AU2016216544B2 - Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane - Google Patents
Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane Download PDFInfo
- Publication number
- AU2016216544B2 AU2016216544B2 AU2016216544A AU2016216544A AU2016216544B2 AU 2016216544 B2 AU2016216544 B2 AU 2016216544B2 AU 2016216544 A AU2016216544 A AU 2016216544A AU 2016216544 A AU2016216544 A AU 2016216544A AU 2016216544 B2 AU2016216544 B2 AU 2016216544B2
- Authority
- AU
- Australia
- Prior art keywords
- composition
- hcfo
- hfo
- hcfc
- compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 149
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 title claims description 43
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 title claims description 33
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical compound ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 title description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 32
- -1 HCFO5 1233zd Chemical compound 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 16
- 239000000443 aerosol Substances 0.000 claims description 14
- FDOPVENYMZRARC-UHFFFAOYSA-N 1,1,1,2,2-pentafluoropropane Chemical compound CC(F)(F)C(F)(F)F FDOPVENYMZRARC-UHFFFAOYSA-N 0.000 claims description 13
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000003380 propellant Substances 0.000 claims description 9
- AUCDWYVJFVHEHQ-UHFFFAOYSA-N 1,1,2,3-tetrachloro-1-fluoropropane Chemical compound FC(Cl)(Cl)C(Cl)CCl AUCDWYVJFVHEHQ-UHFFFAOYSA-N 0.000 claims description 7
- JAQKPYNFGZPKTM-UHFFFAOYSA-N 1,2,3-trichloro-1,1-difluoropropane Chemical compound FC(F)(Cl)C(Cl)CCl JAQKPYNFGZPKTM-UHFFFAOYSA-N 0.000 claims description 7
- CNNJBYUJTYGLGG-UHFFFAOYSA-N 2-chloro-1,1,1,3-tetrafluoropropane Chemical compound FCC(Cl)C(F)(F)F CNNJBYUJTYGLGG-UHFFFAOYSA-N 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 60
- 239000003054 catalyst Substances 0.000 description 49
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 31
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 29
- 229910052751 metal Inorganic materials 0.000 description 24
- 239000002184 metal Substances 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 238000012546 transfer Methods 0.000 description 18
- 239000012808 vapor phase Substances 0.000 description 17
- 239000003507 refrigerant Substances 0.000 description 16
- 238000005057 refrigeration Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000004378 air conditioning Methods 0.000 description 15
- 238000007033 dehydrochlorination reaction Methods 0.000 description 15
- 150000002739 metals Chemical class 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000007791 liquid phase Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 238000003682 fluorination reaction Methods 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- QJMGASHUZRHZBT-UHFFFAOYSA-N 2,3-dichloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)C(Cl)CCl QJMGASHUZRHZBT-UHFFFAOYSA-N 0.000 description 5
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 5
- 229910000423 chromium oxide Inorganic materials 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 229910001026 inconel Inorganic materials 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000005297 pyrex Substances 0.000 description 5
- 239000006200 vaporizer Substances 0.000 description 5
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 4
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 description 4
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000700 radioactive tracer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- INEMUVRCEAELBK-UHFFFAOYSA-N 1,1,1,2-tetrafluoropropane Chemical compound CC(F)C(F)(F)F INEMUVRCEAELBK-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- 239000013529 heat transfer fluid Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- ZDCWZRQSHBQRGN-UHFFFAOYSA-N 1,1,1,2,3-pentafluoropropane Chemical compound FCC(F)C(F)(F)F ZDCWZRQSHBQRGN-UHFFFAOYSA-N 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- UDPHJTAYHSSOQB-UHFFFAOYSA-N 1,2,2,3-tetrachloropropane Chemical compound ClCC(Cl)(Cl)CCl UDPHJTAYHSSOQB-UHFFFAOYSA-N 0.000 description 2
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013058 crude material Substances 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- PNWJILFKWURCIR-UPHRSURJSA-N (e)-1-chloro-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C(Cl)=C/C(F)(F)F PNWJILFKWURCIR-UPHRSURJSA-N 0.000 description 1
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- IYFMQUDCYNWFTL-UHFFFAOYSA-N 1,1,2,2,3-pentachloropropane Chemical compound ClCC(Cl)(Cl)C(Cl)Cl IYFMQUDCYNWFTL-UHFFFAOYSA-N 0.000 description 1
- GRSQYISVQKPZCW-UHFFFAOYSA-N 1,1,2-trichloropropane Chemical compound CC(Cl)C(Cl)Cl GRSQYISVQKPZCW-UHFFFAOYSA-N 0.000 description 1
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 description 1
- ISCYUDAHBJMFNT-UHFFFAOYSA-N 1,1-dichloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C(Cl)Cl ISCYUDAHBJMFNT-UHFFFAOYSA-N 0.000 description 1
- SEVDNWAHOHGISX-UHFFFAOYSA-N 1-chloro-1,1,2,3-tetrafluoropropane Chemical compound FCC(F)C(F)(F)Cl SEVDNWAHOHGISX-UHFFFAOYSA-N 0.000 description 1
- IAOGXBHBKZGVGJ-UHFFFAOYSA-N 2,3,3-trichloro-3-fluoroprop-1-ene Chemical compound FC(Cl)(Cl)C(Cl)=C IAOGXBHBKZGVGJ-UHFFFAOYSA-N 0.000 description 1
- IAPGBTZUBKUKOR-UHFFFAOYSA-N 2,3-dichloro-3,3-difluoroprop-1-ene Chemical compound FC(F)(Cl)C(Cl)=C IAPGBTZUBKUKOR-UHFFFAOYSA-N 0.000 description 1
- FALCMQXTWHPRIH-UHFFFAOYSA-N 2,3-dichloroprop-1-ene Chemical compound ClCC(Cl)=C FALCMQXTWHPRIH-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- VTOPKRLXDFCFGJ-UHFFFAOYSA-N 3-chloro-2,3,3-trifluoroprop-1-ene Chemical compound FC(=C)C(F)(F)Cl VTOPKRLXDFCFGJ-UHFFFAOYSA-N 0.000 description 1
- 229910017050 AsF3 Inorganic materials 0.000 description 1
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 description 1
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 description 1
- 206010006326 Breath odour Diseases 0.000 description 1
- 208000006545 Chronic Obstructive Pulmonary Disease Diseases 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 208000032139 Halitosis Diseases 0.000 description 1
- 241001546602 Horismenus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910008433 SnCU Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000001088 anti-asthma Effects 0.000 description 1
- 239000000924 antiasthmatic agent Substances 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JCMGUODNZMETBM-UHFFFAOYSA-N arsenic trifluoride Chemical compound F[As](F)F JCMGUODNZMETBM-UHFFFAOYSA-N 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229940060367 inert ingredients Drugs 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002483 medication Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Abstract
The present disclosure relates to a composition comprising HFO 1234yf and at least three additional compounds selected from the group consisting of HCFO-1 233xf, HFO-1 234ze, HFO-1 243zf, and HFO-1 225zc, 5 HCFO-1 232xf, provided that the composition comprises HCFO-1 233xf and HCFO-1 232xf. oc AL 0 qL +q + A A1 p N4 AN N- C)0 + I N- N NN a)20 E: 00 )
Description
COMPLETE SPECIFICATION
FOR A DIVISIONAL PATENT
ORIGINAL
Name of Applicant: | E. I. DU PONT DE NEMOURS AND COMPANY |
Actual Inventors: | NAPPA Mario Joseph |
Address for Service: | Houlihan2, Level 1, 70 Doncaster Road, Balwyn North, Victoria 3104, Australia |
Invention Title: | COMPOSITIONS COMPRISING 2,3,3,3- TETRAFLUOROPROPENE, 1,1,2,3- TETRACHLOROPROPENE, 2-CHLORO-3,3,3 - TRIFLUOROPROPENE, OR 2-CHLORO-l,l,l,2- TETRAFLUOROPROPANE |
The following statement is a full description of this invention, including the best method of performing it known to the Applicant: 1
TITLE
2016216544 15 Aug 2016
COMPOSITIONS COMPRISING 2,3,3,3-TETRAFLUOROPROPENE,
1,1,2,3-TETRACHLOROPROPENE, 2-CHLORO-3,3,3TRIFLUOROPROPENE, OR 2-CHLORO-1,1,1,25 TETRAFLUOROPROPANE
The present Application is a Divisional Application from Australian Patent Application No. 2015201437, which is in turn a Divisional Application from Australian Patent Application No. 2010341533. The io entire disclosures of Australian Patent Application No.’s 2015201437
2010341533 and their corresponding International Patent Application No., PCT/US2010/061716, are incorporated herein by reference.
