1-Ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane refrigerant compositions comprising functionalized organic compounds and uses thereof

Abstract

The present invention relates to compositions for use in refrigeration and air-conditioning systems comprising 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane and at least one chlorocarbon, alcohol, ketone, ether, ester, N-(difluoromethyl)-N,N-dimethylamine, or mixtures thereof. Further, the present invention relates to compositions for use in refrigeration and air-conditioning systems employing a centrifugal compressor comprising 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane and at least one chlorocarbon, alcohol, ketone, ether, ester, N-(difluoromethyl)-N,N-dimethylamine, or mixtures thereof. The compositions of the present invention may be azeotropic or near-azeotropic and are useful in processes for producing cooling or heat or as heat transfer fluids.

1 . A refrigerant or heat transfer fluid composition comprising C 4 F 9 OC 2 H 5  and at least one compound selected from the group consisting of: 
 acetone;    1,1-dichloroethane;    diisopropyl ether;    1,2-dimethoxyethane;    dimethoxymethane;    ethanol;    ethyl acetate;    ethyl formate;    isopropanol;    methanol;    methyl acetate    methylformate;    tert-butyl methyl ether;    trans-1,2-dichloroethylene; and    N-(difluoromethyl)-N,N-dimethylamine.    
     
     
         2 . A refrigerant or heat transfer fluid composition suitable for use in refrigeration apparatus or air-conditioning apparatus employing (i) centrifugal compressor or (ii) multi-stage centrifugal compressor or (iii) single slab/single pass heat exchanger, said composition comprising C 4 F 9 OC 2 H 5  and at least one compound selected from the group consisting of: 
 acetone;    1,1-dichloroethane;    diisopropyl ether;    1,2-dimethoxyethane;    dimethoxymethane;    ethanol;    ethyl acetate;    ethyl formate;    isopropanol;    methanol;    methyl acetate    methylformate;    tert-butyl methyl ether;    trans-1,2-dichloroethylene; and    N-(difluoromethyl)-N,N-dimethylamine.    
     
     
         3 . An azeotropic or near-azeotropic composition comprising: 
 about 66 to about 99 weight percent C 4 F 9 OC 2 H 5  and about 34 to about 1 weight percent acetone;    about 1 to about 99 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 1 weight percent 1,1-dichloroethane;    about 1 to about 88 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 12 weight percent diisopropyl ether;    about 1 to about 76 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 24 weight percent dimethoxymethane;    about 35 to about 80 weight percent C 4 F 9 OC 2 H 5  and about 65 to about 20 weight percent ethyl formate;    about 39 to about 82 weight percent C 4 F 9 OC 2 H 5  and about 61 to about 18 weight percent methyl acetate;    about 27 to about 81 weight percent C 4 F 9 OC 2 H 5  and about 73 to about 19 weight percent methyl formate;    about 1 to about 80 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 20 weight percent tert-butyl methyl ether; or    about 1 to about 66 weight percent C 4 F 9 OC 2 H 5  and about 99 to about 34 weight percent N-(difluoromethyl)-N,N-dimethylamine.    
     
     
         4 . An azeotropic composition comprising: 
 96.4 weight percent C 4 F 9 OC 2 H 5  and 3.6 weight percent acetone having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 67.2° C.;    7.8 weight percent C 4 F 9 OC 2 H 5  and 92.2 weight percent 1,1-dichloroethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 57.1° C.;    55.5 weight percent C 4 F 9 OC 2 H 5  and 44.5 weight percent diisopropyl ether having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 63.0° C.;    39.2 weight percent C 4 F 9 OC 2 H 5  and 60.8 weight percent dimethoxymethane having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 43.9° C.;    55.7 weight percent C 4 F 9 OC 2 H 5  and 44.3 weight percent ethyl formate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 45.6° C.;    59.9 weight percent C 4 F 9 OC 2 H 5  and 40.1 weight percent methyl acetate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.6° C.;    43.7 weight percent C 4 F 9 OC 2 H 5  and 56.3 weight percent methyl formate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 29.0° C.;    41.7 weight percent C 4 F 9 OC 2 H 5  and 58.3 weight percent tert-butyl methyl ether having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 57.2° C.; or    11.1 weight percent C 4 F 9 OC 2 H 5  and 88.9 weight percent N-(difluoromethyl)-N,N-dimethylamine having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 48.9° C.    
     
