-propene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2, 3,3-trifluoro-1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3).

[0034] One embodiment of the present invention relates to a partially regenerated composition formed by any combination of the aforementioned methods.

[0035] The embodiments can be used alone or in combination with each other. Other features and advantages of the present invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the invention. [Brief description of the drawings]

[0036] [Figure 1] 1 is a schematic diagram of one embodiment of a flooded evaporator heat pump apparatus according to the present invention; [Diagram 2] 1 is a schematic diagram of one embodiment of a direct expansion heat pump device according to the present invention; [Diagram 3] 1 is a schematic diagram of a cascade heat pump system according to the present invention; [Figure 4] FIG. 1 is a schematic diagram of an organic Rankine cycle (ORC) according to the present invention. [Diagram 5] 1 is a graphical representation of the ORC efficiency of the composition E-F23E / R-1336mzzZ. [Figure 6] 1 is a graphical representation of the ORC volumetric capacity of the composition E-F23E / R-1336mzzZ. [Figure 7] 1 is a graphical representation of COPh of a composition comprising E-F23E / E-F12E. [Figure 8] 1 is a graphical representation of COPh for the composition E-F23E / R-1336mzzZ. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] A one-step synthesis for the preparation of fluorinated alkenes is provided.

[0038] The embodiments of the present disclosure provide a one-step synthesis for the production of fluorinated alkenes, for example, as compared to concepts that may not include one or more of the features disclosed herein. More specifically, the present disclosure provides a one-step synthesis for the production of fluorinated alkenes having perfluorinated alkyl chains.

[0039] The process can be carried out in any reactor suitable for gas phase fluorination reactions. The reactor is made of materials that are resistant to the reactants used. The reactor may be constructed from materials that are resistant to the corrosive effects of hydrogen fluoride, such as stainless steel, Hastelloy®, Inconel®, Monel®, gold or gold wire, or quartz. The reaction may be carried out batchwise, continuously, semi-continuously, or combinations thereof. Suitable reactors include batch reactor vessels and tubular reactors.

[0040] In one embodiment, a reagent of formula (1) R f CH=CHF(1) In the formula, R f is C1~C 10is a perfluorinated alkyl group, charging a reactor, heating and contacting in the presence of a catalyst with a fluorinated ethylene compound of formula (2); CX1X2=CX3X4(2) In the formula, X1, X2, X3, and X4 are each independently H, Cl, or F; At least one of X1, X2, X3 or X4 is F.

[0041] the reactor temperature and pressure are maintained at levels sufficient to result in the formation of a composition comprising a compound of formula (3) in the presence of a Lewis acid catalyst; R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(3) In the formula, X5, X6, X7, and X8 are each independently H, Cl, or F; n is an integer of 0 or 1; X5, X6, X7, X8, X9, X 10 , X 11 and X 12 is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2).

[0042] In some embodiments, the compound of formula (1) comprises 1,3,3,3-tetrafluoro-1-propene, CFCH=CHF(1234ze). In one embodiment, the compound of formula (1) is CFCH=CHF(1234ze).

[0043] In some embodiments, the fluorinated ethylene of formula (2) comprises at least one of tetrafluoro-ethene, CF2=CF2 (TFE) or CFCl=CF2 (1-chloro-1,2,2-trifluoro-ethene), CF2=CH2 (1,1-difluoro-ethene), CH2=CHF (1-fluoro-ethene), CF2=CCl2 (1,1-dichloro-2,2-difluoro-ethene), CFCl=CFCl (1,2-chloro-1,2-difluoro-ethene). In one embodiment, the fluorinated ethylene of formula (2) comprises tetrafluoro-ethene, CF2=CF2 (TFE).

[0044] In one embodiment, the compound of formula (1) comprises CF3CH=CHF (1234ze) and the fluorinated ethylene of formula (2) comprises CF2=CF2 (TFE). The reaction of CF3CH=CHF (1234ze) with CF2=CF2 (TFE) can result in the formation of a composition comprising 1,1,1,4,4,5,5,5-octafluoropent-2-ene, CF3CH=CHC2F5 (F12E).

[0045] If desired, 1,1,1,4,4,5,5,5-octafluoropent-2-ene can be isolated and optionally purified prior to use. Suitable uses for 1,1,1,4,4,5,5,5-octafluoropent-2-ene include, but are not limited to, reactive intermediates, refrigerants, heat transfer fluids, and solvents.

[0046] In some embodiments, the fluorinated ethylene of formula (2) may include multiple compounds of formula (2). The resulting compound of formula (3) may include multiple compounds of formula (3). In one embodiment, the fluorinated ethylene of formula (2) may include tetrafluoro-ethene, CF2=CF2 (TFE) and 1-chloro-1,2,2-trifluoro-ethene. In a further embodiment, the compound of formula (1) may include CF3CH=CHF (1234ze).

[0047] The compounds of formula (3) obtained include 1,1,1,4,4,5,5,5-octafluoropent-2-ene, CF3CH=CHC2F5 (F12E), 4-chloro-1,1,1,4,5,5,5-heptafluoropent-2-ene, CF3CH=CHCFClCF3, 5-chloro-1,1,1,4,4,5,5-heptafluoropent-2-ene, CF3CH=CHCF2CF2Cl, 4,5-dichloro-1,1,1,4,5,5,hexafluoropent-2-ene, CF3CH=CHCFClCF2Cl, and 1,1,1,5,5,5-hexafluoropent-2-ene, CF3CH=CHCH2CF3.

[0048] The molar ratio of the compound of formula (2) and the compound of formula (1) contacted according to the present invention can be used to control the ratio of the composition and reaction products. In some embodiments, the compound of formula (2) and the compound of formula (1) are contacted in an amount that results in a molar ratio of 0.01:1 to 5:1. In one embodiment, the compound of formula (2) and the compound of formula (1) are contacted in an amount that results in a molar ratio of (2):(1) of 0.1:1 to 2:1. A contact molar ratio of about 1:1 can produce C5 compounds, and a molar ratio of about 2:1 can produce product C7 compounds. Any desired ratio can be used, but a ratio of about 2:1 is useful. In one embodiment, the compound of formula (2) and the compound of formula (1) are contacted in an amount that results in a molar ratio of (2):(1) of 1:1 to 2:1. In one embodiment, the compound of formula (2) is (TFE) and the compound of formula (1) is (1234ze).

[0049] The reaction conditions and stoichiometry may be selected to allow a compound of formula (3), such as 1,1,1,4,4,5,5,5-octafluoropent-2-ene, CF3CH=CHC2F5 (F12E), described above, to act as a reactive intermediate. In some embodiments, the fluorinated ethylene of formula (2) may be provided in a stoichiometric excess relative to the amount of compound of formula (1). In some embodiments, an excess of a compound of formula (2), such as (TFE), may allow one or more additional units of the compound of formula (2) to react with the 1,1,1,4,4,5,5,5-octafluoropent-2-ene to form additional compounds of formula (3) having extended carbon chains. In one embodiment, a composition comprising a compound of formula (3) may include 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, CF7CH=CHC2F5 (F23E).

