IP Library › Granted Patent US 9,174,896
Granted Patent B2
US 9,174,896 · App. 13/988,111 · Granted Nov 3, 2015

Catalytical synthesis of internal fluorobutenes and internal fluoropentenes

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Quick Facts
Patent No.
US 9,174,896
App. No.
13/988,111
Granted
Nov 3, 2015
Kind
B2
Abstract

A vapor phase process is disclosed for making internal fluorobutenes. The process involves contacting a halobutane starting material selected from the group consisting of CF 2 HCHClCH 2 CCl 2 H, CF 2 HCHClCH 2 CCl 3 , CF 3 CHClCH 2 CCl 2 H, CF 3 CHClCH 2 CCl 3 , CF 3 CHClCHClCCl 2 H, CF 3 CHClCHClCCl 3 , CF 3 CCl 2 CH 2 CCl 2 H, CF 3 CCl 2 CH 2 CCl 3 , CF 3 CCl 2 CHClCCl 2 H, CF 3 CCl 2 CHClCCl 3 , CF 3 CClFCHClCCl 2 H, CF 3 CClFCHClCCl 3 , CF 3 CClFCH 2 CCl 2 H, CF 3 CClFCH 2 CCl 3 , CF 3 CClFCHFCCl 2 H, CF 3 CClFCHFCCl 3 , CF 3 CClHCHFCCl 2 H and CF 3 CClHCHFCCl 3 , with HF in a reaction zone in the presence of a chromium oxyfluoride catalyst to produce a product mixture comprising an internal fluorobutene. Another vapor phase process is disclosed for making internal fluoropentenes. The process involves contacting a halopentane starting material selected from the group consisting of CF 2 HCHXCH 2 CX 2 CX 3 , CF 3 CHXCH 2 CX 2 CX 3 , CF 3 CHXCHXCX 2 CX 3 , CF 3 CX 2 CH 2 CX 2 CX 3 , CF 3 CX 2 CHXCX 2 CX 3 and CF 3 CHXCHFCX 2 CX 3 , with HF in a reaction zone in the presence of a chromium oxyfluoride catalyst to produce a product mixture comprising an internal fluoropentene, wherein each X is independently selected from the group consisting of F, Cl and Br, provided that not all X are fluorines.

Claims (20)

1. A vapor phase process for making internal fluorobutenes comprising contacting a halobutane starting material selected from the group consisting of CF 2 HCHClCH 2 CCl 2 H, CF 2 HCHClCH 2 CCl 3 , CF 3 CHClCH 2 CCl 2 H, CF 3 CHClCH 2 CCl 3 , CF 3 CHClCHClCCl 2 H, CF 3 CHClCHClCCl 3 , CF 3 CCl 2 CH 2 CCl 2 H, CF 3 CCl 2 CH 2 CCl 3 , CF 3 CCl 2 CHClCCl 2 H, CF 3 CCl 2 CHClCCl 3 , CF 3 CClFCHClCCl 2 H, CF 3 CClFCHClCCl 3 , CF 3 CClFCH 2 CCl 2 H, CF 3 CClFCHFCCl 2 H, CF 3 CClFCHFCCl 3 , CF 3 CClHCHFCCl 2 H and CF 3 CClHCHFCCl 3 , with HF in a reaction zone in the presence of a catalyst consisting of chromium oxyfluoride to produce a product mixture comprising at least one fully fluorinated internal fluorobutene, wherein the at least one internal fluorobutene is present in the product mixture at an amount of greater than 15 mole percent.

2. The vapor phase process of claim 1 wherein said halobutane starting material is CF 2 HCHClCH 2 CCl 2 H and said at least one fully fluorinated internal fluorobutene is CF 2 HCH═CHCF 2 H.

3. The vapor phase process of claim 1 wherein said halobutane starting material is CF 3 CHClCH 2 CCl 3 and said at least one fully fluorinated internal fluorobutene is CF 3 CH═CHCF 3 .

4. The vapor phase process of claim 1 wherein said halobutane starting material is CF 3 CHClCHClCCl 2 H and said at least one fully fluorinated internal fluorobutene is CF 3 CF═CHCF 2 H, CF 3 CH═CFCF 2 H, or mixtures thereof.

