1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone refrigerant compositions and uses thereof

Abstract

The present invention relates to compositions for use in refrigeration and air conditioning systems comprising 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and at least one chlorocarbon, alcohol, ketone, ether, ester, N-(difluoromethyl)-N,N-dimethylamine, 1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane or mixtures thereof, and which are also useful in systems employing a centrifugal compressor The compositions of the present invention may be azeotropic or near azeotropic and are useful in processes for producing refrigeration or heat or as heat transfer fluids.

1 . A composition selected from the group consisting of: 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1,1-dichloroethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and N-(difluoromethyl)-N,N-dimethylamine; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and acetone; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and diisopropyl ether; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1,2-dimethoxyethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and dimethoxymethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1,1-dimethoxyethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and tert-butylmethyl ether; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and ethanol; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and isopropanol; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and n-propanol; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and ethyl formate; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and methyl acetate; and 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and methyl formate. 
     
     
         2 . A composition as in  claim 1  wherein the composition is a refrigerant or heat transfer fluid composition suitable for use in refrigeration or air conditioning apparatus employing (i) centrifugal compressor, or (ii) multi-stage centrifugal compressor, or (iii) a single slab/single pass heat exchanger, and said composition is selected from the group consisting of: 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1,1-dichloroethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and N-(difluoromethyl)-N,N-dimethylamine; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and acetone; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and diisopropyl ether; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1,2-dimethoxyethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and dimethoxymethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1,1-dimethoxyethane; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and tert-butylmethyl ether; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and ethanol; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and isopropanol; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and n-propanol; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and ethyl formate; 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and methyl acetate; and 
       1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and methyl formate. 
     
     
         3 . A composition as in  claim 1 , wherein the composition is an azeotropic or near-azeotropic composition selected from the group consisting of:
 about 55 to about 91 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 45 to about 9 weight percent 1,1-dichloroethane;   about 43 to about 91 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 57 to about 9 weight percent N-(difluoromethyl)-N,N-dimethylamine;   about 1 to about 99 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 99 to about 1 weight percent 1,1,1,2,2-pentafluoro-2-[(pentafluoroethyl)thio]ethane;   about 1 to about 99 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 99 to about 1 weight percent acetone;   about 63 to about 94 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 37 to about 6 weight percent diisopropyl ether;   about 73 to about 96 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 27 to about 4 weight percent 1,2-dimethoxyethane;   about 60 to about 92 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 40 to about 8 weight percent dimethoxymethane;   about 61 to about 99 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 39 to about 1 weight percent 1,1-dimethoxyethane;   about 63 to about 92 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 37 to about 8 weight percent tert-butyl methyl ether; and   about 87 to about 99 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 13 to about 1 weight percent ethanol;   about 85 to about 99 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 15 to about 1 weight percent isopropanol;   about 87 to about 99 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 13 to about 1 weight percent n-propanol;   about 61 to about 92 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 39 to about 8 weight percent ethyl formate;   about 63 to about 93 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 37 to about 7 weight percent methyl acetate; and   about 53 to about 90 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and about 47 to about 10 weight percent methyl formate.   
     
     
         4 . A composition as in  claim 1  wherein the composition is an azeotropic composition selected from the group consisting of:
 78.7 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 21.3 weight percent 1,1-dichloroethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 38.2° C.;   70.2 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 29.8 weight percent N-(difluoromethyl)-N,N-dimethylamine having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 38.1° C.;   85.3 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 14.7 weight percent diisopropyl ether having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 40.3° C.;   92.6 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 7.4 weight percent 1,2-dimethoxyethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 42.0° C.;   79.5 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 20.5 weight percent dimethoxymethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 29.6° C.;   85.5 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 14.5 weight percent 1,1-dimethoxyethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 44.4° C.;   83.3 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 16.7 weight percent tert-butyl methyl ether having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 35.3° C.; and   96.8 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 3.2 weight percent ethanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 44.7° C.;   96.7 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 3.3 weight percent isopropanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 45.6° C.;   98.4 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 1.6 weight percent n-propanol having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.6° C.;   82.3 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 17.7 weight percent ethyl formate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 34.1° C.;   84.4 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 15.6 weight percent methyl acetate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 35.4° C.; and   73.2 weight percent 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone and 26.8 weight percent methyl formate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 22.6° C.   
     
     
         5 . A process for producing refrigeration, said process comprising evaporating the refrigerant composition of  claim 2 , in the vicinity of a body to be cooled, and thereafter condensing said composition. 
     
     
         6 . A process for producing heat, said process comprising condensing the heat transfer composition of  claim 2  in the vicinity of a body to be heated, and thereafter evaporating said composition. 
     
     
         7 . A process for transferring heat, said process comprising transferring the composition of  claim 1  from the vicinity of a heat source to a heat sink. 
     
     
         8 . The composition of  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. 
     
     
         9 . The composition of  claim 8 , 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. 
     
     
         10 . The composition of  claim 9 , 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 CONR 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 COR 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 selected from the integers 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;   i) fluoroethers represented by the formula R 1 OCF 2 CF 2 H, wherein R 1  is selected from aliphatic and alicyclic 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 of the type HOCH 2 CRR′(CH 2 ) z (CHOH) x CH 2 (CH 2 OH) y , 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   j) 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 
         k) 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. 
       
     
     
         11 . A process for detecting a leak at or in the vicinity of a refrigeration or air conditioning apparatus, said process comprising: providing a composition of  claim 8  into said apparatus, and providing a suitable means for detecting said composition at a leak point or in the vicinity of said apparatus. 
     
     
         12 . A method as in  claim 5  wherein the refrigerant 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. 
     
     
         13 . A method as in  claim 6  wherein the 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 as in  claim 12 , wherein the refrigerant composition further comprises 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. 
     
     
         15 . A method as in  claim 14  wherein the refrigerant composition is introduced into a compression refrigeration or air conditioning apparatus by (i) dissolving the ultraviolet fluorescent dye in the refrigerant composition or heat transfer fluid in the presence of the solubilizing agent, and introducing the combination into said compression refrigeration or air conditioning apparatus or (ii), combining solubilizing agent and UV fluorescent dye and introducing said combination into said compression refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid. 
     
     
         16 . The composition of  claim 1  further comprising a stabilizer, water scavenger, or odor masking agent. 
     
     
         17 . The composition of  claim 16  wherein said stabilizer is selected from the group consisting of nitromethane, hindered phenols, hydroxylamines, thiols, phosphites and lactones. 
     
     
         18 . The composition of  claim 16  wherein said water scavenger is an ortho ester.