# US 10,870,104 B2 · Method for preparing oligomerization catalyst system and oligomerization catalyst system prepared thereby

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- Number: US 10,870,104 B2
- Document ID: US10870104B2
- Status: Granted
- Kind: B2
- Application number: 15/528,576
- Filed: 2016-02-02
- Published: 2018-11-29
- Granted: 2020-12-22
- Earliest claimed: 2015-02-12
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Seul Ki Im; Yong Ho Lee; Eun Ji Shin; Jin Young Park; Seok Pil Sa; Ki Soo Lee
- Web page: https://patentgrep.com/patent/US10870104B2

## CPC

- B01J 31/2409: {with more than one complexing phosphine-P atom}
- B01J 31/0267: {Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen}
- B01J 31/04: containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)}
- B01J 31/143: {of aluminium}
- B01J 31/187: {Amide derivatives thereof}
- B01J 31/188: {Amide derivatives thereof}
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- C07C 2/24: with metals
- C07C 2/32: as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)}
- C07F 9/5022: {Aromatic phosphines (P-C aromatic linkage)}
- C07F 9/505: {Preparation; Separation; Purification; Stabilisation}
- C08F 2/40: using retarding agents
- C08F 4/69: Chromium, molybdenum, tungsten or compounds thereof
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 10/02: Ethene
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08K 5/00: Use of organic ingredients
- C08K 5/05: Alcohols; Metal alcoholates
- C08K 5/17: Amines; Quaternary ammonium compounds
- B01J 2231/12: Olefin polymerisation or copolymerisation
- B01J 2231/20: Olefin oligomerisation or telomerisation
- B01J 2523/67: Chromium
- B01J 2531/004: Ligands
- B01J 2531/31: Aluminium
- B01J 2531/62: Chromium
- C07C 2523/26: Chromium
- C07C 2531/04: containing carboxylic acids or their salts
- C07C 2531/14: of aluminium or boron
- C07C 2531/18: containing nitrogen, phosphorus, arsenic or antimony
- C07C 2531/22: Organic complexes
- C07C 2531/24: Phosphines
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The present invention relates to a method for preparing an oligomerization catalyst system and the method comprises preparing a catalyst composition by mixing a PNP-based ligand compound and a transition metal compound, and mixing and activating a co-catalyst and the catalyst composition at a temperature from −40 to 80° C. The oligomerization catalyst system prepared by the method may maintain the activity thereof during an oligomerization reaction at a high temperature, and the reaction temperature of oligomerization may be easily controlled. Various merits in processing may be obtained.

## Claims

### Claim 1

A method for preparing an oligomerization catalyst system, the method comprising:
preparing a catalyst composition by mixing a ligand compound comprising a diphosphine moiety of the following Formula 3, and an organic chromium compound; and
activating by mixing a co-catalyst and the catalyst composition for two or more minutes and less than five minutes at a temperature from 20 to 80° C.:
wherein in Formula 3:
R1 to R4 are each independently a C6 aryl or C7 alkylaryl group;
R5 is a methyl group;
R6 is a linear C2-C3 alkyl group or a linear C2-C3 alkenyl group; and
R7 to R9 are hydrogen.

### Claim 2 (depends on 1)

The method for preparing an oligomerization catalyst system of claim 1, wherein an activating time of the co-catalyst and the catalyst composition is from two minutes or more to three minutes or less.

### Claim 3 (depends on 1)

The method for preparing an oligomerization catalyst system of claim 1, wherein an activating temperature is from 20 to 80° C.

### Claim 4 (depends on 1)

The method for preparing an oligomerization catalyst system of claim 1, wherein R7 to R9 of Formula 3 are hydrogen.

### Claim 5 (depends on 1)

The method for preparing an oligomerization catalyst system of claim 1, wherein the transition metal compound comprises an organic chromium compound, and the organic chromium compound comprises at least one selected from the group consisting of chromium(III) acetyl acetonate, trichlorochromium tris tetrahydrofuran, chromium(III)-2-ethylhexanoate, chromium(III) tris (2,2,6,6-tetramethyl-3,5-heptanedionate), chromium(III) benzoyl acetonate, chromium(III) hexafluoro-2,4-pentanedionate and chromium(III) acetate hydroxide.

### Claim 6 (depends on 1)

The method for preparing an oligomerization catalyst system of claim 1, wherein the co-catalyst is at least one selected from the compounds of the following Formulae 4 to 6:
−[Al(R5)−O]c— [Formula 4]
wherein in the above Formula 4, R5 is the same or different and is independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a halogen substituted hydrocarbyl radical having 1 to 20 carbon atoms, and c is an integer of at least 2;
D(R6)3 [Formula 5]
wherein in the above Formula 5, D is aluminum or boron, each R6 is the same or different and is independently hydrogen, halogen, hydrocarbyl having 1 to 20 carbon atoms, or halogen substituted hydrocarbyl having 1 to 20 carbon atoms;
[L-H]+[Q(E)4]− [Formula 6]
wherein in the above Formula 6, L is a neutral Lewis base, [L-H]+ is a brönsted acid, Q is boron or aluminum with an oxidation state of +3, and each E is independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms, where at least one hydrogen atom is substituted with halogen, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy functional group or a phenoxy functional group or is unsubstituted.

### Claim 7 (depends on 1)

A method for oligomerizing olefin, the method comprising:
performing a oligomerization reaction of olefin in a reaction temperature range of 30 to 150° C. in the presence of the oligomerization catalyst system prepared by the preparation method according to claim 1.

### Claim 8 (depends on 7)

The method for oligomerizing olefin of claim 7, wherein the reaction temperature is in a range of 60 to 130° C.

### Claim 9 (depends on 7)

The method for oligomerizing olefin of claim 7, wherein an activity of the catalyst system in a whole reaction temperature range is 100,000 kg/molCr/hr or more in a batch type process, and 100,000 kg/molCr or more in a continuous type process.

### Claim 10 (depends on 7)

The method for oligomerizing olefin of claim 7, wherein an activity decreasing ratio of the catalyst system according to temperature increase is less than 6% in a whole reaction temperature range.

### Claim 11 (depends on 7)

The method for oligomerizing olefin of claim 7, wherein selectivity of 1-hexene and 1-octene relative to a total amount of a product is 80 wt % or more in a whole reaction temperature range.