Heat transfer and refrigerant compositions comprising 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and a hydrofluorocarbon

Abstract

Disclosed herein are 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene compositions for use in refrigeration and air conditioning systems, particularly in centrifugal compressor systems. Also disclosed are 5 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene in combination with hydrofluorocarbons, which are azeotropic or near azeotropic.

1 . A refrigerant or heat transfer fluid composition comprising 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and at least one hydrofluorocarbon selected from the group consisting of: 
 1,1,3-trifluoropropane;    1,3-difluoropropane;    1,2-difluorobutane;    1,3-difluorobutane;    1,4-difluorobutane;    1,3-difluoro-2-methylpropane;    2,3-difluorobutane;    1,1,1-trifluoropentane;    1,1,1-trifluoro-3-methylbutane;    1,1-difluoropentane;    1,2-difluoropentane;    2,2-difluoropentane;    1,1,1-trifluorohexane;    1,1,2,2-tetrafluorocyclobutane; and    1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene.    
     
     
         2 . A refrigerant or heat transfer fluid composition as in  claim 1 , wherein the composition is selected from the group consisting of: 
 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,1,3-trifluoropropane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,3-difluoropropane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,2-difluorobutane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,3-difluorobutane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,4-difluorobutane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,3-difluoro-2-methylpropane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 2,3-difluorobutane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,1,1-trifluoropentane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,1,1-trifluoro-3-methylbutane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,1-difluoropentane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,2-difluoropentane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 2,2-difluoropentane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,1,1-trifluorohexane;    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,1,2,2-tetrafluorocyclobutane; and    3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene.    
     
     
         3 . A refrigerant or heat transfer fluid composition as in  claim 1 , wherein the composition is an azeotropic or near-azeotropic composition selected from the group consisting of: 
 about 1 to about 77 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 23 to about 99 weight percent of 1,1,3-trifluoropropane;    about 1 to about 76 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 24 to about 99 weight percent of 1,3-difluoropropane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,2-difluorobutane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,3-difluorobutane;    about 56 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 44 weight percent of 1,4-difluorobutane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,3-difluoro-2-methylpropane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 2,3-difluorobutane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,1,1-trifluoropentane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,1,1-trifluoro-3-methylbutane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,1-difluoropentane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,2-difluoropentane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 2,2-difluoropentane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,1,1-trifluorohexane;    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,1,2,2-tetrafluorocyclobutane; and    about 1 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 99 weight percent of 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene.    
     
     
         4 . A refrigerant or heat transfer fluid composition as in  claim 1 , wherein the composition is an azeotropic or near-azeotropic composition selected from the group consisting of: 
 about 20 to about 77 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 23 to about 80 weight percent of 1,1,3-trifluoropropane;    about 20 to about 76 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 24 to about 80 weight percent of 1,3-difluoropropane;    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 1,2-difluorobutane;    about 40 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 60 weight percent of 1,3-difluorobutane;    about 60 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 40 weight percent of 1,4-difluorobutane;    about 40 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 60 weight percent of 1,3-difluoro-2-methylpropane;    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 2,3-difluorobutane;    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 1,1,1-trifluoropentane;    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 1,1,1-trifluoro-3-methylbutane;    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 1,1-difluoropentane;    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 1,2-difluoropentane;    about 40 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 60 weight percent of 2,2-difluoropentane;    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 1,1,1-trifluorohexane;    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 1,1,2,2-tetrafluorocyclobutane; and    about 20 to about 99 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and about 1 to about 80 weight percent of 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene.    
     
     
         5 . A refrigerant or heat transfer fluid composition as in  claim 1 , wherein the composition is an azeotropic composition selected from the group consisting of: 
 42.4 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 57.6 weight percent of 1,1,3-trifluoropropane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 41.7° C.;    43.3 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 56.7 weight percent of 1,3-difluoropropane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 37.8° C.;    42.0 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 58.0 weight percent of 1,2-difluorobutane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.5° C.;    67.8 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 32.2 weight percent of 1,3-difluorobutane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 53.5° C.;    88.3 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 11.7 weight percent of 1,4-difluorobutane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 57.6° C.;    72.9 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 27.1 weight percent of 1,3-difluoro-2-methylpropane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 54.6° C.;    30.1 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 69.9 weight percent of 2,3-difluorobutane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 46.3° C.;    69.7 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 30.3 weight percent of 2,2-difluoropentane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 57.5° C.;    39.6 weight percent of 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene and 60.4 weight percent of 1,1,2,2-tetrafluorocyclobutane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 46.8° C.    
     
     
         6 . A method for producing refrigeration, said method comprising evaporating the refrigerant or heat transfer composition of  claim 1  in the vicinity of a body to be cooled, and thereafter condensing said composition.  
     
     
         7 . A method for producing heat, said method comprising condensing the refrigerant or heat transfer composition of  claim 1  in the vicinity of a body to be heated, and thereafter evaporating said composition.  
     
     
         8 . A method for transferring heat, said method comprising transferring the compositions of  claim 1  from a heat source to a heat sink.  
     
     
         9 . A composition as in  claim 1  further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.  
     
     
         10 . A composition as in  claim 9 , further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, hydrofluoroethers, and 1,1,1-trifluoroalkanes; and wherein the refrigerant and solubilizing agent are not the same compound.  
     