FIELD OF THE INVENTION
The present disclosure relates to the field of compositions which may be useful as heat transfer compositions, aerosol propellants, foaming agents (blowing agents), solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, foaming agents for polyolefins and polyurethane, gaseous dielectrics, extinguishing agents, and fire suppression agents in liquid or gaseous form. In particular, the present disclosure relates to compositions which may be useful as heat transfer compositions, such as 2,3,3,3tetrafluoropropene (HFO-1234yf, or 1234yf) or the compositions comprising 1,1,1,2,3-pentafluoropropane (HFC-245eb, or 245eb) which are useful in processes to produce HFO-1234yf.
BACKGROUND OF THE INVENTION
New environmental regulations have led to the need for new compositions for use in refrigeration, air-conditioning and heat pump apparatus. Low global warming potential compounds are of particular interest.
2016216544 12 Feb 2018
SUMMARY OF THE INVENTION
Applicants have found that in preparing such new low global warming potential compounds, such as HFO-1234yf, that certain additional compounds are present in small amounts.
Therefore, in accordance with the present invention, there is provided a composition comprising HFO-1234yf and at least three additional compounds selected from the group consisting of HCO-1250xf, HCC260da, HCC-260db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HCFO1233zd, HCFC-244bb, HCFC-244db, HFO-1234ze, HFC-245cb, HFO10 1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFC-241db,
HCFC-242dc, HCFO-1232xf, HCFO-1231xf, and HCFO-1233yf, provided the composition comprises HCFC-244bb, HCFC-244db, and HCFO1233yf, and provided the composition does not comprise HFO-1234yf, HCFO-1233xf, HCFO-1232xf and at least one additional compound selected from the group consisting of HFO-1234ze, HFO-1243zf and HFO1225zc.
The composition ofthe present invention may contain less than about 1 weight percent ofthe at least one additional compound, based on the total weight ofthe composition. The composition may further comprise
HFC-245cb, preferably from about 1 ppm to about 1000 ppm. More preferably, the composition further comprises HF. In a preferred embodiment, the composition is acid free.
The present invention is also directed to a method for producing cooling comprising evaporating the composition ofthe invention in the vicinity of a body to be cooled, and thereafter condensing said composition. Further, the present invention is also directed to a method for producing heat comprising condensing the composition of the invention in the vicinity of a body to be heated, and thereafter evaporating said composition.
The present invention is further directed to a method of forming a foam comprising: (a) adding to a foamabie composition the composition of
2016216544 12 Feb 2018 the present invention; and (b) processing the foamable composition under conditions effective to form a foam. In a further aspect, the present invention is directed to a process for producing aerosol products comprising the step of adding the composition of the present invention to
3a
2016216544 15 Aug 2016 a formulation, including active ingredients in an aerosol container, wherein said composition functions as a propellant.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a reaction sequence useful for formation of compositions of the present invention.
DETAILED DESCRIPTION io Compositions
HFO-1234yf (2,3,3,3-tetrafluoropropene) has been suggested for use as a refrigerant, heat transfer fluid, aerosol propellant, foam expansion agent, among other uses. It has also, advantageously, been found that HFO-1234yf has a low global warming potential (GWP) as reported by
V.C. Papadimitriou, et al. in Physical Chemistry Chemical Physics, 2007, volume 9, pages 1 -13. Thus, HFO-1234yf is a good candidate for replacing the higher GWP saturated HFC refrigerants.
In one embodiment, the present disclosure provides a composition comprising HFO-1234yf and at least one additional compound selected from the group consisting of HCO-1250xf, HCC-260da, HCC-260db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HCFO-1233zd, HCFC-244bb, HCFC-244db, HFO-1234ze, HFC-245cb, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFC-241db, HCFC-242dc, HCFO-1232xf, HCFO-1231xf, and HCFO-1233yf.
The compositions of the present invention may comprise HFO1234yf and one additional compound, or two additional compounds, or three or more additional compounds.
In another embodiment, the compositions of the present invention comprise HFO-1234yf and HCFO-1232xf.
In another embodiment, the compositions of the present invention comprise HFO-1234yf and at least one compound selected from HCFC243db, HCFO-1233xf, HCFO-1231xf, HCFC-242dc and HCFC-241db.
In another embodiment, the compositions of the present invention comprise at least one compound selected from the group consisting of 4
2016216544 15 Aug 2016
HCFC-243db and HFC-245fa.
In one embodiment, the total amount of additional compound(s) in the composition comprising HFO-1234yf ranges from greater than zero weight percent to less than 1 weight percent, based on the total weight of the composition. In another embodiment, the total amount of additional compound(s) ranges from greater than zero weight percent to less than 0.5 weight percent, based on the total weight of the composition.
In one embodiment, the compositions comprising HFO-1234yf and other compounds may further comprise a specific tracer compound, such io as HFC-245cb. In this embodiment, the HFC-245cb tracer may be present at a concentration from about 1 part per million (ppm) to about 1000 ppm in the composition. In another embodiment, the HFC-245cb tracer may be present at a concentration from about 1 ppm to about 500 ppm. Alternatively, the HFC-245cb tracer may be present at a concentration from about 10 ppm to about 300 ppm.
