1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane 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 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane and at least one chlorocarbon, alcohol, 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 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane and at least one chlorocarbon, alcohol, 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 OCH 3  and at least one compound selected from the group consisting of:
 N-(difluoromethyl)-N,N-dimethylamine;   ethyl formate;   methyl acetate;   methyl formate;   tert-butyl methyl ether; and   C 4 F 9 OC 2 H 5  and trans-1,2-dichloroethylene.   
     
     
         2 . The refrigerant or heat transfer fluid composition of  claim 1 , wherein the composition comprises a composition selected from the group consisting of:
 C 4 F 9 OCH 3  and N-(difluoromethyl)-N,N-dimethylamine;   C 4 F 9 OCH 3  and ethyl acetate;   C 4 F 9 OCH 3  and methyl acetate;   C 4 F 9 OCH 3  and methyl formate;   C 4 F 9 OCH 3  and tert-butyl methyl ether; and   C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5  and trans-1,2-dichloroethylene.   
     
     
         3 . The refrigerant or heat transfer fluid composition of  claim 1 , wherein the composition is an azeotropic or near-azeotropic composition comprising:
 about 1 to about 99 weight percent C 4 F 9 OCH 3  and about 99 to about 1 weight percent N-(difluoromethyl)-N,N-dimethylamine;   about 46 to about 86 weight percent C 4 F 9 OCH 3  and about 54 to about 14 weight percent ethyl formate;   about 49 to about 87 weight percent C 4 F 9 OCH 3  and about 51 to about 13 weight percent methyl acetate;   about 37 to about 83 weight percent C 4 F 9 OCH 3  and about 63 to about 17 weight percent methyl formate; or   about 10 to about 70 weight percent C 4 F 9 OCH 3 , about 5 to about 60 weight percent C 4 F 9 OC 2 H 5 , and about 25 to about 80 weight percent trans-1,2-dichloroethylene.   
     
     
         4 . The refrigerant or heat transfer fluid composition of  claim 1 , wherein the composition is an azeotropic composition comprising:
 41.1 weight percent C 4 F 9 OCH 3  and 58.9 weight percent N-(difluoromethyl)-N,N-dimethylamine having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 47.5° C.;   68.6 weight percent C 4 F 9 OCH 3  and 31.4 weight percent ethyl formate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 41.0° C.;   72.1 weight percent C 4 F 9 OCH 3  and 27.9 weight percent methyl acetate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 42.5° C.; or   57.4 weight percent C 4 F 9 OCH 3  and 42.6 weight percent methyl formate having a vapor pressure of about 14.7 psia (101 kPa) at a temperature of about 26.0° C.   
     
     
         5 . A process for producing cooling, said process comprising evaporating the composition of  claim 1  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  in the vicinity of a body to be heated, and thereafter evaporating said composition. 
     
     
         7 . A method of using the compositions of  claim 1  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  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  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  into said apparatus, and providing a suitable means for detecting said composition in the vicinity of said apparatus. 
     
     
         14 . The method of  claim 5 , wherein the refrigerant or heat transfer fluid 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, and derivatives thereof. 
     
     
         15 . The method of  claim 6 , wherein the refrigerant or heat transfer fluid 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, and derivatives thereof. 
     
     
         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 method of  claim 5 , wherein said method further comprises producing 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 method of  claim 6 , wherein said method further comprises producing heating in a refrigeration or air-conditioning apparatus employing a multi-stage centrifugal compressor. 
     
     
         21 . The method of  claim 20  wherein said multi-stage centrifugal compressor is a two-stage centrifugal compressor 
     
     
         22 . The composition of  claim 16  wherein said water scavenger is an ortho ester. 
     
     
         23 . A process to produce cooling comprising compressing a composition of  claim 1  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. 
     
     
         24 . The process of  claim 5 , wherein the refrigerant or heat transfer composition is compressed in a mini-centrifugal compressor powered by a ratioed gear drive assembly with a ratioed belt drive; prior to the said condensing of said composition. 
     
     
         25 . A method for replacing CFC-113 in existing refrigeration apparatus or air-conditioning apparatus, said method comprising providing a composition of  claim 1  as the replacement.