Method for olefin oligomerization

Patent metadata

Field	Value
Publication number	US-10688482-B2
Application number	US-201615544236-A
Country	US
Kind code	B2
Filing date	Feb 5, 2016
Priority date	Feb 12, 2015
Publication date	Jun 23, 2020
Grant date	Jun 23, 2020

Abstract

A method for olefin oligomerization comprising i) injecting an olefin monomer and a solvent into a continuous stirred tank reactor; ii) injecting an oligomerization catalyst system comprising a ligand compound, a transition metal compound, and a co-catalyst into the continuous stirred tank reactor; and iii) performing a multimerization reaction of the olefin monomer, wherein a ratio of the flowing rates of the olefin monomer and the solvent is from 1:1 to 2:1.

First claim

The invention claimed is:

1. A method for oligomerizing ethylene, the method comprising:
i) injecting ethylene and a solvent into a continuous stirred tank reactor;
ii) injecting an oligomerization catalyst system comprising a ligand compound, an organic chromium compound, and a co-catalyst into the continuous stirred tank reactor; and
iii) oligomerizing the ethylene in the continuous stirred tank reactor to produce an oligomerization product, wherein a ratio of mass flow rates of the ethylene and the solvent is from 1.5:1 to 1.75:1, such that a weight ratio of the oligomerization product to the solvent is >1.0,
wherein the solvent is selected from the group consisting of heptane, toluene, cyclohexane, methylcyclohexane, 1-hexene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, and acetone, wherein the ligand compound comprises at least two diphosphine moieties represented by the following Formula 2:

wherein in Formula 2, A is N, As or Sb, and R1 to R4 are each independently alkylaryl having 7 to 20 carbon atoms,
wherein * is a hydrocarbyl linker connecting the at least two diphosphine moieties,
wherein a carbon number of the shortest distance between the at least two diphosphine moieties is from 2 to 30, and
wherein the linker connecting the at least two diphosphine moieties comprises a combination of at least one aliphatic group having 2 to 20 carbon atoms and at least one alicyclic group having 3 to 20 carbon atoms such that the at least one aliphatic group is directly bonded to group A of one of the at least two diphosphine moieties and the at least one alicylic group is directly bonded to group A of the other of the at least two diphosphine moieties.

2. The method for oligomerizing ethylene of claim 1 , wherein the oligomerization of ethylene in the continuous stirred tank reactor is conducted under a pressure of 30 bar to 150 bar.

3. The method for oligomerizing ethylene of claim 1 , wherein the oligomerization of ethylene in the continuous stirred tank reactor is conducted at a temperature of 30° C. to 150° C.

4. The method for oligomerizing ethylene of claim 1 , wherein a concentration of the ligand compound of the oligomerization catalyst system injected in step ii) is from 3 μM to 15 μM.

5. The method for oligomerizing ethylene of claim 1 , wherein an amount of the co-catalyst of the oligomerization catalyst system injected in step ii) is from 300 equivalents to 3,000 equivalents relative to an equivalent of chromium included in the organic chromium compound.

6. The method for oligomerizing ethylene of claim 1 , wherein the oligomerization catalyst system is produced by a method comprising:
preparing a catalyst composition by mixing the ligand compound and the organic chromium compound; and
mixing the co-catalyst and the catalyst composition and activating the resulting mixture at a temperature of −40° C. to 80° C.

7. The method for oligomerizing ethylene of claim 1 , wherein 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-heptanedioate), chromium(III) benzoyl acetonate, chromium(III) hexafluoro-2,4-pentanedionate, and chromium(III)acetate hydroxide.

8. The method for oligomerizing ethylene of claim 1 , wherein the co-catalyst is at least one selected from compounds represented by the following Formulae 4 to 6:
—[Al(R 5 )—O] c -  [Formula 4]

wherein in Formula 4, each R 5 is the same or different and is independently a halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a halogen substituted hydrocarbyl group having 1 to 20 carbon atoms, and c is an integer of at least 2;
D(R 6 ) 3   [Formula 5]

wherein in Formula 5, D is aluminum or boron, each R 6 is the same or different and is independently hydrogen or a halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a halogen substituted hydrocarbyl group having 1 to 20 carbon atoms;
[L-H] + [Q(E) 4 ] −   [Formula 6]

wherein in Formula 6, L is a neutral Lewis acid, [L-H] + is a Brønsted acid, Q is boron or aluminum with an oxidation state of +3, and each E is independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, where at least one hydrogen atom is optionally substituted with a halogen, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy functional group or a phenoxy functional group.

Assignees

• Lg Chemical Ltd

Inventors

• Hong Yoon Ki
• Lee Yong Ho
• Shin Eun Ji
• Lee Ki Soo
• Park Jin Young
• Sa Seok Pil
• Im Seul Ki

Classifications

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C07C2/36

  as phosphines, arsines, stilbines or bismuthines · CPC title

• B01J31/143 Primary

  of aluminium · CPC title

• C07C2/32

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title

• B01J2523/67

  Chromium · CPC title