Ligand compound, organic chromium compound, catalyst system for ethylene oligomerization, preparation method thereof, and ethylene oligomerization method using the same

Patent metadata

Field	Value
Publication number	US-9731282-B2
Application number	US-201314440683-A
Country	US
Kind code	B2
Filing date	Apr 12, 2013
Priority date	Nov 15, 2012
Publication date	Aug 15, 2017
Grant date	Aug 15, 2017

Abstract

The present invention relates to a ligand compound, an organic chromium compound, a catalyst system for ethylene oligomerization, a preparation method thereof, and an ethylene oligomerization method using the same. The catalyst system for ethylene oligomerization according to the present invention is used to prepare a low-density polyethylene in one reactor by using a small amount of comonomers such as alpha-olefin or by using only ethylene without comonomers, because it maintains high catalytic activity and high alpha-olefin selectivity even though supported on a support.

First claim

What is claimed is:

1. A ligand compound represented by the following Chemical Formula 1:

wherein X is phosphorus, arsenic or antimony;
W is ethylene or propylene;
R 1 , R 2 , R 3 and R 4 are each independently hydrocarbyl;
Z is nitrogen;
R 5 is hydrocarbyl; and
n is 2.

2. The ligand compound of claim 1 , wherein the ligand compound represented by Chemical Formula 1 is selected from the group consisting of (C 6 H 5 ) 2 PN(CH 2 CH 2 NMe 2 )P(C 6 H 5 ) 2 , (C 6 H 5 ) 2 PN(CH 2 CH 2 NEt 2 )P(C 6 H 5 ) 2 , (C 6 H 5 ) 2 PN(CH 2 CH 2 NPr 2 )P(C 6 H 5 ) 2 , and (C 6 H 5 ) 2 PN(CH 2 CH 2 CH 2 NMe 2 )P(C 6 H 5 ) 2 .

3. An organic chromium compound represented by the following Chemical Formula 2:

wherein X is phosphorus, arsenic or antimony;
W is ethylene or propylene;
R 1 , R 2 , R 3 and R 4 are each independently hydrocarbyl;
Z is nitrogen;
R 5 is hydrocarbyl;
Y is each independently halogen, hydrogen, or hydrocarbyl having 1 to 4 carbon atoms; and
n is 2.

4. The organic chromium compound of claim 3 , wherein Y is Cl or methyl.

5. A catalyst system for ethylene oligomerization, comprising i) a ligand compound represented by the following Chemical Formula 1 and a chromium source, or ii) an organic chromium compound represented by the following Chemical Formula 2; and a cocatalyst:

wherein X is phosphorus, arsenic or antimony;
W is ethylene or propylene;
R 1 , R 2 , R 3 and R 4 are each independently hydrocarbyl;
Z is nitrogen;
R 5 is hydrocarbyl;
Y is each independently halogen, hydrogen, or hydrocarbyl having 1 to 4 carbon atoms; and
n is 2.

6. The catalyst system for ethylene oligomerization of claim 5 , wherein the ligand compound represented by Chemical Formula 1 is selected from the group consisting of (C 6 H 5 ) 2 PN(CH 2 CH 2 NMe 2 )P(C 6 H 5 ) 2 , (C 6 H 5 ) 2 PN(CH 2 CH 2 NEt 2 )P(C 6 H 5 ) 2 , (C 6 H 5 ) 2 PN(CH 2 CH 2 NPr 2 )P(C 6 H 5 ) 2 and (C 6 H 5 ) 2 PN(CH 2 CH 2 CH 2 NMe 2 )P(C 6 H 5 ) 2 .

7. The catalyst system for ethylene oligomerization of claim 5 , wherein in Chemical Formula 2, Y is Cl or methyl.

8. The catalyst system for ethylene oligomerization of claim 5 , wherein the chromium source is selected from the group consisting of chromium (III) acetylacetonate, tris(tetrahydrofuran) trichlorochromium, and chromium (III) 2-ethylhexanoate.

