Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same

Patent metadata

Field	Value
Publication number	US-9701699-B2
Application number	US-201414892679-A
Country	US
Kind code	B2
Filing date	Nov 18, 2014
Priority date	Nov 18, 2013
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

This disclosure relates to a ligand compound, a catalyst system for olefin oligomerization, and a method for olefin oligomerization using the same. The catalyst system for olefin oligomerization according to the present invention has excellent catalytic activity, and yet, exhibits high selectivity to 1-hexene and 1-octene, thus enabling efficient preparation of alpha-olefin. The ligand compound is of the following Chemical Formula 1:

wherein at least one of R1 to R6 is a substituent of the following Chemical Formula

2:

First claim

The invention claimed is:

1. A ligand compound of Chemical Formula 1:

wherein in the Chemical Formula 1,
at least one of R 1 to R 6 is a substituent of Chemical Formula 2,
the other R 1 to R 6 , which are not the substituent of the Chemical Formula 2, are independently hydrogen, a C1-20 alkyl group which may or may not contain at least one heteroatom, a C3-20 cycloalkyl group, a C6-20 aryl group, a C7-20 arylalkyl group, a C7-20 alkylaryl group, or a C5-30 heteroaryl group, provided that all the other R 1 to R 6 which are not the substituent of the Chemical Formula 2 cannot be hydrogen,
R 7 to R 10 are independently hydrogen, a C1-20 alkyl group which may or may not contain at least one heteroatom, a C3-20 cycloalkyl group, a C6-20 aryl group, a C7-20 arylalkyl group, a C7-20 alkylaryl group, or a C5-30 heteroaryl group, or two different neighboring groups of the R 7 to R 10 may be connected to each other to form a C6-20 aromatic ring,

wherein in the Chemical Formula 2,
R 11 to R 14 are independently a C1-20 alkyl group, a C2-20 alkenyl group, a C6-20 aryl group, a C7-20 arylalkyl group, a C7-20 alkylaryl group, or a C7-20 alkoxyaryl group.

2. The ligand compound according to claim 1 , wherein in the Chemical Formula 1, at least one of R 1 to R 6 that are not the substituent of the Chemical Formula 2 is a C1-4 alkyl group, a C3-10 cycloalkyl group, a C6-10 aryl group, or a C7-15 arylalkyl group.

3. The ligand compound according to claim 1 , wherein R 7 to R 10 in the Chemical Formula 1 are independently hydrogen or a C1-20 alkyl group which may or may not contain at least one heteroatom, or two different neighboring groups of the R 7 to R 10 may be connected to each other to form a C6-20 aromatic ring.

4. The ligand compound according to claim 1 , wherein R 11 to R 14 in the Chemical Formula 2 are identical to each other.

5. The ligand compound according to claim 1 , wherein R 11 to R 14 in the Chemical Formula 2 are phenyl.

6. The ligand compound according to claim 1 , wherein the compound of the Chemical Formula 1 is selected from the group consisting of

7. A catalyst system for olefin oligomerization comprising the ligand compound according to claim 1 , a source of transition metal and a cocatalyst.

8. The catalyst system according to claim 7 , wherein the source of transition metal is at least one selected from the group consisting of chromium(III)acetylacetonate, tris(tetrahydrofuran)chromium trichloride, chromium(III)-2-ethylhexanoate, chromium(III)tris(2,2,6,6-tetramethyl-3,5-heptanedionate), chromium(III)benzoylacetonate, chromium(III)hexafluoro-2,4-pentanedionate, and chromium(III)acetate hydroxide.

9. The catalyst system according to claim 7 , wherein the cocatalyst is at least one compound selected from the group consisting of a compound of Chemical Formula 3, a compound of Chemical Formula 4, and a compound of Chemical Formula to 5:
—[Al(R 15 )—O] c -  [Chemical Formula 3]

wherein in the Chemical Formula 3, R 15 's are identical or different, and are independently a halogen radical, a C1-20 hydrocarbyl radical, or a C1-20 hydrocarbyl radical substituted with halogen, and c is an integer of 2 or more,
D(R 16 ) 3   [Chemical Formula 4]

wherein in the Chemical Formula 4,
D is aluminum or boron, R 16 's are identical or different, and are independently hydrogen, halogen, a C1-20 hydrocarbyl or a C1-20 hydrocarbyl substituted with halogen,
[L-H] + [Q(E) 4 ] −   [Chemical Formula 5]

wherein in the Chemical Formula 5,
L is a neutral Lewis base, [L-H] + is a Bronsted acid, Q is B 3+ or Al 3+ , and E's are independently a C 6-20 aryl group or a C 1-20 alkyl group, unsubstituted or substituted with at least one group selected from the group consisting of halogen, a C 1-20 hydrocarbyl, an alkoxy and a phenoxy group.

10. A method for olefin oligomerization, comprising the step of multimerizing olefins in the presence of the catalyst system for olefin oligomerization of claim 7 .

11. The method for olefin oligomerization according to claim 10 , wherein the olefin is ethylene.

12. The method for olefin oligomerization according to claim 10 , wherein the multimerization temperature is 5 to 200° C.

13. The method for olefin oligomerization according to claim 10 , wherein the multimerization pressure is 1 to 300 bar.

Assignees

• Lg Chemical Ltd

Inventors

• Lee Yong Ho
• Shin Eun Ji
• Sa Seok Pil
• Lee Ki Soo

Classifications

• C07F9/46 Primary

  Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids {including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof} · CPC title

• C07C211/54

  having amino groups bound to two or three six-membered aromatic rings · CPC title

• C07C11/107

  with six carbon atoms · CPC title

• C07C2531/22

  Organic complexes · CPC title

• C08F110/02

  Ethene · CPC title