Deactivator and method for decreasing by-products in olefin oligomerization using the same

Patent metadata

Field	Value
Publication number	US-10413893-B2
Application number	US-201615517758-A
Country	US
Kind code	B2
Filing date	Feb 2, 2016
Priority date	Feb 12, 2015
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

The method for oligomerizing olefin according to the present disclosure is a method for oligomerizing olefin using an oligomerization catalyst system and includes deteriorating the activity of the oligomerization catalyst system by injecting a deactivator in a latter part of a multimerization reaction of olefin. The deactivator may include an additive for polymer containing at least one functional group selected from the group consisting of a hydroxyl group, an amine group and an amide group. According to the oligomerizing method, the isomer of 1-hexene and/or 1-octene and alpha-olefins with C 10 to C 40 may be decreased via the restraint of the additional side reaction of a product. Since the deactivator is an additive for enhancing the physical properties of a polymer, a separating process thereof is not required, thereby improving economic feasibility and productivity.

First claim

The invention claimed is:

1. A method for oligomerizing an olefin using an oligomerization catalyst system, the method comprising:
injecting a deactivator into a product mixture of an oligomerization reaction of an olefin to deteriorate activity of the oligomerization catalyst system, and
separating the product mixture into an alpha-olefin product and a polymer resin product after deteriorating the activity of the oligomerization catalyst system,
wherein the polymer resin product contains a mixture of polyethylene and the deactivator,
wherein the deactivator comprises an additive including at least one functional group selected from the group consisting of a hydroxyl group, an amine group and an amide group,
wherein the additive comprises at least one selected from the group consisting of an antistatic agent, an antioxidant, a lubricant, a stabilizer, and a phase transfer catalyst, and
wherein the method does not include separating the deactivator from the polymer resin product.

2. The method for oligomerizing an olefin of claim 1 , wherein a molar ratio of the oligomerization catalyst system to the deactivator is from 1:1 to 1:100.

3. The method for oligomerizing an olefin of claim 1 , wherein the additive comprises the antistatic agent, and wherein the antistatic agent comprises at least one selected from the group consisting of bis(2-hydroxyethyl)pentadecylamine, an ethoxylated fatty amine having 12 to 18 carbon atoms, glycerol monostearate, erucamide, stearamide, oleamide and benenamide.

4. The method for oligomerizing an olefin of claim 1 , wherein the additive comprises the antioxidant, and wherein the antioxidant comprises butylated hydroxytoluene (BHT).

5. The method for oligomerizing an olefin of claim 1 , wherein the additive comprises the lubricant, and wherein the lubricant comprises at least one selected from the group consisting of erucamide, stearamide, oleamide, benenamide, an ethoxylated fatty amine having 12 to 18 carbon atoms and glycerol monostearate.

6. The method for oligomerizing an olefin of claim 1 , wherein the additive comprises the stabilizer, and wherein the stabilizer comprises triisopropanolamine (TIPA), quadrol(N,N,N,N-tetrakis(2-hydroxypropyl)-ethylenediamine) or a mixture thereof.

7. The method for oligomerizing an olefin of claim 1 , wherein the deactivator comprises a light stabilizer, and wherein the light stabilizer comprises a benzotriazole-based compound.

8. The method for oligomerizing an olefin of claim 1 , wherein the additive comprises the phase transfer catalyst, and wherein the phase transfer catalyst comprises tricaprylmethylammonium chlorine.

9. The method for oligomerizing an olefin of claim 1 , wherein the oligomerization catalyst system comprises a diphosphine-based ligand compound; a transition metal compound; and a co-catalyst.

10. The method for oligomerizing an olefin of claim 9 , 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, trichloro chromium 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.

11. The method for oligomerizing an olefin of claim 9 , wherein the diphosphine-based ligand compound comprises at least two diphosphine moieties represented by Formula 1, or a compound represented by Formula 2:

wherein in Formula 1, A is N, As or Sb; R1 to R4 are each independently aryl groups having 6 to 20 carbon atoms or alkylaryl groups having 7 to 20 carbon atoms, and * is a linker connecting the at least two diphosphine moieties;

wherein in Formula 2,
R1 to R4 are the same as defined in Formula 1, and R5 is an alkyl group having 1 to 20 carbon atoms,
with the proviso that when R5 is a methyl group, R6 is (i) a linear alkyl group, a linear alkenyl group, a linear heteroalkyl group, a linear heteroalkenyl group, or a heteryl group thereof having 2 or 3 carbon atoms; (ii) an alkyl group, an alkenyl group, an arylalkyl group, an arylalkenyl group, a heteroalkyl group, a heteroalkenyl group, a heteroarylalkyl group, a heteroarylalkenyl group, or a heteryl group thereof having 4 to 20 carbon atoms; (iii) a cycloalkyl group, a cycloalkenyl group, an arylcycloalkyl group, an arylcycloalkenyl group, a heteroarylcycloalkyl group, a heteroarylcycloalkenyl group, or a heteryl group thereof having 3 to 20 carbon atoms; (iv) an aryl group, a heteroaryl group, or a heteryl group thereof having 6 to 20 carbon atoms; or (v) an alkylaryl group, a heteroalkylaryl group, or a heteryl group thereof having 7 to 20 carbon atoms;
with the proviso that when R5 is an alkyl group having 2 to 20 carbon atoms, R6 is: (i) an alkyl group, an alkenyl group, an arylalkyl group, an arylalkenyl group, a heteroalkyl group, a heteroalkenyl group, a heteroarylalkyl group, a heteroarylalkenyl group, or a heteryl group thereof having 2 to 20 carbon atoms; (ii) a cycloalkyl group, a cycloalkenyl group, an arylcycloalkyl group, an arylcycloalkenyl group, a heterocycloalkyl group, a heterocycloalkenyl group, a heteroarylcycloalkyl group, a heteroarylcycloalkenyl group, or a heteryl group thereof having 3 to 20 carbon atoms; an aryl group, a heteroaryl group, or a heteryl group thereof having 6 to 20 carbon atoms; or (iv) an alkylaryl group, a heteroalkylaryl group, or a heteryl group thereof having 7 to 20 carbon atoms; and
R7 to R9 are each independently: (i) hydrogen; (ii) an alkyl group, an alkenyl group, an arylalkyl group, or an arylalkenyl group having 1 to 20 carbon atoms; (iii) a cycloalkyl group, a cycloalkenyl group, an arylcycloalkyl group, or an arylcycloalkenyl group having 3 to 20 carbon atoms; (iv) an aryl group having 6 to 20 carbon atoms; or (v) an alkylaryl group having 7 to 20 carbon atoms.

12. The method for oligomerizing an olefin of claim 11 , wherein the linker in Formula 1 is selected from the group consisting of an aliphatic group having 1 to 20 carbon atoms, a hetero aliphatic group having 2 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, a hetero alicyclic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a heteroaromatic group having 6 to 20 carbon atoms.

Assignees

• Lg Chemical Ltd

Inventors

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

Classifications

• B01J31/188

  Amide derivatives thereof · CPC title

• C07C2531/24

  Phosphines · CPC title

• C08K5/00

  Use of organic ingredients · CPC title

• C08K5/17

  Amines; Quaternary ammonium compounds · CPC title

• C07C2531/14

  of aluminium or boron · CPC title