Ethylene oligomerization

• US 5,233,115 A
• Filed: 12/09/1992
• Issued: 08/03/1993
• Est. Priority Date: 12/09/1992
• Status: Expired due to Fees

• Current Assignee: Phillips Petroleum Company (ConocoPhillips)
• Original Assignee: Phillips Petroleum Company (ConocoPhillips)
• Inventors: Wu, An-hsiang
• Primary Examiner(s): Garvin, Patrick P.
• Assistant Examiner(s): WOOD, ELIZABETH D
• Application Number:
  US07/988,042
• Time in Patent Office: 237 Days
• Field of Search: 585/521, 585/525, 585/527, 585/530, 585/531
• US Class Current: 585/521
• CPC Class Codes: C07C 2/36 as phosphines, arsines, stilbines or bismuthines
• CPC Class Codes: C07C 2527/128 Compounds comprising a halogen and an iron group metal or a platinum group metal
• CPC Class Codes: C07C 2531/24 Phosphines
• CPC Class Codes: C07C 2531/30 Halides
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

An ethylene oligomerization process is provided wherein ethylene is contacted with a nickel(II) halide compound, a phosphine compound, and a carboxylate compound in a solvent to produce a precursor reaction mixture, followed by contacting ethylene with the precursor reaction mixture and a borohydride compound to produce a product reaction mixture comprising the desired oligomerization product.

Claims

1. A process for oligomerizing ethylene to an oligomerization product comprising:

(a) contacting ethylene, a nickel(II) halide compound, a phosphine compound of the formula PR₃ where each R independently represents H or a C₁ to C₂₀ hydrocarbyl radical and where at least one R is not H, and a carboxylate compound of the formula R'"'"'COOM where R'"'"' is a C₁ to C₁₀ fluorinated hydrocarbyl radical having at least one fluorine atom and M is an alkali metal, wherein the ethylene is in a gaseous phase and the nickel(II) halide compound, phosphine compound, and carboxylate compound are in a solvent and in a liquid phase, thereby producing a precursor reaction mixture in a liquid phase; and

(b) contacting, after step (a), ethylene in a gaseous phase, the precursor reaction mixture, and a borohydride compound of the formula M'"'"'BH_4-n R_n " where n=1, 2, or 3, M'"'"' is an alkali metal, and each R" independently represents a C₁ to C₂₀ hydrocarbyl radical, thereby producing a product reaction mixture in a liquid phase comprising the oligomerization product.

2. A process as recited in claim 1 wherein step (a) is carried out at a pressure of about 5 to about 5000 psig, at a temperature of about 0°

C. to about 100°

C., and for a time of about 1 minute to about 2 hours.

3. A process as recited in claim 2 wherein step (a) is carried out at a pressure of about 20 to about 1000 psig, at a temperature of about 20°

C. to about 75°

C., and for a time of about 3 minutes to about 30 minutes.

4. A process as recited in claim 1 wherein step (b) is carried out at a pressure of about 5 to about 5000 psig, at a temperature of about 25°

C. to about 125°

C., and for a time of about 1 minute to about 15 hours.

5. A process as recited in claim 4 wherein step (b) is carried out at a pressure of about 200 to about 1000 psig, at a temperature of about 50°

C. to about 100°

C., and for a time of about 15 minutes to about 5 hours.

6. A process as recited in claim 1 wherein the nickel(II) halide compound is a nickel(II) chloride compound.

7. A process as recited in claim 6 wherein the nickel(II) chloride compound is nickel(II) chloride hexahydrate.

8. A process as recited in claim 1 wherein the phosphine compound is dicyclohexylphosphine.

9. A process as recited in claim 1 wherein the carboxylate compound is potassium trifluoroacetate.

10. A process as recited in claim 1 wherein in the borohydride compound of the formula M'"'"'BH_4-n R_n ", n=3 and R" is a C₁ to C₁₂ alkyl radical.

11. A process as recited in claim 10 wherein the borohydride compound is sodium triethylborohydride.

12. A process as recited in claim 1 wherein the molar ratio of (i) the phosphine compound, (ii) the carboxylate compound, and (iii) the borohydride compound, respectively, to the nickel(II) halide compound are as follows:

(i) about 0.1-5 to 1;

(ii) about 0.1-5 to 1; and

(iii) about 1-10 to 1.

13. A process as recited in claim 1 wherein the solvent is a C₁ to C₁₂ hydroxylated hydrocarbon selected from the group consisting of an alcohol and a phenol.

14. A process as recited in claim 13 wherein the solvent is an alcohol.