     
         11 . A composition as in  claim 10 , wherein said solubilizing agent is selected from the group consisting of: 
 a) polyoxyalkylene glycol ethers represented by the formula R 1 [(OR 2 ) x OR 3 ] y , wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R 1  is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2  is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3  is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R 1  and R 3  is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units;    b) amides represented by the formulae R 1 C(O)NR 2 R 3  and cyclo-[R 4 CON(R 5 )—], wherein R 1 , R 2 , R 3  and R 5  are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R 4  is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units;    c) ketones represented by the formula R 1 C(O)R 2 , wherein R 1  and R 2  are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units;    d) nitriles represented by the formula R 1 CN, wherein R 1  is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units;    e) chlorocarbons represented by the formula RCl x , wherein; x is 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units;    f) aryl ethers represented by the formula R 1 OR 2 , wherein: R 1  is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R 2  is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units;    g) 1,1,1-trifluoroalkanes represented by the formula CF 3 R 1 , wherein R 1  is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms;    h) fluoroethers represented by the formula R 1 OCF 2 CF 2 H, wherein R 1  is selected from aliphatic, alicyclic and aromatic hydrocarbon radicals having from about 5 to about 15 carbon atoms; or wherein said fluoroethers are derived from fluoro-olefins and polyols, wherein said fluoro-olefins are of the type CF 2 ═CXY, wherein X is hydrogen, chlorine or fluorine, and Y is chlorine, fluorine, CF 3  or OR f , wherein R f  is CF 3 , C 2 F 5 , or C 3 F 7 ; and said polyols are linear or branched, wherein said linear polyols are of the type HOCH 2  (CHOH) x (CRR′) y CH 2 OH, wherein R and R′ are hydrogen, CH 3  or C 2 H 5 , x is an integer from 0-4, y is an integer from 0-3 and z is either zero or 1, and said branched polyols are of the type C(OH) t (R) u (CH2OH) v [(CH2) m CH2OH] w , wherein R may be hydrogen, CH 3  or C 2 H 5 , m is an integer from 0 to 3, t and u are 0 or 1, v and w are integers from 0 to 4, and also wherein t+u+v+w=4;    i) lactones represented by structures [B], [C], and [D]:                          wherein, R 1  through R 8  are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and    j) esters represented by the general formula R 1 CO 2 R 2 , wherein R 1  and R 2  are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.    
     
     
         12 . A method for detecting the composition of  claim 9  in a compression refrigeration or air conditioning apparatus, said method comprising providing said composition to said apparatus, and providing a suitable means for detecting said composition at a leak point or in the vicinity of said apparatus.  
     
     
         13 . A method of producing refrigeration as in  claim 6 , wherein the refrigerant or heat transfer composition further comprises at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.  
     
     
         14 . A method of producing heat as in  claim 7 , wherein the refrigerant or heat transfer composition further comprises at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.  
     
     
         15 . A composition as in  claim 1  further comprising a stabilizer, water scavenger, or odor masking agent.  
     
     
         16 . A composition as in  claim 15  wherein said stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones.  
     
     
         17 . A method as in  claim 6 , wherein said method comprises producing refrigeration in a refrigeration or air conditioning apparatus employing a multi-stage centrifugal compressor.  
     
     
         18 . The method as in  claim 17  wherein said multi-stage centrifugal compressor is a two-stage centrifugal compressor.  
     
     
         19 . A method as in  claim 7 , wherein said method comprises producing heat in a refrigeration apparatus employing a multi-stage centrifugal compressor.  
     
     
         20 . A method as in  claim 19  wherein said multi-stage centrifugal compressor is a two-stage centrifugal compressor.  
     
     
         21 . The composition as in  claim 15  wherein said water scavenger is an ortho ester.  
     
     
         22 . A method as in  claim 6 , wherein said method comprises producing refrigeration in a refrigeration or air conditioning apparatus employing a mini-centrifugal compressor powered by an engine exhaust gas driven turbine.  
     
     
         23 . A method as in  claim 6 , wherein said method comprises producing refrigeration in a refrigeration or air conditioning apparatus employing a mini-centrifugal compressor powered by a ratioed gear drive assembly with a ratioed belt drive.  
     
     
         24 . A process for removing residue from a surface comprising: 
 (a) contacting the surface with an azeotropic or azeotrope-like composition comprising perfluorobutylethylene (3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene (PFBE)) and at least one hydrofluorocarbon is selected from the group consisiting of: 
 1,1,3-trifluoropropane;  
 1,3-difluoropropane;  
 1,2-difluorobutane;  
 1,3-difluorobutane;  
 1,4-difluorobutane;  
 1,3-difluoro-2-methylpropane;  
 2,3-difluorobutane;  
 1,1,1-trifluoropentane;  
 1,1,1-trifluoro-3-methylbutane;  
 1,1-difluoropentane;  
 1,2-difluoropentane;  
 2,2-difluoropentane;  
 1,1,1-trifluorohexane;  
 1,1,2,2-tetrafluorocyclobutane; and  
   1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene;    (b) recovering the surface from the composition.    
     
     
         25 . A process as in  claim 24  wherein said residue comprises an oil.  
     
     
         26 . A process as in  claim 24  wherein said residue comprises a rosin flux.  
     
     
         27 . A process as in  claim 24  wherein the surface is an integrated circuit device.