Process for the production of fluorinated cyclobutane

Patent metadata

Field	Value
Publication number	US-9856193-B2
Application number	US-201715582981-A
Country	US
Kind code	B2
Filing date	May 1, 2017
Priority date	Nov 12, 2015
Publication date	Jan 2, 2018
Grant date	Jan 2, 2018

Abstract

The production of 1,1,2-trifluoro-2-(trifluoromethyl)cyclobutane (TFMCB). More specifically, the present invention relates to a process for making 1,1,2-trifluoro-2-(trifluoromethyl)cyclobutane via a continuous catalytic reaction from commercially available raw materials ethylene and hexafluoropropene.

First claim

The invention claimed is:

1. A continuous process for producing 1,1,2-trifluoro-2-(trifluoromethyl)cyclobutane (TFMCB), comprising the following steps:
(a) introducing hexafluoropropene and ethylene into a reaction vessel;
(b) reacting the hexafluoropropene and ethylene in the reaction vessel in the presence of at least one metal catalyst;
(c) removing TFMCB product from the reaction vessel;
(d) repeating said introducing, reacting and removing steps (a) through (c); and
wherein the metal catalyst includes at least one metal catalyst selected from the group consisting of nickel and nickel-based alloys.

2. The process of claim 1 , further comprising the additional steps of:
removing at least one of unreacted hexafluoropropene and unreacted ethylene from the reaction vessel; and
recycling the at least one of unreacted hexafluoropropene and unreacted ethylene back into the reaction vessel.

3. The process of claim 1 , further comprising the additional steps of:
removing unreacted hexafluoropropene and unreacted ethylene from the reaction vessel; and
recycling the unreacted hexafluoropropene and unreacted ethylene back into the reaction vessel.

4. The process of claim 1 , wherein said reacting step is conducted at a pressure between 600 psig and 1500 psig.

5. The process of claim 4 , wherein said reacting step is conducted at a pressure between 800 psig and 1200 psig.

6. The process of claim 1 , wherein said reacting step is conducted at a temperature between 300° C. and 500° C.

7. The process of claim 6 , wherein said reacting step is conducted at a temperature between 300° C. and 400° C.

8. The process of claim 1 , wherein during said reacting step, the hexafluoropropene and ethylene are present at a molar ratio of from 1:1 to 1:6.

9. The process of claim 8 , wherein during said reacting step, the hexafluoropropene and ethylene are present at a molar ratio of from 1:1 to 1:3.

10. A continuous process for producing 1,1,2-trifluoro-2-(trifluoromethyl)cyclobutane (TFMCB), comprising the following steps:
(a) introducing hexafluoropropene and ethylene into a reaction vessel;
(b) reacting the hexafluoropropene and ethylene in the reaction vessel in the presence of at least one metal catalyst;
(c) removing TFMCB product from the reaction vessel;
(d) repeating said introducing, reacting and removing steps (a) through (c); and
wherein said reacting step is carried out in the presence of at least one oligomerization/polymerization (OP) inhibitor selected from the group consisting of catechol and catechol derivatives, terpenes, quinones and combinations thereof.

11. The process of claim 10 , wherein the oligomerization/polymerization (OP) inhibitor is present at from about 50 ppm to about 2,000 ppm by weight based on the total weight of the reaction composition in the reaction vessel.

12. The process of claim 11 , wherein the oligomerization/polymerization (OP) inhibitor is present at from about 500 ppm to about 1,000 ppm based on the total weight of the reaction composition in the reaction vessel.

13. A continuous process for producing 1,1,2-trifluoro-2-(trifluoromethyl)cyclobutane (TFMCB), comprising the following steps:
(a) introducing hexafluoropropene and ethylene into a reaction vessel;
(b) reacting the hexafluoropropene and ethylene in the reaction vessel in the presence of at least one metal catalyst and at least one oligomerization/polymerization (OP) inhibitor;
(c) removing TFMCB product from the reaction vessel; and
(d) repeating said introducing, reacting and removing steps (a) through (c).

14. The process of claim 13 , wherein the at least one metal catalyst includes at least one metal catalyst selected from the group consisting of nickel and nickel-based alloys.

15. The process of claim 13 , wherein said reacting step is carried out in the presence of at least one oligomerization/polymerization (OP) inhibitor selected from the group consisting of catechol and catechol derivatives, terpenes, quinones and combinations thereof.

16. The process of claim 13 , wherein the oligomerization/polymerization (OP) inhibitor is gas phase nitric oxide (NO).

17. The process of claim 13 , wherein the oligomerization/polymerization (OP) inhibitor is present at from about 50 ppm to about 2,000 ppm by weight based on the total weight of the reaction composition in the reaction vessel.

18. The process of claim 13 , wherein at least one of the following conditions is present during said reacting step:
said reacting step is conducted at a pressure between 600 psig and 1500 psig;
said reacting step is conducted at a temperature between 300° C. and 500° C.; and
during said reacting step, the hexafluoropropene and ethylene are present at a molar ratio of from 1:1 to 1:6.

19. A continuous process for producing 1,1,2-trifluoro-2-(trifluoromethyl) cyclobutane (TFMCB), comprising the following steps:
(a) introducing hexafluoropropene and ethylene into a reaction vessel;
(b) reacting the hexafluoropropene and ethylene in the reaction vessel in the presence of at least one oligomerization/polymerization (OP) inhibitor;
(c) removing TFMCB product from the reaction vessel; and
(d) repeating said introducing, reacting and removing steps (a) through (c).

20. The process of claim 19 , wherein the oligomerization/polymerization (OP) inhibitor is gas phase nitric oxide (NO).

21. The process of claim 19 , wherein the oligomerization/polymerization (OP) inhibitor is present at from about 50 ppm to about 2,000 ppm by weight based on the total weight of the reaction composition in the reaction vessel.

22. The process of claim 21 , wherein the oligomerization/polymerization (OP) inhibitor is present at from about 500 ppm to about 1,000 ppm based on the total weight of the reaction composition in the reaction vessel.

23. The process of claim 19 , further comprising the additional steps of:
removing at least one of unreacted hexafluoropropene and unreacted ethylene from the reaction vessel; and
recycling the at least one of unreacted hexafluoropropene and unreacted ethylene back into the reaction vessel.

24. The process of claim 19 , further comprising the additional steps of:
removing unreacted hexafluoropropene and unreacted ethylene from the reaction vessel; and
recycling the unreacted hexafluoropropene and unreacted ethylene back into the reaction vessel.

25. The process of claim 19 , wherein said reacting step is conducted at a pressure between 600 psig and 1500 psig.

26. The process of claim 25 , wherein said reacting step is conducted at a pressure between 800 psig and 1200 psig.

27. The process of claim 19 , wherein said reacting step is conducted at a temperature between 300° C. and 500° C.

28. The process of claim 27 , wherein said reacting step is conducted at a temperature between 300° C. and 400° C.

29. The process of claim 19 , wherein during said reacting step, the hexafluoropropene and ethylene are present at a molar ratio of from 1:1 to 1:6.

30. The process of claim 29 , wherein during said reacting step, the hexafluoropropene and ethylene are present at a molar ratio of from 1:1 to 1:3.

Assignees

• Honeywell Int Inc

Inventors

• Nair Haridasan K
• Banavali Rajiv
• Zhai Yian
• Matthies Glenn

Classifications

• C07C17/275 Primary

  of hydrocarbons and halogenated hydrocarbons · CPC title

• C07C2601/04

  with a four-membered ring · CPC title