[0050] The reaction is typically carried out in a closed system. In some embodiments, the Lewis acid is a strong Lewis acid. In one embodiment, the catalyst is aluminum chloride (AlCl3), or antimony pentafluoride (SbF5), or aluminum chlorofluoride AlCl x F 3-x In some embodiments, for the aluminum based catalyst, x can be an integer from 1 to 3. In some embodiments, x can be from 0.01 to 0.5. The amount of catalyst can range from about 0.1 to about 20 weight percent of the reaction mixture, in some cases from about 1 to about 15, and in some cases from about 5 to about 10 weight percent.

[0051] Additional suitable strong Lewis acids are described in Chemical Reviews, 1996, v. 96, pp. 3269-3301, a list of strong Lewis acids can be found at p. 3271, which is incorporated herein by reference. In some embodiments, the reaction mixture is heated to sub-ambient or ambient temperature. In some embodiments, the reaction mixture is heated to a temperature between -50°C and 50°C. In one embodiment, the reaction mixture is heated to a temperature between -50°C and 25°C. In some embodiments, the reaction is carried out at a reactor pressure between 0.1 pounds per square inch gauge (psig) and 300 pounds per square inch gauge (psig). In one embodiment, the reaction is carried out under autogenous pressure.

[0052] In some embodiments, the formation of the compound of formula (3) may be carried out in the presence of at least one of a solvent or diluent, depending on whether all components of the reaction mixture are soluble. In some embodiments, the solvent or diluent is a perfluorinated saturated compound. In some embodiments, the perfluorinated saturated compound may be perfluoropentane, perfluorohexane, cyclic dimers of hexafluoropropene (a mixture of perfluoro-1,2- and perfluoro-1,3-dimethylcyclobutane), and combinations thereof, or reaction products thereof, may be used as the reaction medium. The amount of at least one solvent or diluent may range from about 10 to about 50 volume percent, about 15 to 40, and in some cases about 20 to 30 volume percent of the reaction vessel.

[0053] In one particular embodiment, the at least one diluent or solvent comprises a reaction product formed by contacting Formulas (1) and (2). The reaction product diluent or solvent can be supplied to the reaction environment by recycling a portion of the recovered reaction product in a continuous process and leaving a remaining portion of the reaction product in the reaction environment in a batch process, among other suitable techniques for delivering the diluent or solvent to the reaction environment.

[0054] In one embodiment of the present invention, the reaction is carried out in an environment that is free or substantially free of compounds with OH groups. Examples of such OH-containing compounds are hydrocarbon greases or oils, as well as solvents with OH groups, such as water or alcohol. By substantially free, it is meant that there is less than 50 ppm, less than 25 ppm, or even less than 10 ppm of OH-containing compounds present.

[0055] The compounds of formula (3) can be used in many applications for the transfer of heat, such as heat transfer fluids or refrigerants. In one embodiment, the compounds of formula (3) (e.g., reaction product mixtures obtained by contacting with the compounds of formulas (1) and (2)) are used to transfer heat from an article. The article can be contacted with a heat transfer medium comprising at least one compound of formula (3).

[0056] In one embodiment, a heat transfer process may include providing an article and contacting the article with a heat transfer medium. The heat transfer medium comprises a composition comprising a compound of formula (4): R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(4) In the formula, R f is C1~C 10 X5, X6, X7, and X8 are each independently H, Cl, or F, n is an integer of 0 or 1, and X5, X6, X7, X8, X9, and X 10 Also X 11 and X 12 is at least 2. In some embodiments, the compound of formula (3) comprises 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5(F23E).

[0057] The heat transfer medium composition includes (E)-1,1,1,4,4,4-hexafluoro-2-butene, (HFO-1336mzz(E),CF3CH=CHCF3), (Z)-1,1,1,4,4,4-hexafluoro-2-butene, (HFO-1336mzz(Z),CF3CH=CHCF3), (E)-2,3-bis(trifluoromethyl)oxirane, (HFO-1336mzz(E)(epoxide),CFCH(-O-)CHCF3), (Z)-2,3-bis(trifluoromethyl)oxirane, (HFO-1336mzz(Z)(epoxide),CFCH(-O -)CHCF3), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), HFO-1438mzz(E), HFO-1438mzz(Z), heptafluoro-4-(trifluoromethyl)-pent-2-ene, ((HFO-153-10mzzy), (mixture of HFO-153-10 isomers)), HFO-162-13mcyz, HFO-162-13mczy, (E)-1,3,4,4,4-Pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(E),CFH=CHCF(CF 3)2), (Z)-1,3,4,4,4-pentafluoro-3-(trifluoromethyl)-1-butene, (HFO-1438ezy(Z),CFH=CHCF(CF3)2), HFO-1336ze(E), HFO-1336ze(Z), HFC-245fa, HFC-245ea, HFC-365mfc, HFC-43-10mee, (E)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(E),CHCl=CHCF3), (Z)-1-chloro-3,3,3-trifluoro-propene, (HCFO-1233zd(Z) ,CHCl=CHCF3), HCFO-1224yd(E), HCFO-1224yd(Z), iso-pentane, n-pentane, cyclopentane, n-hexane, cyclohexane, heptane, methyl formate, dimethoxymethane, dimethoxyethane, propanal, methanol, ethanol, isopropanol, N-propanol, trans-1,2-dichloro-ethylene, cis-1,2-dichloro-ethylene, 1-methoxyheptafluoropropane (HFE-7000, CH3OCF2CF2CF3), methyl nonafluorobutyl ether (HFE-71DA,C4F9OCH3), methoxy-nonafluorobutane (HFE-7100, C4F9OCH3, CH3O-3(CF2)-CH3), ethoxy-nonafluorobutane (HFE-7200, CH3CH2OCF2CF2CF2CF3, C4F9OC2H5), dodecafluoro-2-methylpentan-3-one (NOVEC-649 or Novec-1230, CF3CF2C(O)CF(CF3)2), 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane (Novec-7300; C7H3F, 13 O;n-C2F5CF(OCH3)CF(CF3)2), siloxane, methylperfluoroheptene ether, methoxy-perfluoro-heptene ether or MPHE (HFX-110;C7F 13(OCH3), MPPE (HFX-75), perfluorohept-2-ene / perfluorohept-3-ene (HFO-161-14myy / HFO-161-14mcyy, PFH, mixture, CF3CF=CFCF2CF2CF2CF3 / CF3CF2CF=CFCF2CF2CF3), perfluorohept-1-ene (FC-141-10cy, CF2=CFCF2CF2CF2CF2CF3), 1-bromo-1,2,3,3,3-pentafluoropropene, (R-1215ybB, CF3CF=CFBr), 2-bromo-1,1,1, 3,3-Pentafluoro-2-propene, (R-1215xbB1, CF3CBr=CF2), (E)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(E), CF3CF=CHBr), (Z)-1-Bromo-2,3,3,3-tetrafluoropropene, (HBFO-1224ydB(Z), CF3CF=CHBr), 2-Bromo-3,3,3-trifluoropropene, (BFO-1233xfB, CF3CBr=CH2), trans-DCE / R-1336mzz(Z) mixture (preferred mixture) Examples of suitable mixtures include those disclosed in WO 2008 / 134061), (trans-DCE / methyl perfluoroheptene ether, (suitable mixtures include those disclosed in U.S. Patent Publication No. 2012 / 0227764(Al)), (trans-DCE / HFC-43-10mee mixture, (CHCl=CHCl / CF3CHFCHFCF2CF3), (suitable mixtures include those disclosed as disclosed in U.S. Patent No. 5,196,137), 2-bromo-2-chloro-1, 1,1-trifluoroethane, (R-123B1, CHBrClCF3), 2,3-dichloro-3,3-difluoropropene, (R-1232xf, CClF2CCl=CH2), (E)-1,1,4,4-tetrafluoro-2-butene, (R-1345mzz(E), CHF2CH=CHCHF2), 2-bromo-1,1-difluoroethane, (BDFE, CHF2CH2Br), 1-chloro-2,3,3,4,4,4-hexafluoro-1-butene, (HCFO-1326yd-Z, CF3CF2CF=CHCl), 1-chloro-2,3,3-Trifluoro-propene, (HCFO-1233yd-Z, CHF2CF=CHCl), 2-(1,1,2,2-tetrafluoroethoxy)-1-fluoroethylene, (HFO-1345ezcEβγ, CFH=CHOCF2CF2H), 2,3,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy)prop-1-ene, (HFO-1438mzycEγδ, CF3CF=CHOCF2CF2H), 1-(difluoromethoxy)-2,3,3,3-tetrafluoroprop-1-ene, (HFO-1336pzEαβ, CF3CF=CHOCF2H), 2,3,3-trifluoro- and further comprising one or more co-compounds comprising at least one of 1-(trifluoromethoxy)prop-1-ene, (HFO-1336mzyEαβ, CHF2CF=CHOCF3), 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene, (F22E, C2F5CH=CHC2F5), 1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluoro-5-decene, (F44E, C4F9CH=CHC4F9), or 1,1,1,2,3,4,4,5,5,5-decafluoropentane, (HFC-43-10mee, CF3CHFCHFCF2CF3). In some embodiments, the co-compound comprises at least one of HFO-1336mzz(E), HFO-1336mzz(Z), HFO-1234ze(Z), HFO-1234ye(E), HFO-1234ye(Z), or ethanol.

