Carbonyl-containing perfluorohydrocarbyl-N2-phosphinyl amidine compounds, chromium salt complexes and their use to oligomerize ethylene

Patent metadata

Field	Value
Publication number	US-10294171-B2
Application number	US-201715712295-A
Country	US
Kind code	B2
Filing date	Sep 22, 2017
Priority date	Sep 22, 2017
Publication date	May 21, 2019
Grant date	May 21, 2019

Abstract

A composition comprising a perfluoro-N 2 -phosphinylamidine chromium salt complex having Structure PFAHNPACr I:

wherein R f1 is a substituted phenyl group comprising alkyl groups at the 2 and 6 positions and at least one fluoro group or perfluoroalkyl group at the 3, 4, and/or 5 positions, R 2 is a C 1 to C 30 organyl group, R 4 and R 5 are each independently a C 1 to C 30 organyl group, and CrX p is a chromium salt where X is a monoanion, and p is an integer from 2 to 6.

First claim

What is claimed is:

1. A composition comprising a perfluoro-N 2 -phosphinylamidine chromium salt complex having Structure PFAHNPACr I:

wherein
Rf 1 is a substituted phenyl group comprising alkyl groups at the 2 and 6 positions and at least one fluoro group or perfluoroalkyl group at the 3, 4, and/or 5 positions,
R 2 is a C 1 to C 30 organyl group,
R 4 and R 5 are each independently a C 1 to C 30 organyl group, and
CrX p is a chromium salt where X is a monoanion, and p is an integer from 2 to 6.

2. The composition of claim 1 , wherein Rf 1 is a 2,6-dimethyl-4-trifluoromethylphenyl group or a 2,6-dimethyl-3,4,5-trifluorophenyl group.

3. The composition of claim 1 , wherein R 2 is a C 1 to C 15 alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group.

4. The composition of claim 1 , wherein R 2 is a 4-alkylphenyl group.

5. The composition of claim 1 , wherein R 4 and R 5 are each independently a C 1 to C 5 alkyl group, a C 4 to C 10 cycloalkyl group, a phenyl group, or a C 6 to C 10 aryl group.

6. The composition of claim 1 , wherein the chromium salt is a chromium(III) carboxylate, a chromium(III) β-diketonate, or a chromium(III) halide.

7. The composition of claim 1 , wherein the chromium salt is chromium (III) chloride or chromium(III) acetylacetonate.

8. The composition of claim 1 , wherein the composition further comprises an organoaluminum compound.

9. The composition of claim 8 , wherein the organoaluminum compound comprises an aluminoxane.

10. The composition of claim 9 , wherein the aluminoxane comprises methylaluminoxane (MAO), a modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-bulylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

11. The composition of claim 1 , wherein the perfluoro-N 2 -phosphinylamidine chromium salt complex has Structure PFAHNPA 1, Structure PFAHNPA 2, or Structure PFAHNPA 3

12. A process comprising:
a) contacting
i) ethylene; and
ii) a perfluoro-N 2 -phosphinylamidine chromium salt complex having Structure PFAHNPACr I:

wherein
Rf 1 is a substituted phenyl group comprising alkyl groups at the 2 and 6 positions and at least one fluoro group or perfluoroalkyl group at the 3, 4, and/or 5 positions,
R 2 is a C 1 to C 30 organyl group,
R 4 and R 5 are each independently a C 1 to C 30 organyl group, and
CrX p is a chromium salt where X is a monoanion, and p is an integer from 2 to 6, and

b) forming an oligomer product in a reaction zone.

13. The process of claim 12 , wherein Rf 1 is a 2,6-dimethyl-4-trifluoromethylphenyl group or a 2,6-dimethyl-3,4,5-trifluorophenyl group.

14. The process of claim 12 , wherein R 2 is a C 1 to C 15 alkyl group, a C 4 to C 20 cycloalkyl group, a C 4 to C 20 substituted cycloalkyl group, a C 6 to C 20 aryl group, a C 6 to C 20 substituted aryl group, a C 7 to C 20 aralkyl group, or a C 7 to C 20 substituted aralkyl group.

15. The process of claim 12 , wherein R 2 is a 4-alkylphenyl group.

16. The process of claim 12 , wherein R 4 and R 5 are each independently a C 1 to C 5 alkyl group, a C 4 to C 10 cycloalkyl group, a phenyl group, or a C 6 to C 10 aryl group.

17. The process of claim 12 , wherein the chromium salt is a chromium(III) carboxylate, a chromium(III) β-diketonate, or a chromium(III) halide.

18. The process of claim 12 , wherein the chromium salt is chromium (III) chloride or chromium(III) acetylacetonate.

19. The process of claim 12 , wherein the process further comprises contacting the perfluoro-N 2 -phosphinylamidine chromium salt complex with an organoaluminum compound.

20. The process of claim 19 , wherein the organoaluminum compound is an aluminoxane.

21. The process of claim 20 , wherein the aluminoxane comprises methylaluminoxane (MAO), a modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

22. The process of claim 12 , wherein the perfluoro-N 2 -phosphinylamidine chromium salt complex has Structure PFAHNPA 1, Structure PFAHNPA 2, or Structure PFAHNPA 3

23. The process of claim 12 , wherein the oligomer product comprises a C 6 oligomer product having a 1-hexene content of at least 90 wt. %.

24. The process of claim 12 , wherein the oligomer product comprises a C 8 oligomer product having a 1-octene content of at least 95 wt. %.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Bischof Steven M
• Kilgore Uriah J
• Sydora Orson L
• Ess DANIEL H
• Fuller Iii Jack T
• Kwon Doo-Hyun

Classifications

• C07C2/34 Primary

  Metal-hydrocarbon complexes · CPC title

• C08F10/02

  Ethene · CPC title

• C07F11/00

  Compounds containing elements of Groups 6 or 16 of the Periodic Table · CPC title

• C07F9/65318

  having the two nitrogen atoms in positions 1 and 3 · CPC title

• C08K5/0091

  Complexes with metal-heteroatom-bonds · CPC title