9. The catalyst system for ethylene oligomerization of claim 5 , wherein the cocatalyst is one or more selected from the group consisting of the compounds represented by the following Chemical Formulae 3 to 5:
—[Al(R 6 )—O] c -  [Chemical Formula 3]

wherein R 6 is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, a halogen-substituted hydrocarbyl radical having 1 to 20 carbon atoms, and c is an integer of 2 or more,
D(R 7 ) 3   [Chemical Formula 4]

wherein D is aluminium or boron, R 7 is hydrocarbyl having 1 to 20 carbon atoms or halogen-substituted hydrocarbyl having 1 to 20 carbon atoms,
[L-H] + [Q(E) 4 ] −   [Chemical Formula 5]

wherein L is a neutral Lewis base, [L-H] + is a Bronsted acid, Q is boron or aluminium in the +3 oxidation state, E is each independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted or unsubstituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, an alkoxy functional group or a phenoxy functional group.

10. The catalyst system for ethylene oligomerization of claim 5 , further comprising a support.

11. The catalyst system for ethylene oligomerization of claim 10 , wherein the organic chromium compound and the cocatalyst are included in an amount of about 0.5 to about 20 parts by weight, and about 1 to about 1,000 parts by weight, respectively, based on 100 parts by weight of the support.

12. The catalyst system for ethylene oligomerization of claim 10 , wherein the support includes hydroxyl groups and siloxane groups on the surface.

13. The catalyst system for ethylene oligomerization of claim 10 , wherein the support includes one or more selected from the group consisting of silica, silica-alumina and silica-magnesia.

14. An ethylene oligomerization method comprising:
oligomerizing ethylene in the presence of the catalyst system for ethylene oligomerization of claim 5 .

15. A preparation method of a catalyst system for ethylene oligomerization, comprising the steps of:
supporting a cocatalyst on a support; and
supporting an organic chromium compound represented by the following Chemical Formula 2 on the cocatalyst-supported support:

wherein X is phosphorus, arsenic or antimony;
W is ethylene or propylene;
R 1 , R 2 , R 3 and R 4 are each independently hydrocarbyl;
Z is nitrogen;
R 5 is hydrocarbyl;
Y is each independently halogen, hydrogen, or hydrocarbyl having 1 to 4 carbon atoms; and
n is 2.

16. The preparation method of claim 15 , wherein the cocatalyst is one or more selected from the group consisting of the compounds represented by the following Chemical Formulae 3 to 5:
—[Al(R 6 )—O] c -  [Chemical Formula 3]

wherein R 6 is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, a halogen-substituted hydrocarbyl radical having 1 to 20 carbon atoms, and c is an integer of 2 or more,
D(R 7 ) 3   [Chemical Formula 4]

wherein D is aluminium or boron, R 7 is hydrocarbyl having 1 to 20 carbon atoms or halogen-substituted hydrocarbyl having 1 to 20 carbon atoms,
[L-H] + [Q(E) 4 ] −   [Chemical Formula 5]

wherein L is a neutral Lewis base, [L-H] + is a Bronsted acid, Q is boron or aluminium in the +3 oxidation state, E is each independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted or unsubstituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, an alkoxy functional group or a phenoxy functional group.

17. The preparation method of claim 15 , wherein the organic chromium compound and the cocatalyst are included in an amount of about 0.5 to about 20 parts by weight, and about 1 to about 1,000 parts by weight, respectively, based on 100 parts by weight of the support.

18. The preparation method of claim 15 , wherein the support includes one or more selected from the group consisting of silica, silica-alumina and silica-magnesia.

19. A preparation method of a catalyst system for ethylene oligomerization, comprising the steps of:
supporting an organic chromium compound represented by the following Chemical Formula 2 on a support; and
supporting a cocatalyst on the organic chromium compound-supported support:

wherein X is phosphorus, arsenic or antimony;
W is ethylene or

Assignees

• Lg Chemical Ltd

Inventors

• Cho Min-Seok
• Lee Yong-Ho
• Sa Seok-Pil
• Kwon Heon-Yong
• Cho Kyung-Jin
• Kim Se-Young
• Lee Sung-Min
• Lee Ki-Soo
• Lim Kyoung-Chan

Classifications

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J2531/62

  Chromium · CPC title

• C07F11/00

  Compounds containing elements of Groups 6 or 16 of the Periodic Table · CPC title

• B01J31/1805

  the ligands containing nitrogen · CPC title

• B01J21/08

  Silica · CPC title