[0058] In one embodiment, a heat transfer process may include providing an article and contacting the article with a heat transfer medium. The heat transfer medium comprises a composition formed by a process comprising contacting a compound of formula (1): R f CH=CHF(1) In the formula, R f is C1~C 10 is a perfluorinated alkyl group, a fluorinated ethylene compound of formula (2), CX1X2=CX3X4(2) wherein X1, X2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, or X4 is F. The process is carried out in the presence of a Lewis acid catalyst in an amount sufficient to form a composition comprising a compound of formula (3). R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(3) In the formula, X5, X6, X7, and X8 are each independently H, Cl, or F; n is an integer of 0 or 1; 10 , X 11 and X 12 is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2). In some embodiments, the compound of formula (3) comprises 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5(F23E).

[0059] One skilled in the art will appreciate that during the reaction of a compound of formula (1) with a compound of formula (2), bond formation can occur at any carbon of the compound of formula (2). In some embodiments, this can result in a mixture of isomers. In some embodiments, one isomer can predominate.

[0060] The heat transfer medium composition may further optionally include one or more co-compounds. In one embodiment, the co-compound may be one of the co-compounds described above.

[0061] In one embodiment, the heat transfer process may include treating the surface by providing a surface and contacting the surface with a treatment composition. The treatment composition includes a composition formed by a process of contacting the surface with a compound of formula (1): R f CH=CHF(1) In the formula, R f is C1~C 10is a perfluorinated alkyl group, a fluorinated ethylene compound of formula (2), CX1X2=CX3X4(2) wherein X1, X2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, or X4 is F. The reaction is carried out in the presence of a Lewis acid catalyst in a sufficient amount to form a composition comprising a compound of formula (3). R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(3) In the formula, X5, X6, X7, and X8 are each independently H, Cl, or F; n is an integer of 0 or 1; 10 , X 11 and X 12 is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2). In some embodiments, the compound of formula (3) comprises 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5(F23E).

[0062] The surface treatment composition may further optionally include one or more co-compounds. In one embodiment, the co-compound may be any of the co-compounds described above.

[0063] In other embodiments, the heat transfer system may include a refrigerant system, the refrigerant system including an evaporator, a condenser, a compressor, an expansion device, and a heat transfer medium. The heat transfer medium includes a composition formed by a process of contacting a compound of formula (1): R f CH=CHF(1) In the formula, R f is C1~C 10 is a perfluorinated alkyl group, comprising a fluorinated ethylene compound of formula (2), CX1X2=CX3X4(2) wherein X1, X2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, or X4 is F. The process is carried out in the presence of a Lewis acid catalyst in an amount sufficient to form a composition comprising a compound of formula (3). R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(3) In the formula, X5, X6, X7, and X8 are each independently H, Cl, or F; n is an integer of 0 or 1; 10 , X 11 and X 12 is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2). In some embodiments, the compound of formula (3) comprises 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5(F23E).

[0064] In some embodiments, the condenser operates at temperatures greater than 100°C, greater than 150°C, greater than 175°C, and / or greater than 200°C.

[0065] The heat transfer medium may further optionally include one or more co-compounds. In one embodiment, the co-compound may be one of the co-compounds described above.

[0066] In one embodiment, a heat pipe system includes a heat pipe having a working fluid therein. The working fluid comprises a composition formed by a process of contacting a compound of formula (1): R f CH=CHF(1) In the formula, R f is C1~C 10 is a perfluorinated alkyl group, a fluorinated ethylene compound of formula (2), CX1X2=CX3X4(2) wherein X1, X2, X3, and X4 are each independently H, Cl, or F, and at least one of X1, X2, X3, or X4 is reacted in the presence of a Lewis acid catalyst in a sufficient amount to form a composition comprising a compound of formula (3). R f CF3(CX5X6CX7X8) n CH=CHCX9X 10 CX 11 X 12 F(3) In the formula, X5, X6, X7, and X8 are each independently H, Cl, or F; n is an integer of 0 or 1; 10 , X 11 and X 12 is the same as the total number of H, Cl, and F provided by the fluorinated ethylene compound of formula (2). In some embodiments, the compound of formula (3) comprises 1,1,1,2,2,5,5,6,6,7,7,7 dodecafluorohept-2-ene, C3F7CH=CHC2F5(F23E).

[0067] The working fluid may further optionally include one or more co-compounds. In one embodiment, the co-compound may be one of the co-compounds described above.

[0068] In some embodiments, the compound of formula (3) undergoes a phase transition from a liquid to a gaseous state at a temperature of at least 25° C., at least 30° C., at least 40° C., at least 50° C., at least 60° C., less than 140° C., less than 130° C., less than 120° C., less than 110° C., less than 100° C., less than 90° C., less than 80° C., less than 70° C., and combinations thereof. In one embodiment, the compound of formula (3) undergoes a phase transition from a liquid to a gaseous state at a temperature between 50° C. and 90° C. In one embodiment, the compound of formula (3) undergoes a phase transition from a liquid to a gaseous state at a temperature between 75° C. and 80° C.