The compositions disclosed herein comprising HFO-1234yf are useful as low global warming potential (GWP) heat transfer compositions, aerosol propellant, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, expansion agents for polyolefins and polyurethane, gaseous dielectrics, extinguishing agents, and fire suppression agents in liquid or gaseous form. The disclosed compositions can act as a working fluid used to carry heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as a refrigerant in a cycle wherein the fluid undergoes a phase change; that is, from a liquid to a gas and back or vice versa.
Examples of heat transfer systems include but are not limited to air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units and combinations thereof.
As used herein, mobile refrigeration apparatus, mobile air conditioning or mobile heating apparatus refers to any refrigeration, air conditioner, or heating apparatus incorporated into a transportation unit for 5
2016216544 15 Aug 2016 the road, rail, sea or air. In addition, mobile refrigeration or air conditioner units, include those apparatus that are independent of any moving carrier and are known as “intermodal” systems. Such intermodal systems include “containers’ (combined sea/land transport) as well as “swap bodies” (combined road/rail transport).
As used herein, stationary heat transfer systems are systems associated within or attached to buildings of any variety. These stationary applications may be stationary air conditioning and heat pumps (including but not limited to chillers, high temperature heat pumps, residential, io commercial or industrial air conditioning systems, and including window, ductless, ducted, packaged terminal, chillers, and those exterior but connected to the building such as rooftop systems). In stationary refrigeration applications, the disclosed compositions may be useful in high temperature, medium temperature, and/or low temperature refrigeration equipment including commercial, industrial or residential refrigerators and freezers, ice machines, self-contained coolers and freezers, flooded evaporator chillers, direct expansion chillers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the disclosed compositions may be used in supermarket refrigerator and/or freezer systems.
The compounds making up the disclosed compositions are defined in Table 1.
2016216544 15 Aug 2016
TABLE 1
Code | Formula | Name |
Propylene | ||
HCO-1260zf | CH2=CHCH2CI | 3-chloropropene |
HCO-1250xf | ch2=ccich2ci | 2,3-dichloropropene |
HCC-260da | ch2cichcich2ci | 1,2,3-trichloropropane |
HCC-260db | ch3chcichci2 | 1,1,2-trichloropropane |
HCC-250aa | ch2cicci2ch2ci | 1,2,2,3-tetrachloropropane |
HCC-240aa | chci2cci2ch2ci | 1,1,2,2,3-pentachloropropane |
HCO-1230xa | cci2=ccich2ci | 1,1,2,3-tetrachloropropene |
HCFO-1233xf | cf3cci=ch2 | 2-chloro-3,3,3-trifluoropropene |
HCFO-1233zd | cf3ch=chci | 1 -chloro-3,3,3-trifluoropropene |
HCFC-244bb | cf3cfcich3 | 2-chloro-1,1,1,2-tetrafluoropropane |
HCFC-244db | cf3chcich2f | 2-chloro-1,1,1,3-tetrafluoropropane |
HFO-1234ze | cf3ch=chf | 1,3,3,3-tetrafluoropropene |
HFC-245cb | cf3cf2ch3 | 1,1,1,2,2-pentafluoropropane |
HFO-1243zf | cf3ch=ch2 | 3,3,3-trifluoropropene |
HCFO-1223za | cf3ch=cci2 | 1,1 -dichloro-3,3,3-trifluoropropene |
HCFO-1224zb | cf3ch=ccif | 1 -chloro-1,3,3,3-tetrafluoropropene |
HFO-1225zc | cf3ch=cf2 | 1,1,3,3,3-pentafluoropropene |
HCFC-241db | cci2fchcich2ci | 1 -chloro-1,1,2,3-tetrafluoropropane |
HCFC-242dc | ccif2chcich2ci | 1,1 -dif luoro-1,2,3-trichloropropane |
HCFO-1232xf | ccif2cci=ch2 | 2,3-dichloro-3,3-difluoropropene |
HCFO-1231xf | cci2fcci=ch2 | 2,3,3-trichloro-3-fluoropropene |
HCFO-1233yf | ccif2cf=ch2 | 3-chloro-2,3,3-trifluoropropene |
HCFC-243db | cf3chcich2ci | 2,3-dichloro-1,1,1 -trifluoro-propane |
HFC-245fa | cf3ch2chf2 | 1,1,1,3,3-pentafluoropropane |
HCFO-1233xf, HCFC-244bb, and many other compounds as listed in Table 1 are available from specialty chemical manufacturers, including
SynQuest Laboratories, Inc. (Alachua, FL, U.S.A.) or may be made by methods known in the art. For instance, HCFO-1233xf, and HCFC-244bb may be prepared by non-catalytic chlorination of HFO-1243zf, as
2016216544 15 Aug 2016 described in International Patent Application Publication No. W02008/054782, published May 8, 2008. Also, HCFO-1233xf and HCFC244bb may be prepared by catalytic fluorination of HCFC-243db as described in International Patent Application Publication No.
W02008/054781, published May 8, 2008. The additional compounds present in each disclosed composition will depend upon the method of manufacture.
Alternatively, HCO-1230xa can be produced from 1,2,3trichloropropane as described in US2007/0197842 A1. Additionally, io disclosed in US2007/0197842 is the reaction of HCO-1230xa with HF in the presence of catalyst in the vapor phase to form HCFO-1233xf. Alternatively, HCFO-1233xf may also be produced by fluorination of
1,1,2,3-tetrachloropropene, (HCO-1230xa) with further fluorination forming HCFC-244bb and then dehydrochlorination forming HFO-1234yf, as described in US2009/0240090.
Certain of the compounds listed in Table 1 may exist in more than one isomer, in particular HFO-1234ze, HCFO-1233zd, and HCFO-1224zb. For instance, HFO-1234ze may exist as the E-isomer or Z- isomer. As used herein HFO-1234ze is intended to refer to either of the E- isomer, the
Z- isomer or any mixtures of these isomers. As used herein HCFO1233zd is intended to refer to either of the E- isomer, the Z- isomer or any mixtures of these isomers. As used herein HFO-1224zb is intended to refer to either of the E- isomer, the Z- isomer or any mixtures of these isomers.
In addition, in accordance with the present invention, there is provided a composition comprising HCO-1230xa and at least one additional compound selected from the group consisting of propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO-1250xf, HCC-250aa, and HCC-240aa.
In another embodiment, the compositions of the present invention comprise HCO-1230xa and HCC-240aa. And in another embodiment, the compositions of the present invention may comprise HCO-1230xa, HCC240aa, and at least one compound selected from th egroup consisting of HCC-250aa and HCC-260da.
2016216544 15 Aug 2016
In addition, in accordance with the present invention, there is provided a composition comprising HCFO-1233xf and at least one additional compound selected from the group consisting of propylene, HCO-1260zf, HCC-260da, HCC-260db, HCO-1250xf, HCC-250aa, HCC5 240aa, HCO-1230xa, HFO-1243zf, HCFO-1223za, HCFO-1224zb, HFO1225zc, HCFO-1233yf, HCFO-1232xf, HCFC-1231xf, HCFC-241db, and HCFC-242dc.