5. The vapor phase process of claim 1 wherein said halobutane starting material is selected from the group consisting of CF 3 CHClCHClCCl 3 , CF 3 CCl 2 CH 2 CCl 3 , and CF 3 CClHCHFCCl 3 , and said at least one fully fluorinated internal fluorobutene is CF 3 CF═CHCF 3 .

6. The vapor phase process of claim 1 wherein said halobutane starting material is CF 3 CCl 2 CH 2 CCl 2 H, CF 3 CClFCH 2 CCl 2 H, or mixtures thereof, and said at least one fully fluorinated internal fluorobutene is CF 3 CF═CHCF 2 H.

7. The vapor phase process of claim 1 wherein said halobutane starting material is selected from the group consisting of CF 3 CCl 2 CHClCCl 2 H, CF 3 CClFCHClCCl 2 H and CF 3 CClFCHFCCl 2 H, and said at least one fully fluorinated internal fluorobutene is CF 3 CF═CFCF 2 H.

8. The vapor phase process of claim 1 wherein said halobutane starting material is selected from the group consisting of CF 3 CCl 2 CHClCCl 3 , CF 3 CClFCHClCCl 3 , CF 3 CClFCHFCCl 3 , and said at least one fully fluorinated internal fluorobutene is CF 3 CF═CFCF 3 .

9. The vapor phase process of claim 1 wherein said halobutane starting material is CF 3 CClHCHFCCl 2 H and said at least one fully fluorinated internal fluorobutene is CF 3 CH═CFCF 2 H.

10. A vapor phase process for making internal fluoropentenes comprising contacting a halopentane starting material selected from the group consisting of CF 2 HCHXCH 2 CX 2 CX 3 , CF 3 CHXCH 2 CX 2 CX 3 , CF 3 CHXCHXCX 2 CX 3 , CF 3 CX 2 CH 2 CX 2 CX 3 , CF 3 CX 2 CHXCX 2 CX 3 and CF 3 CHXCHFCX 2 CX 3 , with HF in a reaction zone in the presence of a catalyst consisting of chromium oxyfluoride to produce a product mixture comprising at least one fully fluorinated internal fluoropentene, wherein each X is independently selected from the group consisting of F, Cl and Br, provided that not all X are fluorines, and wherein the at least one fully fluorinated internal fluorobutene is present in the product mixture at an amount of greater than 15 mole percent.

11. The vapor phase process of claim 10 wherein said halopentane starting material is CF 2 HCHXCH 2 CX 2 CX 3 and said at least one fully fluorinated internal fluoropentene is CF 2 HCH═CHCF 2 CF 3 .

12. The vapor phase process of claim 11 wherein said halopentane starting material is selected from the group consisting of CF 2 HCHClCH 2 CCl 2 CCl 3 , CF 2 HCHClCH 2 CClFCCl 3 , CF 2 HCHClCH 2 CCl 2 CF 3 , CF 2 HCHClCH 2 CClFCF 3 , CF 2 HCHClCH 2 CCl 2 CClF 2 , CF 2 HCHBrCH 2 CCl 2 CCl 3 , CF 2 HCHBrCH 2 CClFCCl 3 , CF 2 HCHBrCH 2 CClBrCF 3 , CF 2 HCHBrCH 2 CBr 2 CF 3 , CF 2 HCHBrCH 2 CBr 2 CCl 3 and CF 2 HCHBrCH 2 CCl 2 CClF 2 .

13. The vapor phase process of claim 10 wherein said halopentane starting material is CF 3 CHXCH 2 CX 2 CX 3 and said at least one fully fluorinated internal fluoropentene is CF 3 CH═CHCF 2 CF 3 .

14. The vapor phase process of claim 13 wherein said halopentane starting material is selected from the group consisting of CF 3 CHClCH 2 CCl 2 CCl 3 , CF 3 CHClCH 2 CClFCCl 3 , CF 3 CHClCH 2 CCl 2 CF 3 , CF 3 CHClCH 2 CClFCF 3 , CF 3 CHClCH 2 CCl 2 CClF 2 , CF 3 CHBrCH 2 CCl 2 CCl 3 , CF 3 CHBrCH 2 CClFCCl 3 , CF 3 CHBrCH 2 CClBrCF 3 , CF 3 CHBrCH 2 CBr 2 CF 3 , CF 3 CHBrCH 2 CBr 2 CCl 3 and CF 3 CHBrCH 2 CCl 2 CClF 2 .

