Oligomerization Catalyst and Method for Preparing Ethylene Oligomer Using Same

• US 20190308178A1
• Filed: 05/11/2017
• Published: 10/10/2019
• Est. Priority Date: 05/27/2016
• Status: Active Grant

• Current Assignee: SK Geo Centric Company Limited
• Original Assignee: SK Global Chemical Co., Ltd. (SK Innovation Company Limited), SK Innovation Company Limited
• Inventors: Lee, Sang Ick, Baek, Eun Jung, Kim, Sun Young, Park, Hyo Seung, Jung, Min Seon
• Granted Patent: US 11,235,315 B2
• Time in Patent Office: Days
• CPC Class Codes: B01J 2231/20 Olefin oligomerisation or telomerisation
• CPC Class Codes: B01J 2531/0205 Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
• CPC Class Codes: B01J 2531/62 Chromium
• CPC Class Codes: B01J 2540/225 comprising perfluoroalkyl groups or moieties
• CPC Class Codes: B01J 31/143 of aluminium
• CPC Class Codes: B01J 31/181 Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
• CPC Class Codes: B01J 31/223 At least two oxygen atoms present in one at least bidentate or bridging ligand
• CPC Class Codes: B01J 31/2234 Beta-dicarbonyl ligands, e.g. acetylacetonates
• CPC Class Codes: B01J 31/2409 with more than one complexing phosphine-P atom
• CPC Class Codes: B01J 31/2495 Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 2/32 as complexes, e.g. acetyl-acetonates complexes of salts of acids of halogen C07C2/20
• CPC Class Codes: C07C 2/36 as phosphines, arsines, stilbines or bismuthines
• CPC Class Codes: C07C 2531/24 Phosphines
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 10/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: C08F 4/12 of boron, aluminium, gallium, indium, thallium or rare earths
• CPC Class Codes: C08F 4/69 Chromium, molybdenum, tungsten or compounds thereof

Abstract

The present invention relates to an oligomerization catalyst a transition metal or transition metal precursor, a halogen-substituted organic ligand, and a heteroatom ligand, and to a method for selectively preparing 1-hexene or 1-octene from ethylene using the catalyst.

Claims

1. An oligomerization catalyst comprising:

a transition metal or transition metal precursor,

a halogen-substituted organic ligand, and

a heteroatom ligand.

2. The oligomerization catalyst of claim 1, wherein the halogen-substituted organic ligand is a monovalent anionic bidentate organic ligand.

3. The oligomerization catalyst of claim 2, wherein the halogen-substituted organic ligand is a ligand that coordinates to a transition metal through a non-bonding electron pair of a carbon atom or a heteroatom selected from nitrogen, oxygen and sulfur.

4. The oligomerization catalyst of claim 3, wherein the halogen-substituted organic ligand is selected from the following structures:

5. The oligomerization catalyst of claim 4, wherein the halogen-substituted organic ligand is an enolate-based ligand represented by Chemical Formula 1 below:

6. The oligomerization catalyst of claim 5, wherein at least one of R⁶ to R⁸ is fluorine-substituted hydrocarbyl or fluorine-substituted heterohydrocarbyl.

7. The oligomerization catalyst of claim 1, wherein the heteroatom ligand is represented by General Formula (R)_nA-B—

C(R)_m, wherein A and C are independently selected from the group consisting of phosphorus, arsenic, antimony, oxygen, bismuth, sulfur, selenium, and nitrogen, B is a linking group between A and C, R is the same as or different from each other and is each independently selected from the group consisting of hydrocarbyl, heterohydrocarbyl, substituted hydrocarbyl and substituted heterohydrocarbyl groups, and n and m are each determined as a valence and an oxidation state of A or C.

8. The oligomerization catalyst of claim 7, wherein B is selected from the group consisting of an organic linking group including hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, and substituted heterohydrocarbyl;

an inorganic linking group including a single atom link;

an ion link; and

methylene, dimethylmethylene, 1,2-ethylene, 1,2-phenylene, 1,2-propylene, 1,2-catechol, 2,3-butylene, 1,2-dimethyl hydrazine, —

B(R′

)—

, —

Si(R′

)₂—

, —

P(R′

)—

, and —

N(R′

)—

, and R′

is hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, substituted heterohydrocarbyl, substituted heteroatom or halogen.

9. The oligomerization catalyst of claim 7, wherein the heteroatom ligand is a ligand having a P—

C—

C—

P skeleton structure represented by Chemical Formula 2 below, a ligand having a P—

N—

P skeleton structure represented by Chemical Formula 3 below, or a ligand having a P—

C═

C—

P skeleton structure represented by Chemical Formula 4 below;

10. The oligomerization catalyst of claim 1, wherein the oligomerization catalyst is mononuclear or binuclear.

11. The oligomerization catalyst of claim 1, wherein the transition metal or transition metal precursor is a Group 4, Group 5 or Group 6 transition metal, or a precursor thereof.

12. The oligomerization catalyst of claim 11, wherein the transition metal or transition metal precursor is chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium or a precursor thereof.

13. The oligomerization catalyst of claim 12, wherein the transition metal or transition metal precursor is a chromium or chromium precursor.

14. The oligomerization catalyst of claim 13, wherein the chromium precursor is selected from the group consisting of chromium (III) acetylacetonate, chromium (III) chloride tris-tetrahydrofuran, and chromium (III) 2-ethylhexanoate.

15. The oligomerization catalyst of claim 1, wherein the oligomerization catalyst is a complex in which a chromium or chromium precursor coordinates with an enolate-based ligand represented by Chemical Formula 1 below, and a ligand having a P—

C—

C—

P skeleton structure represented by Chemical Formula 2 below, a ligand having a P—

N—

P skeleton structure represented by Chemical Formula 3 below, or a ligand having a P—

C═

C—

P skeleton structure represented by Chemical Formula 4 below;

16. A method for preparing an ethylene oligomer using a catalyst composition including the oligomerization catalyst of claim 1 and a cocatalyst.

17. The method of claim 16, wherein the cocatalyst is an organoaluminum compound, an organoboron compound, an organic salt, or a mixture thereof.

18. The method of claim 17, wherein the cocatalyst is one or a mixture of two or more selected from the group consisting of methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane (EAO), tetraisobutyl aluminoxane (TIBAO), isobutyl aluminoxane (IBAO), trimethyl aluminum (TMA), triethyl aluminum (TEA), triisobutyl aluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethylaluminum sesquichloride, and methylaluminum sesquichloride.

19. The method of claim 16, wherein an aliphatic hydrocarbon is used as a reaction solvent.

20. The method of claim 19, wherein the aliphatic hydrocarbon is at least one selected from hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2-methylhexane, 3-methylhexane, 2,2-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethylhexane, 2-methylheptane, 4-methylheptane, cyclohexane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, 1,4-dimethylcyclohexane, and 1,2,4-trimethylcyclohexane.

21. The method of claim 16, wherein the ethylene oligomer includes 1-octene in an amount of 30 wt % or more.

22. The method of claim 21, wherein the ethylene oligomer includes 1-octene in an amount of 50 wt % or more.