Liquid phase process for preparing (E)-1,1,1,4,4,4-hexafluorobut-2-ene

Patent metadata

Field	Value
Publication number	US-10611709-B2
Application number	US-201816126560-A
Country	US
Kind code	B2
Filing date	Sep 10, 2018
Priority date	Sep 11, 2017
Publication date	Apr 7, 2020
Grant date	Apr 7, 2020

Abstract

Disclosed herein are methods of producing E-CF3CH═CHCF3 in a liquid phase. Also disclosed are methods of preparing CF3CH2CHClCF3 and CF3CHClCH2CCl3.

First claim

What is claimed is:

1. A process for preparing E-CF 3 CH═CHCF 3 , comprising:
treating CF 3 CH 2 CHClCF 3 with an effective amount of a base in the presence of a phase transfer catalyst and a solvent component consisting of water, to form a mixture comprising the E-CF 3 CH═CHCF 3 ,
wherein the process is a liquid phase process and the base is sodium hydroxide.

2. The process of claim 1 , wherein the mixture further comprises one or more of hexafluoroisobutylene, 1,1,1,4,4,4-hexafluorobutane, (E)-1-chloro-1,1,4,4,4-pentafluorobut-2-ene, and Z—CF 3 CH═CHCF 3 .

3. The process of claim 1 , wherein the base is in an aqueous solution of from about 4 M to about 12 M.

4. The process of claim 1 , wherein the phase transfer catalyst is selected from the group consisting of a quaternary ammonium salt, a heterocyclic ammonium salt, an organic phosphonium salt, and a nonionic compound.

5. The process of claim 4 , wherein the phase transfer catalyst is selected from the group consisting of benzyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltricaprylammonium chloride, methyltributylammonium chloride, methyltrioctylammonium chloride, dimethyldiphenylphosphonium iodide, methyltriphenoxyphosphonium iodide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, hexadecyltributylphosphonium bromide, and DL-α-tocopherol methoxypolyethylene glycol succinate.

6. The process of claim 5 , wherein the phase transfer catalyst is methyltrioctylammonium chloride.

7. The process of claim 4 , wherein the base is sodium hydroxide and the phase transfer catalyst is methyltrioctylammonium chloride.

8. The process of claim 1 , wherein the E-CF 3 CH═CHCF 3 is substantially isolated from the mixture.

9. The process of claim 1 , wherein the CF 3 CH 2 CHClCF 3 is prepared according to a second process comprising contacting CF 3 CHClCH 2 CCl 3 with HF in the presence of a catalyst, wherein the second process is a liquid phase process.

10. The process of claim 9 , wherein the catalyst is a metal halide selected from the group consisting of SbF 5 , SbCl 5 , SbCl 3 , SnCl 4 , TaCl 5 , TiCl 4 , NbCl 5 , MoCl 6 , WC 16 , antimony (V) chlorofluorides, and combinations thereof.

11. The process of claim 10 , wherein the metal halide is selected from the group consisting of SbF 5 , TaCl 5 , and antimony (V) chlorofluorides.

12. The process of claim 9 , wherein the second process is performed at a temperature of from about 50° C. to about 100° C.

13. The process of claim 9 , wherein the CF 3 CHClCH 2 CCl 3 is prepared by a third process comprising contacting carbon tetrachloride with 3,3,3-trifluoropropene in the presence of an organophosphorus compound and a catalyst comprising a metal, wherein the third process is a liquid phase process.

14. The process of claim 13 , wherein the organophosphorus compound is selected from the group consisting of a phosphate ester, a phosphate amide, a phosphonic acid, a phosphonic ester, a phosphinic acid, a phosphinic ester, a phosphine oxide, a phosphine imide, a phosphonium salt, a phosphorene, a phosphite, a phosphonate, a phosphinite, and a phosphine.

15. The process of claim 14 , wherein the organophosphorus compound is tributylphosphate.

16. The process of claim 13 , wherein the metal of the catalyst is selected from the group consisting of Fe, Co, Ni, Cu, Mo, Cr, and Mn.

17. The process of claim 16 , wherein the metal is Fe.

18. The process of claim 13 , wherein the third process takes place at a temperature of from about 100° C. to about 120° C.

19. A process for preparing E-CF 3 CH═CHCF 3 , comprising:
(a) contacting carbon tetrachloride with 3,3,3-trifluoropropene in the presence of an organophosphorus compound and a catalyst comprising a metal to produce CF 3 CHClCH 2 CCl 3 ;
(b) contacting the CF 3 CHClCH 2 CCl 3 with HF in the presence of a catalyst to produce CF 3 CH 2 CHClCF 3 ; and
(c) treating the CF 3 CH 2 CHClCF 3 with an effective amount of a base in the presence of a phase transfer catalyst and a solvent component consisting of water, to form a mixture comprising the E-CF 3 CH═CHCF 3 ,
wherein the process is a liquid phase process, and the base of step (c) is sodium hydroxide.

20. The process of claim 19 , wherein the mixture of step (c) further comprises one or more of hexafluoroisobutylene, 1,1,1,4,4,4-hexafluorobutane, (E)-1-chloro-1,1,4,4,4-pentafluorobut-2-ene, and Z—CF 3 CH═CHCF 3 .

21. The process of claim 19 , wherein the E-CF 3 CH═CHCF 3 is substantially isolated from the mixture.

22. A composition, consisting of comprising:
E-CF 3 CH═CHCF 3 ,
hexafluoroisobutylene, 1,1,1,4,4,4-hexafluorobutane, (E)-1-chloro-1,1,4,4,4-pentafluorobut-2-ene, and Z—CF 3 CH═CHCF 3 .

23. The composition of claim 22 , wherein the composition consists of greater than about 99 mol % E-CF 3 CH═CHCF 3 .

24. The composition of claim 22 , which is prepared according to a process comprising treating CF 3 CH 2 CHClCF 3 with an effective amount of a base in the presence of a phase transfer catalyst and a solvent component consisting of water, wherein the process is a liquid phase process and the base is sodium hydroxide.

Assignees

• Chemours Co Fc Llc

Inventors

• Peng Sheng
• Jackson Andrew
• Brandstadter Stephan
• Nappa Mario Joseph

Classifications

• B01J31/0268

  Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous · CPC title

• C07C17/206

  the other compound being HX · CPC title

• B01J23/745

  Iron · CPC title

• C07C21/185

  Tetrafluoroethene · CPC title

• B01J2531/98

  Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases · CPC title