In another embodiment, the compositions of the present invention comprise HCO-1230xa and HCFO-1232xf. And in another embodiment io the compositions of the present invention comprise, HCO-1230xa, HCFO1232xf and HCFO-1231 xf.
In addition, in accordance with the present invention, there is provided a composition composition comprising HCFC-244bb and at least one additional compound selected from the group consisting of propylene,
HCO-1250xf, HCC-260da, HCC-260db, HCC-240aa, HCO-1230xa,
HCFO-1233xf, HFO-1243zf, HCFO-1223az, HCFO-1224zb, HFO-1225zc, HCFC-241db, HCFC-242dc, HCFO-1232xf, HCFO-1231 xf, and HCFC1233yf.
In another embodiment, the compositions of the present invention comprising HCFC-244bb may further comprise at least one compoiund selected from the group consisting of HCFC-243db and HFC-245fa.
The series of reactions that may form the compositions of the present invention are shown in FIG. 1. The sequence of steps begins with the chorination of propylene by reaction with chlorine, Cb to form allyl chloride or HCO-1260zf (CH2=CHCH2CI). The next step involves further chlorination in the presence of Cl2 to product HCC-260db (CH2CICHCICH2CI). Reaction of HCC-260db with aqueous NaOH (or other caustic solution) forms HCO-1250xf (ΟΗ2=ΟΟΙΟΗ2ΟΙ). And reaction of HCO-1250xf with chlorine, Cl2 produces HCC-250aa (ΟΗ2ΟΙΟΟΙ2ΟΗ2ΟΙ, or 1,2,2,3-tetrachloropropane). Further chlorination with Cl2 will produce HCC-240da (CHCI2CCI2CH2CI). Reaction of HCC-240da with aqueous NaOH (or other caustic solution) will form HCO-1230xa (CCl2=CCICH2CI).
In another embodiment, any of the compositions as described previously may additionally comprise hydrogen fluoride (HF), due to the 9
2016216544 15 Aug 2016 presence of HF as either a reactant or a by-product of the reaction chemistry to produce each composition.
Of note are composiitons which are free of HCI, compositions which are free of HF and compositions which are free of both HCI and HF. Of particular note are compositions which are acid free. Acids can be removed by processes known in the art such as distillation and water or caustic washing.
Fluorination of HCQ-1230xa io The HCO-1230xa may be fluorinated by reaction with hydrogen fluoride (HF) in the presence of a catalyst to produce HCFO-1233xf. This reaction is shown in FIG. 1.
The fluorochlorination reaction may be carried out in the liquid or vapor phase. For liquid phase embodiments of the invention, the reaction of HCO-1230xa with HF may be conducted in a liquid-phase reactor operating in batch, semi-batch, semi-continuous, or continuous modes. In the batch mode, HCO-1230xa and HF are combined in an autoclave or other suitable reaction vessel and heated to the desired temperature.
In one embodiment, this reaction is carried out in semi-batch mode by feeding HCO-1230xa to a liquid-phase reactor containing HF. In another embodiment, HF may be fed to a liquid-phase reactor containing a mixture of HCO-1230xa and reaction products formed by reacting HF and HCO-1230xa. In another embodiment of the liquid-phase process, HF and HCO-1230xa may be fed concurrently in the desired stoichiometric ratio to the reactor containing a mixture of HF and reaction products formed by reacting HF and HCO-1230xa.
Suitable temperatures for the reaction of HF with HCO-1230xa in the liquid-phase reactor are, in one embodiment, from about 80°C to about 180°C, and in another embodiment, from about 100°C to about 150°C.
Higher temperatures typically result in greater conversion of the HCO1230xa.
A suitable molar ratio of HF to total amount of HCO-1230xa fed to the liquid-phase reactor is, in one embodiment, at least stoichiometric (about 3:1, HF to HCO-1230xa) and in another embodiment, is from about 10
2016216544 15 Aug 2016
5:1 to about 100:1. Of note are embodiments wherein the molar ratio of HF to HFO-1243zf is from about 8:1 to about 50:1.
The reactor pressure in the liquid-phase process is not critical and in batch reactions is usually the autogenous pressure of the system at the reaction temperature. The pressure of the system increases as hydrogen chloride is formed by replacement of hydrogen substituents by chlorine, and by replacement of chlorine substituents by fluorine in the starting materials and intermediate reaction products. In a continuous process it is possible to set the pressure of the reactor in such a way that the lower io boiling products of the reaction are vented from the reactor, optionally through a packed column or condenser. In this manner, higher boiling intermediates remain in the reactor and the volatile products are removed. Typical reactor pressures are from about 20 psig (239 kPa) to about 1,000 psig (6,994 kPa).
In some embodiments, in which the reaction is conducted using a liquid-phase process, catalysts which may be used include carbon, AIF3, BF3, FeCI3.aFa (where a = 0 to 3), FeX3 supported on carbon, SbCI3.aFa, AsF3, MCI5-bFb (where b = 0 to 5 and M = Sb, Nb, Ta, or Mo), and M’Cl4-cFc (where c = 0 to 4, and M’ = Sn, Ti, Zr, or Hf). In another embodiment, catalysts for the liquid phase process are MCls-bFb (where b = 0 to 5 and M = Sb, Nb, or Ta).
In another embodiment, the reaction of HF with HCO-1230xa is carried out in the vapor phase. Typically a heated reactor is used. A number of reactor configurations are possible including horizontal or vertical orientation of the reactor as well as the sequence of reaction of the HCO-1230xa with HF. In one embodiment of the invention, the HCO1230xa may be initially vaporized and fed to the reactor as a gas.
Suitable temperatures for the vapor-phase reaction are from about 120°C to about 500°C. Higher temperatures result in greater conversion of HCO-1230xa and higher degrees of fluorination and halogenation in the converted compounds.
Suitable reactor pressures for the vapor-phase reactor may be from about 1 to about 30 atmospheres. A pressure of about 15 to about 25 atmospheres may be advantageously employed to facilitate separation of 11
2016216544 15 Aug 2016
HCI from other reaction products, and the suitable reaction time may vary from about 1 to about 120 seconds, preferably from about 5 to about 60 seconds.
The molar ratio of HF to the total amount of HCO-1230xa for the vapor-phase reaction is, in one embodiment, from about the stoichiometric ratio of HF to the total amount of HCO-1230xa (3:1 HF to HCO-1230xa) to about 50:1 and, in another embodiment, from about 10:1 to about 30:1.
In one embodiment, a catalyst is used in the reaction zone for the vapor-phase reaction of HF with (3:1 HF to HCO-1230xa).
io Chlorofluorination catalysts which may be used in the vapor phase reaction include carbon; graphite; alumina; fluorided alumina; aluminum fluoride; alumina supported on carbon; aluminum fluoride supported on carbon; fluorided alumina supported on carbon; magnesium fluoride supported on aluminum fluoride; metals (including elemental metals, metal oxides, metal halides, and/or other metal salts); metals supported on aluminum fluoride; metals supported on fluorided alumina; metals supported on alumina; and metals supported on carbon; mixtures of metals.