[0069] In some embodiments, the one or more co-compounds, if present, also undergo a phase transition from a liquid to a gaseous state at a temperature within the above range. In some embodiments, the one or more co-compounds undergo a phase transition from a liquid to a gaseous state at a temperature within about 5° C. of the temperature of the phase transition from the liquid to the gaseous state of the compound of formula (3). In one embodiment, the co-compounds undergo a phase transition from a liquid to a gaseous state at a temperature within 3° C. of the temperature of the phase transition from the liquid to the gaseous state of the compound of formula (3).

[0070] In further embodiments, any of the compositions disclosed herein may be used in combination with at least one lubricant selected from the group consisting of polyalkylene glycols, polyol esters, polyvinyl ethers, mineral oils, alkylbenzenes, synthetic paraffins, synthetic naphthenes, and poly(alpha)olefins.

[0071] In one embodiment, the lubricants include those suitable for use with refrigeration or air conditioning equipment. These lubricants include those conventionally used in vapor compression refrigeration equipment utilizing chlorofluorocarbon refrigerants. In one embodiment, the lubricants include those commonly known in the field of compression refrigeration lubrication as "mineral oils". Mineral oils include paraffins (i.e., saturated hydrocarbons with linear and branched carbon chains), naphthenes (i.e., cyclic paraffins), and aromatics (i.e., unsaturated cyclic hydrocarbons containing one or more rings characterized by alternating double bonds). In one embodiment, the lubricants include those commonly known in the field of compression refrigeration lubrication as "synthetic oils". Synthetic oils include alkylaryls (i.e., alkylbenzenes with linear and branched alkyls), synthetic paraffins and naphthenes, and poly(alpha olefins). Representative conventional lubricants are commercially available BVM 100 N (a paraffinic mineral oil sold by BVA Oils), naphthenic mineral oils commercially available from Crompton Co. under the trade names Suniso® 3GS and Suniso® 5GS, naphthenic mineral oils commercially available from Pennzoil under the trade name Sontex® 372LT, naphthenic mineral oils commercially available from Calumet Lubricants under the trade name Calumet® RO-30, linear alkyl benzenes commercially available from Shrieve Chemicals under the trade names Zerol® 75, Zerol® 150, and Zerol® 500, and HAB22 (a branched alkyl benzene sold by Nippon Oil).

[0072] In other embodiments, lubricants may include those designed for use with hydrofluorocarbon refrigerants and that are miscible with the refrigerants of the present invention under the operating conditions of compression refrigeration and air conditioning equipment. Such lubricants include, but are not limited to, polyol esters (POEs) such as Castrol® 100 (Castrol, United Kingdom), polyalkylene glycols (PAGs) such as RL-488A manufactured by Dow (Dow Chemical, Midland, Michigan), polyvinyl ethers (PVEs), and polycarbonates (PCs).

[0073] Lubricants for use with the compositions disclosed herein are selected by considering the requirements of a given compressor and the environment to which the lubricant will be exposed.

[0074] In one embodiment, the compositions disclosed herein may further comprise an additive selected from the group consisting of a compatibilizer, a UV dye, a solubilizer, a tracer, a stabilizer, a perfluoropolyether (PFPE), and a functionalized perfluoropolyether.

[0075] In one embodiment, the composition may further comprise about 0.01 weight percent to about 5 weight percent of a stabilizer, free radical scavenger, or antioxidant. Such other additives include, but are not limited to, nitromethane, hindered phenols, hydroxylamines, thiols, phosphites, or lactones. A single additive or a combination may be used.

[0076] In an alternative embodiment, the compound of formula (1) may be dimerized. The compound of formula (1) may be reacted with itself in the presence of a catalyst such as antimony fluoride (SbF5) in the absence of the fluorinated ethylene compound of formula (2). In some embodiments, the reaction may be carried out in the presence of a solvent. Suitable solvents include those described above.

[0077] In one example of an alternative embodiment, the dimer may be formed by reacting 1,3,3,3-tetrafluoro-1-propene, CF3CH=CHF (1234ze), as shown below:

[0078] [ka]

[0079] In one embodiment, the above compositions may be used in combination with a cooling device, referred to herein as a chiller. In one embodiment, the chiller may be a vapor compression chiller. Such a vapor compression chiller may be either a flooded evaporator chiller, as shown in FIG. 1, or a direct expansion chiller, as shown in FIG. 2. Both the flooded evaporator chiller and the direct expansion chiller may be air-cooled or water-cooled. In embodiments where the chiller is water-cooled, such chillers are generally associated with a cooling tower for heat removal from the system. In embodiments where the chiller is air-cooled, the chiller is equipped with a refrigerant-to-air finned tube condenser coil and a fan to remove heat from the system. Air-cooled chiller systems are generally less expensive than equivalent capacity water-cooled chiller systems, including cooling towers and water pumps. However, water-cooled systems may be more efficient under many operating conditions due to their lower condensation temperatures.

[0080] Chillers, including both flooded evaporator and direct expansion chillers, may accompany air conditioning and distribution systems that provide comfort conditioning (cooling and dehumidifying the air) for large commercial facilities such as hotels, office buildings, hospitals, universities, etc. In another embodiment, chillers, most likely air-cooled direct expansion chillers, find further utility in naval submarines and surface ships.

[0081] To illustrate how a chiller operates using the compositions of the present invention, reference is made to the drawings. A water-cooled flooded evaporator chiller is shown in FIG. 1. In this chiller, a first cooling medium, which is a warm liquid including water, and in some embodiments an additive such as glycol (e.g., ethylene glycol or propylene glycol), enters the chiller from a cooling system such as a constituent cooling system, shown entering at arrow 3 through coil 9, in an evaporator 6 having an inlet and an outlet. The warm first cooling medium is delivered to the evaporator where it is cooled by the liquid refrigerant, shown in the cooler section of the evaporator. The liquid refrigerant evaporates at a lower temperature than the temperature of the warm first cooling medium flowing through coil 9. The cooled first cooling medium is recirculated back to the constituent cooling system, shown in arrow 4, through a turn of the coil 9. The liquid refrigerant is evaporated and drawn into a compressor 7, as shown in the cooler section of the evaporator 6 in FIG. 1, increasing the pressure and temperature of the refrigerant vapor. The compressor compresses this vapor so that it can condense in the condenser 5 at a higher pressure and temperature than the pressure and temperature at which the vapor leaves the evaporator. The second cooling medium, which is a liquid in the case of a water-cooled chiller, enters the condenser from the cooling tower, arrow 1 in FIG. 1, through coil 10 in the condenser 5. The second cooling medium is warmed in the process and returned to the cooling tower or to the environment via coil 10 and a return loop, arrow 2. This second cooling medium cools the vapor in the condenser, which causes condensation of the vapor into liquid refrigerant, so that there is liquid refrigerant in the cooler part of the condenser, as shown in FIG. 1. The liquid refrigerant condensed in the condenser flows back to the evaporator through an expansion device 8, which may be an orifice, a capillary tube, or an expansion valve. The expansion device 8 reduces the pressure of the liquid refrigerant, partially converting it to vapor. That is, when the pressure drops between the condenser and the evaporator, the liquid refrigerant is said to spurt out. The jet cools the refrigerant, both liquid refrigerant and refrigerant vapor, to a saturation temperature at the evaporator pressure, so that both liquid refrigerant and refrigerant vapor are present in the evaporator.