     
         5 . A process for producing cooling, said process comprising evaporating the composition of  claim 1 ,  2 ,  3 , or  4  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 composition of  claim 1 ,  2 ,  3 , or  4  in the vicinity of a body to be heated, and thereafter evaporating said composition.  
     
     
         7 . A method of using the compositions of  claim 1 ,  2 ,  3 , or  4 , for heat transfer, said method comprising transferring said composition from 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, and derivatives 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, fluoroethers, and 1,1,1-trifluoroalkanes; and wherein the refrigerant or heat transfer fluid may not be the same compound as the solubilizing agent.  
     
     
         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;    h) 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 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 (CH 2 OH) v [(CH 2 ) m CH 2 OH] 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.    
     
     
         11 . A method for introducing an ultraviolet fluorescent dye into a compression refrigeration or air-conditioning apparatus, said method comprising dissolving the ultraviolet fluorescent dye in the composition of  claim 1 ,  2 ,  3 , or  4 , in the presence of a solubilizing agent, and introducing the combination into said compression refrigeration or air-conditioning apparatus.  
     
     
         12 . A method for solubilizing ultraviolet fluorescent dye in the composition of  claim 1 ,  2 ,  3 , or  4 , said method comprising contacting the ultraviolet fluorescent dye with said composition, in the presence of a solubilizing agent.  
     
     
         13 . A method for detecting leaks, said method comprising providing a compression refrigeration apparatus or air-conditioning apparatus, introducing the composition of  claim 8  or  9  into said apparatus, and providing a suitable means for detecting said composition in the vicinity of said apparatus.  
     
     
         14 . A method of producing cooling, said method comprising: evaporating the refrigerant or heat transfer fluid component of the composition of  claim 8  in the vicinity of a body to be cooled and thereafter condensing said refrigerant or heat transfer fluid component.  
     
     
         15 . A method of producing heat, said method comprising: condensing the refrigerant or heat transfer fluid component of the composition of  claim 8  in the vicinity of the body to be heated and thereafter evaporating said refrigerant or heat transfer fluid component.  
     
     
         16 . The composition of  claim 1 ,  2 ,  3 , or  4  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 . A method of using the composition of  claim 1 ,  2 ,  3 , or  4 , wherein said method comprises producing heat or cooling in a refrigeration or air-conditioning apparatus employing a multi-stage centrifugal compressor.  
     
     
         19 . The method of  claim 18  wherein said multi-stage centrifugal compressor is a two-stage centrifugal compressor.  
     
     
         20 . The composition of  claim 16  wherein said water scavenger is an ortho ester.  
     
     
         21 . A process to produce cooling comprising compressing a composition of  claim 1 ,  2 ,  3 , or  4  in a mini-centrifugal compressor powered by an engine exhaust gas driven turbine; condensing said composition; and thereafter evaporating said composition in the vicinity of a body to be cooled.  
     
     
         22 . A process to produce cooling comprising compressing a composition of  claim 1 ,  2 ,  3 , or  4  in a mini-centrifugal compressor powered by a ratioed gear drive assembly with a ratioed belt drive; condensing said composition; and thereafter evaporating said composition in the vicinity of a body to be cooled.  
     
     
         23 . A method for replacing CFC-113 in existing refrigeration apparatus or air-conditioning apparatus, said method comprising providing a composition of  claim 1 ,  2 ,  3 , or  4  as the replacement.