Suitable metals for use as catalysts (optionally supported on alumina, aluminum fluoride, fluorided alumina, or carbon) include chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium, zirconium, and hafnium, copper, silver, gold, zinc, and/or metals having an atomic number of 58 through 71 (i.e., the lanthanide metals). In one embodiment, when used on a support, the total metal content of the catalyst will be from about 0.1 to about 20 percent by weight based on the total weight of the catalyst; in another embodiment from about 0.1 to about 10 percent by weight based on the total weight of the catalyst.
Suitable chlorofluorination catalysts for the vapor-phase reactions include chromium-containing catalysts including chromium(lll) oxide (Cr2O3); Cr2O3with other metals such as magnesium halides or zinc halides supported on Cr2O3; chromium(lll) halides supported on carbon;
mixtures of chromium and magnesium (including elemental metals, metal oxides, metal halides, and/or other metal salts) optionally supported on 12
2016216544 15 Aug 2016 graphite; and mixtures of chromium and other metals (including elemental metals, metal oxides, metal halides, and/or other metal salts) optionally supported on graphite, alumina, or aluminum halides such as aluminum fluoride.
Chromium-containing catalysts are well known in the art. They may be prepared by either precipitation methods or impregnation methods as generally described by Satterfield on pages 87-112 in Heterogeneous Catalysis in Industrial Practice, 2nd edition (McGraw-Hill, New York, 1991).
Of note are chlorofluorination catalysts that comprise at least one io chromium-containing component selected from the group consisting of crystalline alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms, and crystalline alpha-chromium oxide where from about 0.05 atom % to about 6 atom % of the chromium atoms in the alpha-chromium oxide lattice are replaced by trivalent cobalt atoms which has been treated with a fluorinating agent. These catalysts, including their preparation, have been disclosed in U. S. Patent Application Publication US2005/0228202.
In another embodiment, the vapor phase catalyst for reaction of
HCO-1230xa with HF may be a catalyst composition comprising Cr2C>3 prepared by pyrolysis of (NH4)2Cr2O7 as described in US 5,036,036.
Optionally, the metal-containing catalysts described above can be pretreated with HF. This pretreatment can be accomplished, for example, by placing the metal-containing catalyst in a suitable container, and thereafter, passing HF over the metal-containing catalyst. In one embodiment, such container can be the reactor used to perform the chlorofluorination reaction. In one embodiment, the pretreatment time is from about 15 to about 300 minutes, and the pretreatment temperature is from about 200°C to about 450°C.
Fluorination of HCFO-1233xf
In some embodiments, HCFO-1233xf may be used to make HCFCHCFC-244bb, and/or HFO-1234yf by fluorination. These reactions are shown in FIG. 1.
2016216544 15 Aug 2016
In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb may be carried out in the liquid phase. In another embodiment, the reaction may be carried out in the vapor phase.
In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb 5 may be carried out in batch mode. In another embodiment, the reaction may be carried out in a continuous mode.
In one embodiment, a liquid phase reaction of HCFO-1233xf to HCFC-244bb may be carried out in the presence of a catalyst. In one embodiment, the catalyst may be a Lewis acid catalyst. In one io embodiment, the catalyst may be a metal-halide catalyst. In another embodiment, the catalyst may be at least one catalyst selected from the group consisting of antimony halides, tin halides, thallium halides, iron halides and combinations of two or more thereof. In another embodiment, the catalysts may be at least one catalyst selected from antimony pentachloride (SbCb), antimony trichloride (SbCb), antimony pentafluoride (SbF5), tin tetrachloride (SnCU), titanium tetrachloride (TiCU), iron trichloride (FeCI3, and combinations thereof. In some embodiments, the reaction may be carried out with any known fluorination catalyst for liquid phase reactions.
In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb may be carried out in the absence of catalyst.
In one embodiment, a vapor phase reaction of HCFO-1233xf to HCFC-244bb may be carried out in the presence of a catalyst. In one embodiment, the reaction is carried out in the presence of a chromium25 based catalyst, an iron-based catalyst, or combinations thereof. In one embodiment, the chromium based catalyst is a chromium oxide (e.g. Cr2O3). In one embodiment, the iron-based catalyst may be FeCb on carbon.
In one embodiment, the vapor phase reaction of HCFO-1233xf to
HCFC-244bb is carried out in the absence of catalyst.
Dehydrochlorination of HCFC-244bb
In some embodiments, dehydrochlorination of HCFC-244bb is used to prepare HFO-1234yf.
2016216544 15 Aug 2016
In one embodiment, dehydrochlorination of HCFC-244bb to HFO1234yf is carried out in the vapor phase.
In one embodiment, vapor phase dehydrochlorination is carried out in the presence of catalyst. In one embodiment, the catalyst is selected from carbon and/or metal based catalysts. In one embodiment, the catalyst may be selected from an activated carbon, a nickel-based catalyst, a palladium based catalyst, or any combination of these catalysts. In one embodiment, the catalyst may be selected from the group consisting of Ni-mesh, palladium on carbon, palladium on aluminum oxide, io or combinations thereof.
In one embodiment, the catalyzed vapor phase dehydrochlorination is carried out at a temperature from about 200 to 600 QC. In another embodiment, the catalytic vapor phase dehydrochlorination is carried out at a temperature from about 250 to 500 QC. The reaction pressure is about from 0 to 150 psi.
In another embodiment, HFO-1234yf is prepared by thermal dehydrochlorination of HCFC-244bb. In one embodiment, this reaction occurs in the absence of a catalyst. In one embodiment, HCFC-244bb is introduced into a reaction vessel which temperature is maintained at a temperature high enough to effect the thermal dehydrochlorination of HCFC-244bb. In one embodiment, the temperature is high enough to effect the thermal dehydrochlorination of HCFC-244bb to a percent conversion of at least 50%. In another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of HCFC-244bb to a percent conversion of at least 65%. In yet another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of HCFC-244bb to a percent conversion of at least 80%. In yet another embodiment, the temperature is high enough to effect the thermal dehydrochlorination of HCFC-244bb to a percent conversion of at least
70% for at least 12 hours of continuous operation.
In one embodiment, HCFC-244bb is introduced into a reaction vessel into a reaction vessel which temperature is maintained at a temperature in the range of from about 500 °C to about 700 °C. In another embodiment, the temperature of the reaction vessel is maintained in the 15
2016216544 15 Aug 2016 range from about 500 °C to about 650 °C. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to effect the pyrolysis of HCFC-244bb to HFO-1234yf with a selectivity of 80% or greater. In yet another embodiment, the temperature of the reaction vessel is maintained at a temperature high enough to effect the pyrolysis of HCFC-244bb to HFO-1234yf with a selectivity of 85% or greater.
In one embodiment, for either the catalyzed or non-catalytic dehydrochlorination reaction, the reaction zone is a reaction vessel io comprised of materials which are resistant to corrosion. In one embodiment, these materials comprise alloys, such as nickel-based alloys such as Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp, under the trademark Inconel® (hereinafter “Inconel®”) or nickel-copper alloys commercially available from Special Metals Corp.