[0082] It should be noted that for single component compositions, such as the compound of formula (3) above, the composition of the vapor refrigerant in the evaporator is the same as the composition of the liquid refrigerant in the evaporator. In this case, evaporation occurs at a constant temperature. However, when a refrigerant blend (or mixture) is used, such as a combination of the compound of formula (3) and a co-compound, the liquid refrigerant and the refrigerant vapor in the evaporator (or condenser) may have different compositions.

[0083] Chillers with cooling capacity over 700 kW typically employ flooded evaporators, where the refrigerant in the evaporator and condenser surrounds a coil or other conduit of cooling medium (i.e., the refrigerant is on the shell side). Flooded evaporators require more refrigerant, but allow for closer temperatures and higher efficiency. Chillers with capacities less than 700 kW typically employ evaporators with the refrigerant flowing in the tubes and the cooling medium in the condenser surrounding the evaporator and tubes, i.e., the cooling medium is on the shell side. Such chillers are called direct expansion (DX) chillers. A water-cooled direct expansion chiller is shown in FIG. 2. In a chiller such as that shown in FIG. 2, a first liquid cooling medium, which is a warm liquid such as hot water, enters the evaporator 6' at inlet 14. Most of the liquid refrigerant (along with a small amount of refrigerant vapor) enters the evaporator coil 9' at arrow 3' and evaporates. As a result, the first liquid cooling medium is cooled in the evaporator, and the cooled first liquid cooling medium exits the evaporator at outlet 16 and is sent to the object to be cooled, such as a building. In this embodiment of FIG. 2, it is this cooled first liquid cooling medium that cools the building or other object to be cooled. The refrigerant vapor exits the evaporator at arrow 4' and is sent to the compressor 7' where it is compressed and exits as a high temperature, high pressure refrigerant vapor. This refrigerant vapor enters the condenser 5' through the condenser coil 10' at 1'. The refrigerant vapor is cooled in the condenser by a second liquid cooling medium, such as water, and becomes a liquid. The second liquid cooling medium enters the condenser through the condenser cooling medium inlet 20. The second liquid cooling medium extracts heat from the condensing refrigerant vapor, which becomes a liquid refrigerant, which warms the second liquid cooling medium in the condenser. The second liquid cooling medium exits the condenser through the condenser cooling medium outlet 18. The condensed refrigerant exits the condenser through a colder coil 10', shown in Figure 2, and flows through an expansion device 12, which may include an orifice, a capillary tube, or an expansion valve. The expansion device 12 reduces the pressure of the liquid refrigerant. A small amount of vapor is produced as a result of the expansion and passes through coil 9' into the evaporator along with the liquid refrigerant to repeat the cycle.

[0084] In another embodiment, the cooling apparatus may be a high temperature heat pump apparatus having at least two heating stages arranged as a cascade heating system, each stage having a working fluid circulated therethrough and including: (a) a first expansion device for reducing the pressure and temperature of a first working fluid liquid; (b) an evaporator in fluid communication with the first expansion device and having an inlet and an outlet; (c) a first compressor in fluid communication with the evaporator and having an inlet and an outlet; and (d) a first compressor in fluid communication with the first compressor and having an inlet and an outlet. A high temperature heat pump apparatus including: (i) a cascade heat exchange system having an inlet and a first outlet, and (ii) a second inlet and a second outlet in thermal communication with the first inlet and the first outlet; (e) a second compressor in fluid communication with the second outlet of the cascade heat exchanger, having an inlet and an outlet; (f) a condenser in fluid communication with the second compressor, having an inlet and an outlet; and (g) a second expansion device in fluid communication with the condenser, wherein the second working fluid comprises at least one alkyl perfluoroalkene ether. According to the present invention, a cascade heat pump system is provided having at least two heating loops for circulating a working fluid through each loop. One embodiment of such a cascade system is generally shown at 110 in FIG. 3. The cascade heat pump system 110 of the present invention has at least two heating loops, including a first or lower loop 112, which is a low temperature loop, and a second or upper loop 114, which is a high temperature loop 114, as shown in FIG. 3. Each loop circulates a working fluid through the loop.

[0085] The cascade heat pump system 110 includes a first expansion device 116 having an inlet 116a and an outlet 116b. The first expansion device 116 reduces the pressure and temperature of a first working fluid liquid circulated through the first or cold loop 112.

[0086] The cascade heat pump system 110 also includes an evaporator 118. The evaporator 118 has an inlet 118a and an outlet 118b. The first working fluid liquid from the first expansion device 116 enters the evaporator 118 through the evaporator inlet 118a and is evaporated in the evaporator 118 to form a first working fluid vapor. The first working fluid vapor is then circulated to the evaporator outlet 118b.

[0087] The cascade heat pump system 110 also includes a first compressor 120. The first compressor 120 has an inlet 120a and an outlet 120b. The first working fluid vapor from the evaporator 118 is circulated to the inlet 120a of the first compressor 120 and compressed, thereby increasing the pressure and temperature of the first working fluid vapor. The compressed first working fluid vapor is then circulated to the outlet 120b of the first compressor 120.

[0088] The cascade heat pump system 110 also includes a cascade heat exchanger system 122. The cascade heat exchanger 122 has a first inlet 122a and a first outlet 122b. A first working fluid vapor from the first compressor 120 enters the first inlet 122a of the heat exchanger 122 and releases heat by condensing in the heat exchanger 122 to form a first working fluid liquid. The first working fluid liquid then circulates to the first outlet 122b of the heat exchanger 122. The heat exchanger 122 also includes a second inlet 122c and a second outlet 122d. A second working fluid liquid circulates from the second inlet 122c to the second outlet 122d of the heat exchanger 122 and absorbs the heat released by the first working fluid (as it condenses) by evaporating to form a second working fluid vapor. The second working fluid vapor then circulates to the second outlet 122d of the heat exchanger 122. Thus, in the embodiment of FIG. 3, heat released by the first working fluid is directly absorbed by the second working fluid.

[0089] The cascade heat pump system 110 also includes a second compressor 124. The second compressor 124 has an inlet 124a and an outlet 124b. The second working fluid vapor from the cascade heat exchanger 122 is drawn into the compressor 124 through inlet 124a and compressed, thereby increasing the pressure and temperature of the second working fluid vapor. The second working fluid vapor is then circulated to the outlet 124b of the second compressor 124.

[0090] The cascade heat pump system 110 also includes a condenser 126 having an inlet 126a and an outlet 126b. A second working fluid from the second compressor 124 circulates through inlet 126a and condenses in the condenser 126 to form a second working fluid liquid, thereby producing heat. The second working fluid liquid exits the condenser 126 through outlet 126b.

