Stabilized fluoroolefin compositions and methods for their production, storage and usage

Abstract

The present invention relates to compositions comprising at least one fluoroolefin, HFC-32, and an effective amount of at least one inhibitor. The stabilized compositions may be useful in cooling and heating apparatus, such as refrigeration, air-conditioning, chillers, and heat pumps, as well as in applications as foam blowing agents, solvents, aerosol propellants, fire extinguishants, and sterilants.

1 . A composition comprising at least one fluoroolefin, HFC-32, and an effective amount of at least one inhibitor and wherein the composition is substantially free of oligomeric, homopolymers or other polymeric products derived from the fluoroolefin. 
     
     
         2 . The composition of  claim 1  wherein the composition comprises less than about 0.03 wt. % of oligomeric, homopolymers or other polymeric products. 
     
     
         3 . The composition of  claim 1  further comprising at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates. 
     
     
         4 . The composition of  claim 3  wherein the inhibitor comprises at least one member selected from the group consisting of d-limomene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol. 
     
     
         5 . The composition of  claim 3  further comprising at least one lubricant selected from the group consisting of POE, PAG, and PVE. 
     
     
         6 . (canceled) 
     
     
         7 . The composition of  claim 3  wherein the fluoroolefin comprises at least one member of HFO-1234yf and HFO-1234ze. 
     
     
         8 . The composition of  claim 5  further comprising at least one member selected from the group consisting of HFC-125, HFC-134a, HFC-152a, 236fa, HFC-227ea and carbon dioxide. 
     
     
         9 . The composition of  claim 1  comprising HFO-1234yf, HFC-32, and at least one inhibitor selected from the group consisting of d-limonene and α-terpinene. 
     
     
         10 . The composition of  claim 7 ,  8 , or  9  further comprising at least one member selected from the group consisting of HFC-134a, HFO-1243zf, HFO-1225ye, HFO-1234ze, 3,3,3-trifluoropropyne, HCFO-1233xf, HFC-244bb and HFC-245cb. 
     
     
         11 . The composition of  claim 7 ,  8 , or  9  further comprising at least one member selected from the group consisting of HCC-40, HCFC-22, CFC-115, HCFC-124, HCFC-1122, and CFC-1113. 
     
     
         12 . The composition of  claim 4  wherein the inhibitor is present in an amount of about 30 to about 3,000 ppm (by weight). 
     
     
         13 . (canceled) 
     
     
         14 . The composition of  claim 7  wherein the inhibitor comprises at least one of d-limonene and α-terpinene. 
     
     
         15 . (canceled) 
     
     
         16 . (canceled) 
     
     
         17 . The composition of  claim 7  further comprising at least one member selected from the group consisting of HFO-1225yeZ, HFO-1243zf, HFO-1234ze, HFC-236ea, HFC-245fa, and 3,3,3-trifluoropropyne. 
     
     
         18 . The composition of  claim 1  wherein the composition is substantially free of ammonia and CF 31 . 
     
     
         19 . The composition of  claim 1  wherein the composition consists essentially of HFO-1234yf, HFC-32, and d-limonene and does not contain ammonia or CF 31 . 
     
     
         20 . (canceled) 
     
     
         21 . A method for reducing formation of oligomers and homopolymers comprising contacting a composition comprising at least one fluoroolefin and HFC-32 with an effective amount of at least one member selected from the group consisting of d-limomene, α-terpinene, α-tocopherol, butylated hydroxytoluene, 4-methoxyphenol, and benzene-1,4-diol, that is effective to reduce oligomer or homopolymer formation. 
     
     
         22 . The method of  claim 21  wherein the composition has been exposed to at least one member selected from the group consisting of air, oxygen, cumene hydroperoxide, and fluoroolefin polyperoxides, peroxides, hydroperoxides, persulfates, percarbonates, perborates and hydropersulfates before said contacting. 
     
     
         23 . (canceled) 
     
     
         24 . A container with a refrigerant comprising the composition of any of  claims 1  through  4 . 
     
     
         25 . A refrigeration, air-conditioning, heatpump, or chiller system comprising at least one evaporator, at least one compressor, at least one condenser and at least one expansion device and containing the composition of any of  claims 1  through  4 . 
     
     
         26 . The composition of  claim 1  comprising:
 a) a refrigerant consisting of HFO-1234yf and HFC-32; and 
 b) at least one inhibitor selected from the group consisting of d-limonene and α-terpinene.