PROCESS FOR PRODUCING FLUOROOLEFINS

• US 20030060670A1
• Filed: 09/25/2001
• Published: 03/27/2003
• Est. Priority Date: 09/25/2001
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Nair, Haridasan K., Nalewajek, David, Puy, Michael Van Der, Poss, Andrew J., Bradley, David E., Shankland, Ian R., Demmin, Timothy R.
• Granted Patent: US 6,548,719 B1
• Time in Patent Office: Days
• US Class Current: 570/155
• CPC Class Codes: C07C 17/04 to unsaturated halogenated hydrocarbons
• CPC Class Codes: C07C 17/25 by splitting-off hydrogen halides from halogenated hydrocarbons
• CPC Class Codes: C07C 19/14 and bromine
• CPC Class Codes: C07C 21/18 containing fluorine

Abstract

A process for producing a fluoroolefin of the formula: CF₃CY═CX_nH_p wherein Y is a hydrogen atom or a halogen atom (i.e., fluorine, chlorine, bromine or iodine); X is a hydrogen atom or a halogen atom (i.e., fluorine, chlorine, bromine or iodine); n and p are integers independently equal to 0, 1 or 2, provided that (n+p)=2; comprising contacting, in the presence of a phase transfer catalyst, a compound of the formula: CF₃C(R¹_aR²_b) C(R³_cR⁴_d), wherein R¹, R², R³, and R⁴ are independently a hydrogen atom or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that at least one of R¹, R², R³, and R⁴ is halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms; a and b are independently=0, 1 or 2 and (a+b)=2; and c and d are independently=0, 1, 2 or 3 and (c+d)=3; and at least one alkali metal hydroxide. The alkali metal hydroxide can be, for example, potassium or sodium hydroxide and the phase transfer catalyst can be, for example, at least one: crown ether such as 18-crown-6 and 15-crown-5; or onium salt such as, quaternary phosphonium salt and quaternary ammonium salt. The olefin is useful, for example, as an intermediate for producing other industrial chemicals and as a monomer for producing oligomers and polymers.

Claims

4. Process for the preparation of fluorine-containing olefins of the formula CF₃CY═

CX_nH_p wherein Y is a hydrogen atom or a halogen atom selected from the group consisting of fluorine, chlorine, bromine or iodine;

X is a hydrogen atom or a halogen atom selected from the group consisting of fluorine, chlorine, bromine or iodine;

n and p are integers independently equal to 0, 1 or 2, provided that (n+p)=2 comprising contacting, in the presence of a phase transfer catalyst;

(A) a compound of the formula CF₃C(R¹_aR²_b)C(R³_cR⁴_d), wherein R¹, R², R³, and R⁴ are independently a hydrogen atom or a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, provided that at least one of R¹, R², R³, and R⁴ is halogen and there is at least one hydrogen and one halogen on adjacent carbon atoms;

a and b are independently=0, 1 or 2 and (a+b)=2; and

c and d are independently=0, 1, 2 or 3 and (c+d)=3; and

(B) at least one alkali metal hydroxide.

5. Process of claim 1 wherein R¹ and R² are hydrogen, R³ is F and c is 2, and R⁴ is hydrogen or chlorine.

6. Process of claim 2 wherein said phase transfer catalyst is selected from:

crown ethers;

cryptates;

polyalkylene glycols or derivatives thereof; and

onium salts.

10. Process of claim 6 wherein said onium salt is selected from the group consisting of benzyltriethylammonium chloride, methyltrioctylammonium chloride, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylphosphonium chloride, bis[tris(dimethylamino)phosphine]iminium chloride and tetratris[tris(dimethylamino)phosphinimino] phosphonium chloride.

14. Process of claim 10 wherein said alkali metal is sodium and said phase transfer catalyst is 15-crown-5 ether.

15. Process of claim 10 wherein said alkali metal is potassium and said phase transfer catalyst is 18-crown-6 ether.

16. Process of claim 10 wherein said phase transfer catalyst is benzyltriethylammonium chloride.

7. Process of claim 3 wherein said crown ether is selected from 18-crown-6 and 15-crown-5.

8. Process of claim 3 wherein said polyalkylene glycol is selected from polyethylene glycol and polypropylene glycol.

9. Process of claim 3 wherein said onium salt is selected from ammonium and phosphonium salts.

13. Process of claim 9 wherein said alkali metal is selected from lithium, sodium and potassium.

11. Process of claim 1 conducted in the presence of at least one diluent selected from the group consisting of water, alcohols, ethers, esters, alkanes and fluorinated diluents and chlorofluorocarbons.

12. Process of claim 3 wherein said alkali metal is selected from Group 1 of the Periodic Table of the Elements.

17. Process of claim 1 wherein said process is conducted at from about −

50°

C. to about 100°

C.

18. Process of claim 2 wherein the molar ratio of alkali metal hydroxide to CF₃C(R¹_aR²_b)C(R³_cR⁴_d) is from about 1 to about 10.

19. Process of claim 2 wherein the molar ratio of phase transfer catalyst to CF₃C(R¹_aR²_b)C(R³_cR⁴_d) is from about 0.001 mol % to about 10 mol %.

20. Process of claim 2 wherein R⁴ is hydrogen.

21. Process of claim 1 wherein R¹ is hydrogen and R² is bromine, R³ is F and c is 2, and R⁴ is bromine.

22. Process of claim 1 conducted in a continuous manner.