[0091] The cascade heat pump system 110 also includes a second expansion device 128 having an inlet 128a and an outlet 128b. The second working fluid liquid passes through the second expansion device 128 which reduces the pressure and temperature of the second working fluid liquid exiting the condenser 126. This liquid may partially vaporize during this expansion. The reduced pressure and temperature second working fluid liquid is circulated from the expansion device 128 to a second inlet 122c of the cascade heat exchanger system 122.

[0092] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variation thereof, are intended to cover non-exclusive inclusions. For example, a composition, process, method, article, or device that includes recited elements is not necessarily limited to only those elements, but may include other elements not expressly recited or associated with such composition, process, method, article, device, etc. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or," not an exclusive "or." For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0093] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified. When in a claim, such a phrase excludes the inclusion of materials other than those recited, except for impurities normally accompanying the materials. When the phrase "consisting of" appears within a clause in the body of a claim rather than immediately following the preamble, the phrase is intended to limit only the elements set forth in that clause and does not exclude other elements from the claim as a whole.

[0094] The transitional phrase "consisting essentially of" is used to define compositions, methods, and methods that include materials, steps, features, ingredients, or elements in addition to those literally disclosed, provided that these additionally included materials, steps, features, ingredients, or elements have a substantial effect on the basic and novel characteristics of the claimed invention, particularly the mode of action for achieving any desired result of the inventive process. The term "consisting essentially of" has a meaning intermediate between "comprising" and "consisting of."

[0095] It should be readily understood that where applicants have defined an invention or a portion thereof with open-ended terms such as "comprising," the description should be construed to also include such inventions that use the terms "consisting essentially of" or "consisting of" (unless otherwise expressly stated).

[0096] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0097] The following examples are provided to illustrate certain embodiments of the invention and are not intended to limit the scope of the appended claims. EXAMPLES

[0098] Illustrative examples of the formation of compounds of formula (3) are shown below.

[0099] Example 1 Reaction of HFO-1234ze with chlorotrifluoroethylene catalyzed by SbF5

[0100] [ka]

[0101] A 400 mL Hastelloy® shaker tube was charged with 12 g (0.055 mol) of SbF5, cooled with dry ice, evacuated, and charged with 150 g (1.32 mol) of HFO-1234ze and 150 g (1.29 mol) of chlorotrifluoroethylene (CTFE). It was placed on a barricade, warmed to ambient temperature, and stirred for 16 hours. The reaction vessel was cooled with ice, degassed, and the liquid product was added to 1 L of water. The organic layer was separated, dried over MgSO4, and filtered to give 290 g of crude material. The crude material was fractionated to give a fraction bp of 148 g (50% yield). At 59-62°C, it was identified as a mixture of CF3CH=CHCF2CF2Cl and CF3CH=CHCFClCF3 in the ratio 36:64 (the purity of this fraction was 97.8%). This fraction was redistilled to give 120 g of material, 99.3% purity, bp 60-61°C. E-CF3CH=CHCF2CF2Cl: 19 F NMR(CDCl3):-66.38(3F,m),-71.74(2F,m),-113.98(2F,m)ppm E-CF3CH=CHCFClCF3: 19 F NMR(CDCl3):-66.90(3F,m),-82.15(3F,m),-131.82(1F,m)ppm 1 H NMR (CDCl3, mixed isomers): 6.48(m)ppm GC / MS (m / z, mixture of isomers): 230 (M + , C5H2ClF7 + )

[0102] The ratio of CF3CH=CHCF2CF2Cl and CF3CH=CHCFClCF3 in the reaction product mixture can vary. The reaction product ratio can range from about 30:70, about 32:68, about 34:66, and in some cases about 36:64.

[0103] Example 2 Reaction of HFO-1234ze with chlorotrifluoroethylene catalyzed by AlCl3

[0104] [ka]

[0105] A 400 mL Hastelloy® shaker tube was charged with 12 g (0.09 mol) of anhydrous powdered AlCl3, the shaker tube was cooled, cooled with dry ice, evacuated, and charged with 75 g (0.66 mol) of HFO-1234ze and 75 g (0.64 mol) of chlorotrifluoroethylene (CTFE). The shaker tube was barricaded, warmed to ambient temperature, and stirred for 16 hours. The reactor was cooled with ice, degassed, and the liquid product was added to 1 L of water. The organic layer was separated, dried over MgSO4, and filtered to give 148 g of crude material, which was found to contain 68% of a mixture of CF3CH=CHCF2CF2Cl and CF3CH=CHCFClCF3 (CF3CH=CHCF2CF2Cl and CF3CH=CHCFClCF3 in a ratio of 54:46), along with higher coiling point material. The calculated yield of the C5H2ClF7 fraction was 66%.

[0106] The amount of catalyst can be varied if desired. The ratio of reaction products of CF3CH=CHCF2CF2Cl and CF3CH=CHCFClCF3 can range from about 64:36, to about 62:38, and in some cases, to about 60:40.

[0107] Reaction of HFO-1234ze with SbF5 (Comparative Example). A 1 L Hastelloy® shaker tube stirred reactor was charged with 11 g (0.05 mol) SbF5 cooled with dry ice, pressurized with nitrogen, leaked, vented, and evacuated, and 500 g (4.4 mol) HFO-1234ze was condensed into the reactor. It was brought to ambient temperature and maintained at 25-30°C for 12 hours. Water (100 mL) was pumped into the reactor. The reactor was vented, opened, and the reaction mixture was added to a separatory funnel containing 1 L of water, and the organic layer was separated, dried over MgSO4, and filtered to give 474 g of crude product, which was further flash distilled to give 400 g of crude product. Fractionation was performed using a 36 inch glass column with Hastelloy® packing to give 350 g (70% yield) of material by bp. 86-87°C, identified by NMR and GC / MS as E-CF3CH=CHCH(CF3)CF2H, containing 3% Z isomer. E-CF3CH=CHCH(CF3)CF2H: 19 F NMR(CDCl3):-65.86(3F,m),-67.47(3F,m),-120.00(1F,ddm,300,54.1Hz),-123.60(1F,ddm,300,54.1Hz)ppm 1 H(NMR(CDCl3, mixed isomers)):6.06(1H,m),6.10(1H,t,d,54.1 or 2.5Hz),6.33(1H,m)ppm GC / MS(m / z):228(M + , C6H4F8 + )

[0108] Example 3 Reaction of HFO-153-10ze with chlorotrifluoroethylene catalyzed by AlCl3

[0109] [ka]