(New Hartford, New York) under the trademark Monel®, or vessels having fluoropolymers linings.
In one embodiment, the HCFC-244bb is preheated in a vaporizer to a temperature of from about 30 °C to about 100 °C. In another embodiment, the HCFC-244bb is preheated in a vaporizer to a temperature of from about 30 °C to about 80 °C.
In some embodiments, an inert diluent gas is used as a carrier gas for HCFC-244bb. In one embodiment, the carrier gas is selected is nitrogen, argon, helium or carbon dioxide.
Without further elaboration, it is believed that one skilled in the art 25 can, using the description herein, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative, and do not constrain the remainder of the disclosure in any way whatsoever.
Utility
The compositions disclosed herein comprising HFO-1234yf are useful as low global warming potential (GWP) heat transfer compositions, aerosol propellant, foam expansion agents (also known as foaming agents or blowing agents), solvents, cleaning agents, carrier fluids, displacement 16
2016216544 15 Aug 2016 drying agents, buffing abrasion agents, polymerization media, foaming agents for polyolefins and polyurethane, gaseous dielectrics, extinguishing agents, and fire suppression agents in liquid or gaseous form. The disclosed compositions can act as a working fluid used to carry heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as a refrigerant in a cycle wherein the fluid undergoes a phase change; that is, from a liquid to a gas and back or vice versa.
Examples of heat transfer systems include but are not limited to air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded io evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units and combinations thereof.
In one embodiment, the compositions comprising HFO-1234yf are useful in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or apparatus. In another embodiment, the compositions are useful in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or apparatus.
As used herein, mobile heat transfer systems refers to any refrigeration, air conditioner, or heating apparatus incorporated into a transportation unit for the road, rail, sea or air. In addition, mobile refrigeration or air conditioner units, include those apparatus that are independent of any moving carrier and are known as “intermodal” systems. Such intermodal systems include “containers’ (combined sea/land transport) as well as “swap bodies” (combined road/rail transport).
As used herein, stationary heat transfer systems are systems that are fixed in place during operation. A stationary heat transfer system may be associated within or attached to buildings of any variety or may be stand alone devices located out of doors, such as a soft drink vending machine. These stationary applications may be stationary air conditioning and heat pumps (including but not limited to chillers, high temperature heat pumps, residential, commercial or industrial air conditioning systems, and including window, ductless, ducted, packaged terminal, chillers, and 17
2016216544 15 Aug 2016 those exterior but connected to the building such as rooftop systems). In stationary refrigeration applications, the disclosed compositions may be useful in high temperature, medium temperature and/or low temperature refrigeration equipment including commercial, industrial or residential refrigerators and freezers, ice machines, self-contained coolers and freezers, flooded evaporator chillers, direct expansion chillers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the disclosed compositions may be used in supermarket refrigerator systems.
io Therefore in accordance with the present invention, the compositions as disclosed herein containing HFO-1234yf may be useful in methods for producing cooling, producing heat, and transferring heat.
The compositions disclosed herein may be useful as low global warming potential (GWP) replacements for currently used refrigerants, including but not limited to R134a (or HFC-134a, 1,1,1,2tetrafluoroethane), R22 (or HCFC-22, chlorodifluoromethane), R12 (CFC-12, dichlorodifluoromethane); R407C (ASHRAE designation for a blend of 52 weight percent R134a, 25 weight percent R125 (pentafluoroethane), and 23 weight percent R32 (difluoromethane));
R410A (ASHRAE designation for a blend of 50 weight percent R125 and weight percent R32); and R404A (ASHRAE designation for a blend of 44 weight percent R125, 52 weight percent R143a (1,1,1 -trifluoroethane), and 4.0 weight percent R134a), among others.
In many applications, some embodiments of the present compositions comprising HFO-1234yf are useful as refrigerants and provide at least comparable cooling performance (meaning cooling capacity and energy efficiency) as the refrigerant for which a replacement is being sought.
In another embodiment is provided a method for recharging a heat transfer system that contains a refrigerant to be replaced and a lubricant, said method comprising removing the refrigerant to be replaced from the heat transfer system while retaining a substantial portion of the lubricant in said system and introducing one of the present compositions comprising
HFO-1234yf to the heat transfer system.
2016216544 15 Aug 2016
In another embodiment, a heat exchange system containing any of the present compositions comprising HFO-1234yf is provided, wherein said system is selected from the group consisting of air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units, and systems having combinations thereof. Additionally, the compositions comprising HFO1234yf may be useful in secondary loop systems wherein these compositions serve as the primary refrigerant thus providing cooling to a io secondary heat transfer fluid that thereby cools a remote location.
Vapor-compression refrigeration, air-conditioning, or heat pump systems include an evaporator, a compressor, a condenser, and an expansion device. A vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator, by withdrawing heat from the environment, at a low temperature to form a gas and produce cooling.
The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.
In one embodiment, there is provided a heat transfer system containing any of the present compositions comprising HFO-1234yf. In another embodiment is disclosed a refrigeration, air-conditioning or heat pump apparatus containing any of the present compositions comprising
HFO-1234yf. In another embodiment, is disclosed a stationary refrigeration or air-conditioning apparatus containing any of the present compositions comprising HFO-1234yf. In yet another embodiment is disclosed a mobile refrigeration or air conditioning apparatus containing a composition as disclosed herein.
2016216544 15 Aug 2016
In another embodiment, a method is provided for producing cooling comprising evaporating any of the present compositions comprising HFO1234yf in the vicinity of a body to be cooled, and thereafter condensing said composition.
In another embodiment, a method is provided for producing heat comprising condensing any of the present compositions comprising HFO1234yf in the vicinity of a body to be heated, and thereafter evaporating said compositions.
In another embodiment, disclosed is a method of using the present io compositions comprising HFO-1234yf as a heat transfer fluid composition.
The method comprises transporting said composition from a heat source to a heat sink.
In another embodiment, the present invention relates to foam expansion agent compositions comprising HFO-1234yf for use in preparing foams. In other embodiments the invention provides foamable compositions, and preferably thermoset (like polyurethane, polyisocyanurate, or phenolic) foam compositions, and thermoplastic (like polystyrene, polyethylene, or polypropylene) foam compositions and method of preparing foams. In such foam embodiments, one or more of the present compositions comprising HFO-1234yf are included as a foam expansion agent in foamable compositions, which composition preferably includes one or more additional components capable of reacting and/or mixing and foaming under the proper conditions to form a foam or cellular structure.
The present invention further relates to a method of forming a foam comprising: (a) adding to a foamable composition a composition comprising HFO-1234yf of the present invention; and (b) processing the foamable composition under conditions effective to form a foam.
