Method of olefin oligomerization

Patent metadata

Field	Value
Publication number	US-11021418-B2
Application number	US-201816649900-A
Country	US
Kind code	B2
Filing date	Jul 18, 2018
Priority date	Sep 29, 2017
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

The present invention relates to a method for olefin oligomerization, and can provide a method for olefin oligomerization. The method includes the steps of: introducing an oligomerization transition metal catalyst, olefin monomers, and a solvent into a reactor and performing an olefin oligomerization reaction to produce an oligomer; introducing a catalyst deactivator to a reaction product of the oligomerization reaction to deactivate the catalyst, with the catalyst deactivator including at least one functional group containing at least one selected from the group including oxygen, phosphor, nitrogen, and sulfur and having a number average molecular weight of 400 or more; separating the oligomer through distillation in a distiller; and separating the catalyst deactivator through the bottom end of the distiller.

First claim

The invention claimed is:

1. A method for oligomerizing olefins, the method comprising:
introducing an oligomerization transition metal catalyst, an olefin monomer, and a solvent into a reactor and performing an olefin oligomerization reaction to produce oligomers;
introducing a catalyst deactivator to a reaction product of the oligomerization reaction to deactivate the catalyst, wherein the catalyst deactivator includes one or more functional groups containing at least one selected from the group consisting of oxygen, phosphor, nitrogen, and sulfur, and has a number average molecular weight of 400 or more;
separating the oligomers by distillation in a distiller; and
separating the catalyst deactivator through the bottom end of the distiller,
wherein the catalyst deactivator is a phosphine-based compound, an amine-based compound, a thiol-based compound, an ether-based compound, an ester-based compound, carboxylic acid, or a ketone-based compound,
wherein the transition metal catalyst is represented by ML 1 (L 2 ) p (X) q or M 2 X 1 2 L 1 2 (L 2 ) y (X) z , wherein M is a transition metal, L 1 is a heteroligand, L 2 is an organic ligand, X and X 1 are each independently a halogen, p is an integer of 0 or 1 or more, q is an integer of (oxidation number of M−p), y is an integer of 2 or more, and z is an integer of (2× oxidation number of M) −y,
wherein the heteroligand L 1 has a P—C—C—P backbone structure represented by the following Formula 3, or a P—N—P backbone structure represented by the following Formula 4,

wherein R 51 to R 54 are each independently a hydrocarbyl, a substituted hydrocarbyl, a heterohydrocarbyl, or a substituted heterohydrocarbyl, and
wherein R 55 and R 56 are each independently a hydrocarbyl or a substituted hydrocarbyl, or R 55 and R 56 may be taken together via hydrocarbylene, substituted hydrocarbylene, heterohydrocarbylene, or substituted heterohydrocarbylene to form a ring.

2. The method of claim 1 , wherein the number average molecular weight of the catalyst deactivator is greater than or equal to 600.

3. The method of claim 1 , wherein the catalyst deactivator has 31 or more carbon atoms based on the number average molecular weight thereof.

4. The method of claim 1 , wherein the catalyst deactivator is represented by the following Formula 1:

(wherein n ranges from 11 to 170).

5. The method of claim 1 , wherein 1-octene is included at 30% by weight or more, based on 100% by weight of linear alpha olefins in the reaction product of the oligomerization reaction.

6. The method of claim 1 , wherein the cocatalyst is further introduced when the oligomerization transition metal catalyst, the olefin monomer, and the solvent are introduced into the reactor to perform the olefin oligomerization reaction, and the cocatalyst is an aluminum compound, an organoaluminoxane, an organoboron compound, or a mixture thereof.

7. The method of claim 6 , wherein an amount of the introduced catalyst deactivator is in a range of 1.5 to 20 times higher than the total number of moles of aluminum, boron, or a combination thereof in the cocatalyst based on the number of moles.

8. The method of claim 1 , wherein, in the separating of the oligomers, the oligomers are separated into C5 or less oligomers; 1-hexene; C6 other than the 1-hexene, and C7 oligomers; 1-octene; and C8 other than the 1-octene, and C9-C20 oligomers.

9. The method of claim 1 , wherein the olefin monomer is ethylene, and the oligomers include a mixture of C4-C40 linear alpha olefins.

10. A method for oligomerizing olefins, the method comprising:
introducing an oligomerization transition metal catalyst, an olefin monomer, and a solvent into a reactor and performing an olefin oligomerization reaction to produce oligomers;
introducing a catalyst deactivator to a reaction product of the oligomerization reaction to deactivate the catalyst, wherein the catalyst deactivator includes oxygen, and has a number average molecular weight of 1,000 to 10,000;
separating the oligomers by distillation through the top or middle portion of a distiller; and
separating the catalyst deactivator through the bottom end of the distiller,
wherein the catalyst deactivator is represented by the following Formula 1:

wherein the transition metal catalyst is represented by ML 1 (L 2 ) p (X) q or M 2 X 1 2 L 1 2 (L 2 ) y (X) z , wherein M is a transition metal, L 1 is a heteroligand, L 2 is an organic ligand, X and X 1 are each independently a halogen, p is an integer of 0 or 1 or more, q is an integer of (oxidation number of M−p), y is an integer of 2 or more, and z is an integer of (2× oxidation number of M) −y,
wherein the heteroligand L 1 has a P—C—C—P backbone structure represented by the following Formula 3,

wherein R 51 to R 54 are each independently a hydrocarbyl, a substituted hydrocarbyl, a heterohydrocarbyl, or a substituted heterohydrocarbyl, and
wherein R 55 and R 56 are each independently a hydrocarbyl or a substituted hydrocarbyl, or R 55 and R 56 may be taken together via hydrocarbylene, substituted hydrocarbylene, heterohydrocarbylene, or substituted heterohydrocarbylene to form a ring.

Assignees

• Sk Innovation Co Ltd
• Sk Global Chemical Co Ltd

Inventors

• Son Sungreal
• Park Hyoseung
• Song Inhyoup
• Sim So Hee
• Park Chansaem
• Jung Woosung

Classifications

• C07C11/02

  Alkenes · CPC title

• C07C7/20

  Use of additives, e.g. for stabilisation · CPC title

• C07C7/04

  by distillation · CPC title

• C07C2/32 Primary

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

• C07C2/36 Primary

  as phosphines, arsines, stilbines or bismuthines · CPC title