[0110] A 50 mL flask was charged with 1.0 g (0.007 mol) of anhydrous powdered AlCl3 in a dry box. It was equipped with a thermocouple, a magnetic stir bar, and a dry ice condenser connected to a nitrogen line. The reactor was cooled with ice and 11 g (0.042 mol) of HFO-153-10ze (C4F9CH=CHF) and 5 g (0.042 mol) of chlorotrifluoroethylene (CTFE) were introduced into the reaction mixture through the gas inlet tube over a period of 30 min. The reaction vessel was slowly warmed to ambient temperature in a water bath and stirred for 4 h. The crude reaction mixture was diluted with 300 mL of water and the organic layer was separated, dried over MgSO4 and filtered to give 15 g of crude material which was distilled using a 10 inch Vigreux column to give 7.9 g (75%) of material boiling at 120-129 °C, along with 3% higher boiling material, containing a mixture of C4F9CH=CHCF2CF2Cl and C4F9CH=CHCFClCF3 (ratio 54:56). E-C4F9CH=CHCF2CF2Cl: 19 F NMR(CDCl3, J, Hz):-71.53(2F,t,4.7,Hz),-81.10(3Ft,8.5,Hz),-113.68(2F,m),-114.16(2F,m)-124.35(2F,m),-125.85(2F,m)ppm 1 H NMR(CDCl3J,Hz):6.50(m) E-C4F9CH=CHCFClCF3: 19 F NMR(CDCl3, J, Hz):-81.10(3Ft,8.5,Hz),-81.84(3F,d,7.1,Hz),-113.68(2F,m),-124.35(2F,m),-125.85(2F,m),-131.68(1F,m)ppm 1 H NMR(CDCl3J,Hz):6.50(m) MS (z / e, mixture of isomers): 361 [(MF)+, C8H2ClF 12 + )

[0111] The ratio of the reaction products C4F9CH=CHCF2CF2Cl and C4F9CH=CHCFClCF3 can range from about 64:36, about 62:38, and in some cases about 60:40.

[0112] Example 4 Reaction of HFO-1234ze with tetrafluoroethylene catalyzed by AlCl3

[0113] [ka]

[0114] A 400 mL Hastelloy® shaker tube was charged with 5 g (0.038 mol) of anhydrous powdered AlCl3, the shaker tube was cooled with dry ice, evacuated, and charged with 60 g (0.52 mol) of HFO-1234ze and 50 g (0.5 mol) of tetrafluoroethylene (TFE). The shaker tube was placed in a barricade and warmed to ambient temperature for 2 hours. Another 50 g (0.5 mol) of TFE was charged and stirred for 12 hours. The reactor was cooled with ice, degassed, and the liquid product (140 g) was added to 1 L of water. The organic layer was separated, dried over MgSO4, and filtered to give 130 g of crude material containing 65% E-CF3CH=CHCF2CF3 (F12E) and 35% E-C2F5CH=CHC3F7 (F23E). Fractionation using a 10-inch Vigreux column gave 46 g (43% yield) identified by GC / MS and NMR as CF3CH=CHCF2CF3 (bp 29-30 °C) and 28 g (17% yield) of material identified by NMR and GC / MS as E-C2F5CH=CHC3F7 (98% purity), bp 70-74 °C (mainly 73-74 °C). E-CF3CH=CHCF2CF3 19 F NMR(CDCl3):-66.30(3F,dm,4.1 or 1.5Hz),-85.07(3F,m),-117.98(2F,dm,8.7 or 2.3Hz)ppm GC / MS(m / z):214(M + , C5H2F8 + ) 1 H NMR(CDCl3): 6.46(m)ppm E-C2F5CH=CHC3F7: 19 F NMR(CDCl3):-80.66(3F,t,9.1Hz),-85.07(3F,m),-115.28(2F,quint,8.7Hz),-117.88(2F,dm,8.5 or 2.0Hz),-127.88(2F,s)ppm 1 H NMR(CDCl3): 6.46(m)ppm GC / MS(m / z):314(M + ,C7H2F 12 + )

[0115] If desired, the amount of E-CF3CH=CHCF2CF3 (F12E) and E-C2F5CH=CHC3F7 (F23E) in the reaction product mixture can be varied by varying the amount of reactants. The amount of E-CF3CH=CHCF2CF3 (F12E) and E-C2F5CH=CHC3F7 (F23E) in the reaction product can vary from 1 to 100% by weight, from about 25 to 75% by weight, and in some cases from about 50 to 50% by weight.

[0116] Example 5 Reaction of HFO-1234ze with vinylidene fluoride catalyzed by AlCl3

[0117] [ka]

[0118] This reaction was carried out in a similar manner in a 400 mL Hastelloy® shaker tube using 5 g (0.038 mol) of anhydrous powdered AlCl3, 60 g (0.52 mol) of HFO-1234ze, and 32 g (0.5 mol) of vinylidene fluoride (VF2) added to a single portion of the cold reaction vessel. The reaction mixture was worked up as above. The crude product (89 g) was distilled to give 21 g (24% yield) of a fraction with a boiling point of 63-68 °C that was identified by GC / MS and NMR as a mixture of E-CF3CH=CHCH2CF3 and Z-CF3CH=CHCH2CF3 (ratio 92:8) along with 60 g of uncharacterized high boiling material. E-CF3CH=CHCH2CF3: 19 F NMR(CDCl3):-65.93(3F,t,9.2Hz),-65.31(3F,dm,5.2 or 1.5Hz)ppm 1 H NMR(CDCl3):2.97(2H,quint,8.6Hz),5.91(1H,m),6.33(1H,m)ppm Z-CF3CH=CHCH2CF3: 19 F NMR(CDCl3):-59.36(3F,d,7.9Hz),-66.41(3F,t,9.2Hz)ppm 1 H NMR(CDCl3):3.16(2H,quint,8.6Hz),5.91(m),6.33(1H,m)ppm GC / MS (m / z, mixed isomers): 178 (M + , C5H4F6 + )

[0119] The ratio of E-CF3CH=CHCH2CF3 and Z-CF3CH=CHCH2CF3 in the product mixture can range from about 1-100% by weight, about 25-75% by weight, and in some cases about 50-50% by weight. The ratio can be varied by varying at least one of the ratio of reactants, any solvent, and temperature.

[0120] Reaction of HFO-1234yf with tetrafluoroethylene Catalyst with AlCl3 (Comparative Example) The reaction of 5 g (0.038 mol) of anhydrous powdered AlCl or 115 g (1 mol) of HFO-1234yf (CFCF=CH, an isomer of HFO-1234ze) with 50 g of TFE was carried out in a 400 mL Hastelloy® shaker tube at ambient temperature as described above. No pressure drop was observed over a 16 hour period, and no liquid product was recovered after the shaker tube was evacuated.

[0121] Example 6 Cycle model of organic Rankine cycle FIG. 4 is a schematic diagram of an Organic Rankine Cycle (ORC) model. The ORC efficiency of certain inventive compositions was determined by using mass and energy balances specifying the system and unit operations shown in FIG. 4. Theoretical performance was calculated using typical conditions of an ORC system for generating electricity from a low temperature heat source. Thus, the average condenser and boiler temperatures are 40° C. and 100° C., respectively, with 5 K for both superheat and subcooling. The entropic efficiencies for pump compression and turbine expansion are 85% and 50%, respectively. The efficiency of electricity generation is the fraction of heat input energy utilized as net shaft work, which is calculated as 100% x (WW ポンプ ) / Q h The volumetric power generation capacity is the shaft work multiplied by the density of the fluid leaving the turbine, i.e., (WW ポンプ ) × ρ3. W is the work output from the turbine, and W ポンプ is the work input to the pump, and Q h is the heat input and ρ3 is the density of the fluid exiting the turbine.