15. The vapor phase process of claim 10 wherein said halopentane starting material is CF 3 CHXCHXCX 2 CX 3 and said at least one fully fluorinated internal fluoropentene is CF 3 CH═CFCF 2 CF 3 , CF 3 CF═CHCF 2 CF 3 , or mixtures thereof.

16. The vapor phase process of claim 15 wherein said halopentane starting material is selected from the group consisting of CF 3 CHClCHClCCl 2 CCl 3 , CF 3 CHClCHClCClFCCl 3 , CF 3 CHClCHClCCl 2 CF 3 , CF 3 CHClCHClCClFCF 3 , CF 3 CHClCHClCCl 2 CClF 2 , CF 3 CHBrCHClCCl 2 CCl 3 , CF 3 CHBrCHClCClFCCl 3 , CF 3 CHBrCHClCClBrCF 3 , CF 3 CHBrCHClCBr 2 CF 3 , CF 3 CHBrCHClCBr 2 CCl 3 and CF 3 CHBrCHClCCl2CClF 2 .

17. The vapor phase process of claim 10 wherein said halopentane starting material is CF 3 CX 2 CH 2 CX 2 CX 3 and said at least one fully fluorinated internal fluoropentene is CF 3 CF═CHCF 2 CF 3 .

18. The vapor phase process of claim 17 wherein said halopentane starting material is selected from the group consisting of CF 3 CCl 2 CH 2 CCl 2 CCl 3 , CF 3 CCl 2 CH 2 CClFCCl 3 , CF 3 CCl 2 CH 2 CCl 2 CF 3 , CF 3 CCl 2 CH 2 CClFCF 3 , CF 3 CCl 2 CH 2 CCl 2 CClF 2 , CF 3 CCl 2 CH 2 CCl 2 CCl 3 , CF 3 CClBrCH 2 CClFCCl 3 , CF 3 CClBrCH 2 CClBrCF 3 , CF 3 CClBrCH 2 CBr 2 CF 3 , CF 3 CClBrCH 2 CBr 2 CCl 3 , CF 3 CClBrCH 2 CCl 2 CClF 2 , CF 3 CFClCH 2 CCl 2 CCl 3 , CF 3 CFClCH 2 CClFCCl 3 , CF 3 CFClCH 2 CCl 2 CF 3 , CF 3 CFClCH 2 CClFCF 3 , CF 3 CFClCH 2 CCl 2 CClF 2 , CF 3 CFBrCH 2 CCl 2 CCl 3 , CF 3 CFBrCH 2 CClFCCl 3 , CF 3 CFBrCH 2 CClBrCF 3 , CF 3 CFBrCH 2 CBr 2 CF 3 , CF 3 CFBrCH 2 CBr 2 CCl 3 and CF 3 CFBrCH 2 CCl 2 CClF 2 .

19. The vapor phase process of claim 10 wherein said halopentane starting material is CF 3 CX 2 CHXCX 2 CX 3 and said at least one fully fluorinated internal fluoropentene is CF 3 CF═CFCF 2 CF 3 .

20. The vapor phase process of claim 10 wherein said halopentane starting material is CF 3 CHXCHFCX 2 CX 3 and said at least one fully fluorinated internal fluoropentene is CF 3 CH═CFCF 2 CF 3 .

Assignments (5)
SECURITY INTEREST Recorded Apr 4, 2018
From: THE CHEMOURS COMPANY FC, LLC
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 045846/0011 →
RELEASE OF SECURITY INTEREST Recorded Apr 4, 2018
From: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
To: THE CHEMOURS COMPANY FC, LLC
Reel/Frame 045845/0913 →
SECURITY AGREEMENT Recorded Jun 10, 2015
From: THE CHEMOURS COMPANY FC LLC; THE CHEMOURS COMPANY TT, LLC
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 035839/0675 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 15, 2015
From: E. I. DU PONT DE NEMOURS AND COMPANY
To: THE CHEMOURS COMPANY FC, LLC
Reel/Frame 035432/0023 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 28, 2014
From: NAPPA, MARIO JOSEPH; SWEARINGEN, EKATERINA N
To: E. I. DU PONT DE NEMOURS AND COMPANY
Reel/Frame 032058/0289 →