Another embodiment of the present invention relates to the use of the compositions of the present invention comprising HFO-1234yf as propellants in sprayable compositions. Additionally, the present invention relates to a sprayable compositions comprising HFO-1234yf. The active ingredient to be sprayed together with inert ingredients, solvents and other materials may also be present in a sprayable composition. In one 20
2016216544 15 Aug 2016 embodiment, a sprayable composition is an aerosol. The present compositions can be used to formulate a variety of industrial aerosols or other sprayable compositions such as contact cleaners, dusters, lubricant sprays, mold release sprays, insecticides, and the like, and consumer aerosols such as personal care products (such as, e.g., hair sprays, deodorants, and perfumes), household products (such as, e.g., waxes, polishes, pan sprays, room fresheners, and household insecticides), and automotive products (such as, e.g., cleaners and polishers), as well as medicinal materials such as anti-asthma and anti-halitosis medications.
io Examples of this includes metered dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of medicaments to accessible mucous membranes or intranasally
The present invention further relates to a process for producing aerosol products comprising the step of adding a composition of the present invention comprising HFO-1234yf to a formulation, including active, ingredients in an aerosol container, wherein said composition functions as a propellant. Additionally, the present invention further relates to a process for producing aerosol products comprising the step of adding a composition of the present invention comprising HFO-1234yf to a barrier type aerosol package (like a bag-in-a-can or piston can) wherein said composition is kept separated from other formulation ingredients in an aerosol container, and wherein said composition functions as a propellant. Additionally, the present invention further relates to a process for producing aerosol products comprising the step of adding only a composition of the present invention comprising HFO-1234yf to an aerosol package, wherein said composition functions as the active ingredient (e.g., a duster, or a cooling or freezing spray).
The compositions disclosed herein comprising HCO-1230xa, HCFO-1233xf, and HCFC-244bb are useful in methods to prepare HFO30 1 234yf as described previously herein.
Without further elaboration, it is believed that one skilled in the art can, using the description herein, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be 21
2016216544 15 Aug 2016 construed as merely illustrative, and do not constrain the remainder of the disclosure in any way whatsoever.
EXAMPLES
General Procedure for Product Analysis
The following general procedure is illustrative of the method used for analyzing the products of fluorination reactions. Part of the total reactor effluent was sampled on-line for organic product analysis using a io gas chromatograph equipped with a mass selective detector (GC/MS).
The gas chromatography utilized a 20 ft. (6.1 m) long x 1/8 in. (0.32 cm) diameter tube containing perfluorinated polyether sold under the trademark Krytox® by E. I. du Pont de Nemours and Company (hereinafter “DuPont”) of Wilmington, Delaware on an inert carbon support. The helium flow was 30 mL/min (5.0 x 107 m^/sec). Gas chromatographic conditions were 60°C for an initial hold period of three minutes followed by temperature programming to 200°C at a rate of 6°C/minute.
EXAMPLE 1
Fluorination of HCFO-1233xf to HCFC-244bb The contents of a small PTFE vial containing 20 grams of viscous
SbF5 were poured into a dry 400 mL Hastelloy® shaker tube. The tube was closed and was pressurized with nitrogen for leak testing. The shaker tube was then cooled to less than - 40 QC with dry ice, slowly vented, and then evacuated. 75 grams (3.75-moles) of anhydrous HF was condensed into the shaker tube followed by 165 grams (1.26-moles) of HCFO-1233xf. The shaker tube was placed in a barricade and shaking was started.
The shaker tube was agitated at ambient temperature (~20-23°C) and the pressure was 21 to 25 psig. After 2 hours, shaking was stopped and 150 mL of water was carefully pumped into the shaker tube. The tube was left overnight and then cooled to 0 to 5°C in an ice bath before
2016216544 15 Aug 2016 depressurization and transferring the contents to a plastic container. The container was kept on ice.
The container contents were poured into a polypropylene separatory funnel containing some ice. The lower organic layer was light amber in appearance. The organic layer was separated into a media bottle made of a glass sold under the trademark of Pyrex® by Corning (Lowell, MA) (hereinafter “Pyrex® j containing ~50-mL of 4 molar (pH 7) phosphate buffer and ice (~100-mL). The organic layer was again separated and poured into a dry Pyrex® media bottle containing a small amount of anhydrous magnesium sulfate. Crude yield was 164.3 grams (about 120-mL, 86%).
GC/MS of the crude material showed that it was mostly HCFC244bb. Other components included 0.16% 1233xf, and other byproducts totaling 12.2%.
EXAMPLE 2
Fluorination of HCFO-1233xf to HCFC-244bb
The contents of a small PTFE vial containing 20 grams of viscous SbF5 were poured into a dry 400-mL Hastelloy® shaker tube. The tube was closed and was pressurized with nitrogen for leak testing. The shaker tube was then cooled to less than - 40 QC with dry ice, slowly vented, and then evacuated. 53 grams (2.65 moles) of anhydrous HF was transferred into the shaker tube followed by 227 grams (1.74 moles) of HCFO-1233xf was condensed into the chilled shaker tube. The shaker tube was placed in the barricade and shaking was started.
The shaker tube was agitated at ambient temperature (-18-21 °C) and the pressure was 16 to 20 psig. After 2 hours, shaking was stopped and 100 mL of water was carefully pumped into the shaker tube. The tube was left overnight and cooled to 0 to 5°C in an ice bath before venting and transferring the contents to a plastic container. The container was kept on ice.
The container contents were poured into a polypropylene separatory
2016216544 15 Aug 2016 funnel containing some ice. The lower organic layer was light amber in appearance. The organic layer was separated into a Pyrex® media bottle containing about 50 mL of 4 molar (pH 7) phosphate buffer and ice (~100mL). The organic layer was again separated and poured into a dry Pyrex® media bottle containing a small amount of anhydrous magnesium sulfate. Crude yield was 238.8 grams (about 170-mL, 91%).
GC/MS of the crude material indicated that it was mostly HCFC244bb. Other components included 0.11% HFC-245cb, 0.10% HFC245eb, 0.26% HCFO-1233xf, and other byproducts totaling 9.7%.
io
EXAMPLE 3
Example 3 demonstrates the conversion of HCFC-244bb (2-chloro1,1,1,2-tetrafluoropropane) to HFO-1234yf (2,3,3,3-tetrafluoropropene) in the absence of a catalyst.
An empty Inconel® tube (1/2 inch OD) with a heated zone of about inches was heated to a temperature between 500QC and 626QC, and HFC-244bb was fed at 0.52 mL/hour through a vaporizer set at 40QC using a N2 sweep of 2.4 seem (4.0 x 10'8 m3). The reactor effluent was analyzed using an on-line GCMS, with the results being reported in mole percent.
TABLE 2
Temp., 1C | Mole Percent | |||
1234yf | 244bb | 1233xf | Other | |
500 | 14.2 | 82.6 | 1.2 | 2.0 |
550 | 57.0 | 35.4 | 1.2 | 6.4 |
574 | 77.0 | 13.0 | 1.4 | 8.6 |
603 | 85.0 | 1.3 | 0.7 | 13.0 |
626 | 82.5 | 0.2 | 1.4 | 15.9 |
EXAMPLE 4
Example 4 demonstrates the conversion of HCFC-244bb (2-chloro25 1,1,1,2-tetrafluoropropane) to HFO-1234yf (2,3,3,3-tetrafluoropropane) in the absence of a catalyst.