[0122] The efficiency and capacity of the binary fluid blends over the entire composition range were determined. Figures 5 and 6 show the dependence of efficiency and capacity on fluid composition for the product component, formula (3), E-F23E, with the co-compound R-1336mzzZ. From Figure 5, it can be seen that the theoretical efficiency has a maximum of 37 wt% E-F23E. This maximum efficiency at 37 wt% E-F23E was compared to R-1233zdE or R-1225yeE or R-1225yeZ and R245fa. As shown in Table 1, E-F23E / R-1336mzzZ ranges from about 30 to about 40 wt% F23E, 70 to 60 wt% R-1336mzzZ is efficient, and in particular, the 37 / 63 wt% blend provides the maximum efficiency.

[0123] [Table 1]

[0124] Example 7 HTHP Cycle Model Heat coefficient of performance (COP) of certain inventive compositions h ) and volumetric heating capacity (CAP h ) was determined by using mass and energy balances specifying the system and unit operations shown in Figure 2. The average evaporator and condenser temperatures are 70°C and 100°C, respectively, for a temperature rise of 30 degrees. There is superheat and subcooling of 5 to 10 Kelvin, respectively. The entropic efficiency for compression is 70%. COP h is the ratio of high temperature heat output per kg of working fluid circulating through the condenser to the power input to the compressor (W) per kg of working fluid circulating through it, i.e., Q h / W. CAP h is the product of the heating effect and density of the fluid entering the compressor (ρ1), i.e., Q h Using these conditions, the COP of a particular inventive binary fluid blend over a range of compositions is h and CAP h 7 and 8 show the COP versus fluid composition for two binary working fluids. hThe dependence of COP on the COP ratio is shown for 1) E-F23E with E-F12E, and 2) E-F23E with the co-compound R-1336mzzZ, respectively. h It can be seen from Figs. 7 and 8 that has a maximum for both binary systems at about 51 wt% E-F23E.

[0125] The two-component composition had the highest COP at 51 wt% E-F23E. h This maximum efficiency for both inventive blends at about 51 wt-% E-F23E was compared to neat fluids E-F23E, E-F12E, R-1336mzzZ or R-1233zdE and R245fa. As shown in Table 2, both inventive blends, E-F23E / E-F12E and E-F23E / R-1336mzzZ, both at about 51 wt-% E-F23E, had their maximum COP h The E-F23E / E-F12E has the highest COP at 51 wt% E-F23E. h It has a value.

[0126] [Table 2]

[0127] Although the present invention has been described with reference to one or more embodiments, it will be understood by those skilled in the art that various changes can be made without departing from the scope of the invention and that equivalents can be substituted for its elements. In addition, many modifications can be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope of the invention. Therefore, it is not intended that the invention be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but the invention is intended to include all embodiments falling within the scope of the appended claims. In addition, all numerical values ​​specified in the detailed description should be interpreted as if both exact and approximate values ​​were explicitly specified.

Claims

1. A process for transferring heat, comprising: Providing the goods; contacting the article with a heat transfer medium; The process wherein the heat transfer medium comprises a composition comprising 30-40% by weight of 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene (C 3 F 7 CH═CHC 2 F 5 , F23E) and 70-60% by weight of (Z)-1,1,1,4,4,4-hexafluoro-2-butene (CF 3 CH═CHCF 3 , HFO-1336mzz(Z)).

2. 1. A process for treating a surface, comprising: Providing a surface; contacting the surface with a treatment composition; the surface includes a treatable material deposited thereon; The process wherein the treatment composition comprises a composition comprising 30-40% by weight of 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene (C 3 F 7 CH═CHC 2 F 5 , F23E) and 70-60% by weight of (Z)-1,1,1,4,4,4-hexafluoro-2-butene (CF 3 CH═CHCF 3 , HFO-1336mzz(Z)).

3. 1. A cooling, heating, or power generation system comprising: An evaporator; A condenser; A compressor; An expansion device; a heat transfer medium; The system wherein the heat transfer medium comprises a composition comprising 30-40% by weight of 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene (C 3 F 7 CH═CHC 2 F 5 , F23E) and 70-60% by weight of (Z)-1,1,1,4,4,4-hexafluoro-2-butene (CF 3 CH═CHCF 3 , HFO-1336mzz(Z)).

4. The system of claim 3 , wherein the condenser operates at a temperature greater than 100° C.

5. a heat pipe having a working fluid therein; 1. A heat pipe system comprising: A heat pipe system, wherein the working fluid comprises a composition comprising 30-40% by weight of 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene (C 3 F 7 CH═CHC 2 F 5 , F23E) and 70-60% by weight of (Z)-1,1,1,4,4,4-hexafluoro-2-butene (CF 3 CH═CHCF 3 , HFO-1336mzz(Z)).

6. 1. A process for recovering heat from a heat source and generating mechanical energy, comprising: (a) passing a first working fluid in a liquid phase through a heat exchanger or an evaporator, the heat exchanger or the evaporator being in communication with the heat source providing the heat; (b) removing at least a portion of the first working fluid in a vapor phase from the heat exchanger or the evaporator; (c) passing the at least a portion of the first working fluid in a vapor phase through an expander, wherein at least a portion of the heat is converted to mechanical energy; and (d) passing at least a portion of the first working fluid in a vapor phase from the expander to a condenser, wherein the at least a portion of the first working fluid in a vapor phase is condensed to a second working fluid in a liquid phase; (e) optionally compressing and mixing the second working fluid in liquid phase with the first working fluid in step (a); (f) optionally repeating steps (a)-(e) at least one time. At least one of the first working fluid or the second working fluid is A process comprising a composition comprising 30-40% by weight of 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene (C 3 F 7 CH═CHC 2 F 5 , F23E) and 70-60% by weight of (Z)-1,1,1,4,4,4-hexafluoro-2-butene (CF 3 CH═CHCF 3 , HFO-1336mzz(Z)).

7. 1. A high temperature heat pump apparatus comprising: (a) a first heat exchanger through which a working fluid flows and is heated; (b) a compressor in fluid communication with the first heat exchanger that compresses the heated working fluid to a higher pressure; (c) a second heat exchanger in fluid communication with the compressor through which a high pressure working fluid flows and is cooled; and (d) a pressure reduction device in fluid communication with the second heat exchanger that reduces the pressure of the cooled working fluid, the pressure reduction device being further in fluid communication with the evaporator such that the working fluid then flows repeatedly through components (a), (b), (c) and (d) in a repeating cycle; A high temperature heat pump apparatus, wherein the working fluid comprises a composition comprising 30-40% by weight of 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene (C 3 F 7 CH═CHC 2 F 5 , F23E) and 70-60% by weight of (Z)-1,1,1,4,4,4-hexafluoro-2-butene (CF 3 CH═CHCF 3 , HFO-1336mzz(Z)).

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