2016216544 15 Aug 2016
An empty Inconel® tube (1/2 inch OD) with a heated zone of about 12 inches was heated to 575QC, and HFC-244bb was fed at 0.35 mL/hour through a vaporizer set at 40QC using a N2 sweep of 3.6 seem (6.0 x 10'8 m3). The reactor was operated for a total of 19 hours continuously, and samples were taken periodically and analyzed to determine % conversion of HFC-244bb, and selectivity to HFO-1234yf. The reactor effluent was analyzed using an on-line GCMS, and the data in Table 6 below is an average of at least two on-line injections at a given condition; the percentages are mole percent.
io TABLE 3
Hours | 1234yf | 244bb | 1233xd | 1223 (2 isomers) | Other |
3 | 68.8 | 17.9 | 5.1 | 0.5 | 7.7 |
4 | 61.5 | 22.7 | 7.4 | 1.1 | A3 |
8 | 61.1 | 15.0 | 14.1 | T9 | T9 |
12 | 60.1 | 13.7 | 16.4 | 6.0 | 9.8 |
15 | 66.9 | 14.5 | 12.0 | 2.7 | T9 |
19 | 67.4 | 7.0 | 16.6 | 8.2 | 0.8 |
EXAMPLE 5
Example 5 demonstrates the dehydrochlorination of HCFC-244bb (2-chloro-1,1,1,2-tetrafluoropropane) in the presence of an activated carbon catalyst.
An Inconel® tube (1/2 inch OD) was filled with 4 cc (1.99 gm) of acid washed PCB Polynesian coconut shell based carbon from Calgon (6-10 mesh). HFC-244bb was fed at 1.04 mL/hour through a vaporizer set at
40QC using a N2 sweep of 2.4 seem (4.0 x 10'8 m3) giving a total contact time of about 32 seconds while controlling the reactor temperature at 400QC.
The data in Table 4 shows the reactor effluent composition in mole percent for this process run with an activated carbon catalyst to make
HFC-1234yf via HCI elimination over the period of 7 hours of operation.
2016216544 15 Aug 2016
TABLE 4
Hours | 1234yf | 244bb | 1233xf | Other |
1 | 52.2 | 22.4 | 10.3 | 15.1 |
2 | 44.5 | 24.6 | 13.4 | 17.5 |
3 | 38.0 | 31.9 | 14.8 | 15.3 |
4 | 25.9 | 41.8 | 15.7 | 16.6 |
5 | 15.5 | 49.4 | 17.9 | 17.2 |
6 | ΖΛ | 53.8 | 18.0 | 21.1 |
7 | 2.9 | 54.2 | 17.3 | 25.6 |
Where the terms “comprise”, “comprises”, “comprised” or 5 “comprising” are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof.
2016216544 15 Aug 2016
Claims (10)
- The Claims defining the invention are as follows:1. A composition comprising HFO-1234yf and at least three additional compounds selected from the group consisting of HCO-1250xf, HCC260da, HCC-260db, HCC-240aa, HCO-1230xa, HCFO-1233xf, HCFO5 1233zd, HCFC-244bb, HCFC-244db, HFO-1234ze, HFC-245cb, HFO1243zf, HCFO-1223za, HCFO-1224zb, HFO-1225zc, HCFC-241db, HCFC-242dc, HCFO-1232xf, HCFO-1231 xf, and HCFO-1233yf, provided the composition comprises HCFC-244bb, HCFC-244db, and HCFO1233yf, and provided the composition does not comprise HFO-1234yf, io HCFO-1233xf, HCFO-1232xf and at least one additional compound selected from the group consisting of HFO-1234ze, HFO-1243zf and HFO1225zc.
- 2. The composition of claim 1 containing less than about 1 weight percent of said additional compounds, based on the total weight of the15 composition.
- 3. The composition of claim 1 further comprising HFC-245cb.
- 4. The composition of claim 3 comprising from about 1 ppm to about 1000 ppm of HFC-245cb.
- 5. The composition of any one of claims 1 to 4 further comprising HF.20
- 6. The composition of any one of claims 1 to 4 that are acid free.
- 7. A method for producing cooling comprising evaporating a composition of any one of claims 1 to 4 in the vicinity of a body to be cooled, and thereafter condensing said composition.
- 8. A method for producing heat comprising condensing a composition of25 any one of claims 1 to 4 in the vicinity of a body to be heated, and thereafter evaporating said composition.2016216544 15 Aug 2016
- 9. A method of forming a foam comprising: (a) adding to a foamable composition a composition of any one of claims 1 to 4; and (b) processing the foamable composition under conditions effective to form a foam.
- 10. A process for producing aerosol products comprising the step of 5 adding a composition of any one of claims 1 to 4 to a formulation, comprising active ingredients in an aerosol container, wherein said composition functions as a propellant.1/12016216544 15 Aug 2016
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2016216544A AU2016216544B2 (en) | 2009-12-22 | 2016-08-15 | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US61/289,027 | 2009-12-22 | ||
AU2010341533A AU2010341533B2 (en) | 2009-12-22 | 2010-12-22 | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane |
AU2015201437A AU2015201437B2 (en) | 2009-12-22 | 2015-03-18 | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane |
AU2016216544A AU2016216544B2 (en) | 2009-12-22 | 2016-08-15 | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2015201437A Division AU2015201437B2 (en) | 2009-12-22 | 2015-03-18 | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2016216544A1 AU2016216544A1 (en) | 2016-09-01 |
AU2016216544B2 true AU2016216544B2 (en) | 2018-03-01 |
Family
ID=56802074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU2016216544A Active AU2016216544B2 (en) | 2009-12-22 | 2016-08-15 | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane |
Country Status (1)
Country | Link |
---|---|
AU (1) | AU2016216544B2 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009137658A2 (en) * | 2008-05-07 | 2009-11-12 | E. I. Du Pont De Nemours And Company | Compositions comprising 2,3-dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane or 2,3,3,3-tetrafluoropropene |
-
2016
- 2016-08-15 AU AU2016216544A patent/AU2016216544B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009137658A2 (en) * | 2008-05-07 | 2009-11-12 | E. I. Du Pont De Nemours And Company | Compositions comprising 2,3-dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane or 2,3,3,3-tetrafluoropropene |
Also Published As
Publication number | Publication date |
---|---|
AU2016216544A1 (en) | 2016-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11596824B2 (en) | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetra-chloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane | |
AU2016216544B2 (en) | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane | |
AU2015201437B2 (en) | Compositions comprising 2,3,3,3-tetrafluoropropene, 1,1,2,3-tetrachloropropene, 2-chloro-3,3,3-trifluoropropene, or 2-chloro-1,1,1,2-tetrafluoropropane |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FGA | Letters patent sealed or granted (standard patent) | ||
PC | Assignment registered |
Owner name: THE CHEMOURS COMPANY FC, LLC. Free format text: FORMER OWNER(S): E. I. DU PONT DE NEMOURS AND COMPANY |