Method for oligomerizing an olefin

1. A method for oligomerizing an olefin, the method comprising:

performing a multimerization reaction of an olefin in the presence of an oligomerization catalyst system comprising a ligand compound, a transition metal compound, and a co-catalyst, and

controlling a reaction temperature during the multimerization reaction in a range of 30 to 150° C., such that a product of the multimerization reaction comprising 1-hexene and 1-octene has a predetermined value of a weight ratio of 1-hexene and 1-octene selected from a range of 1:0.5 to 1:7,

wherein the olefin comprises ethylene,

wherein the transition metal compound comprises an organic chromium compound, and

wherein the oligomerization catalyst system is prepared by preparing a catalyst composition by mixing the ligand compound and the transition metal compound, and activated by mixing a co-catalyst and the catalyst composition for less than five minutes at a temperature of 25 to 80° C.

2. The method for oligomerizing an olefin of claim 1 , wherein the predetermined value of the weight ratio is from 1:0.9 to 1:6.6.

3. The method for oligomerizing an olefin of claim 1 , wherein the reaction temperature is controlled in a range of 60 to 130° C.

4. The method for oligomerizing an olefin of claim 1 , wherein a weight ratio of 1-hexene in relation to 1-octene in the product increases when the reaction temperature is increased.

5. The method for oligomerizing an olefin of claim 1 , wherein a selectivity of 1-hexene and 1-octene relative to a total amount of the product is 80 wt % or more in the whole reaction temperature range.

6. The method for oligomerizing an olefin of claim 1 , wherein an activity of the oligomerization catalyst system decreases 9% or less in the whole reaction temperature range when the reaction temperature is increased.

7. The method for oligomerizing an olefin of claim 1 , wherein an activity of the oligomerization catalyst system in the whole reaction temperature range is 100,000 kg/molCr/hr or more in a batch process, and 100,000 kg/molCr/hr or more in a continuous process.

8. The method for oligomerizing an olefin of claim 1 , wherein an activating time of the co-catalyst and the catalyst composition is three minutes or less.

9. The method for oligomerizing an olefin of claim 1 , wherein the ligand compound comprises a diphosphine moiety represented by the following Formula 1:

wherein in Formula 1, A is N, As or Sb, R1 to R4 are each independently a hydrocarbyl group, a heterohydrocarbyl group, or a hydrocarbylheteryl group, each group having 1 to 20 carbon atoms.

10. The method for oligomerizing an olefin of claim 9 , wherein the ligand compound comprises at least two diphosphine moieties represented by the following Formula 2, and

a hydrocarbyl linker connecting the at least two diphosphine moieties and having a carbon number of the shortest distance between the diphosphine moieties of from 2 to 30:

wherein in Formula 2, A and R1 to R4 are the same as defined in Formula 1, and * is the hydrocarbyl linker connecting the at least two diphosphine moieties.

11. The method for oligomerizing an olefin of claim 10 , wherein the hydrocarbyl linker comprises at least one group selected from the group consisting of an aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a combination thereof.

12. The method for oligomerizing an olefin of claim 9 , wherein the ligand compound is represented by the following Formula 3:

wherein in Formula 3,

R1 to R4 are the same as defined in Formula 1,

R5 is an alkyl group having 1 to 20 carbon atoms,

wherein in the case that R5 is a methyl group, R6 is a linear C2-C3 alkyl group, a linear C2-C3 alkenyl group, a linear C2-C3 heteroalkyl group, a linear C2-C3 heteroalkenyl group, or a C2-C3 heteryl group thereof; a C4-C20 alkyl group, a C4-C20 alkenyl group, a C4-C20 arylalkyl group, a C4-C20 arylalkenyl group, a C4-C20 heteroalkyl group, a C4-C20 heteroalkenyl group, a C4-C20 heteroarylalkyl group, a C4-C20 heteroarylalkenyl group, or a C4-C20 heteryl group thereof; a C3-C20 cycloalkyl group, a C3-C20 cycloalkenyl group, a C3-C20 arylcycloalkyl group, a C3-C20 arylcycloalkenyl group, a C3-C20 heterocycloalkyl group, a C3-C20 heterocycloalkenyl group, a C3-C20 heteroarylcycloalkyl group, a C3-C20 heteroarylcycloalkenyl group, or a C3-C20 heteryl group thereof; a C6-C20 aryl group, a C6-C20 heteroaryl group, or a C6-C20 heteryl group thereof; or a C7-C20 alkylaryl group, a C7-C20 heteroalkylaryl group, or a C7-C20 heteryl group thereof;

wherein in the case that R5 is an alkyl group having 2 to 20 carbon atoms, R6 is a C2-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 arylalkyl group, a C2-C20 arylalkenyl group, a C2-C20 heteroalkyl group, a C2-C20 heteroalkenyl group, a C2-C20 heteroarylalkyl group, a C2-C20 heteroarylalkenyl group, or a C2-C20 heteryl group thereof; a C3-C20 cycloalkyl group, a C3-C20 cycloalkenyl group, a C3-C20 arylcycloalkyl group, a C3-C20 arylcycloalkenyl group, a C3-C20 heterocycloalkyl group, a C3-C20 heterocycloalkenyl group, a C3-C20 heteroarylcycloalkyl group, a C3-C20 heteroarylcycloalkenyl group, or a C3-C20 heteryl group thereof; a C6-C20 aryl group, a C6-C20 heteroaryl group, or a C6-C20 heteryl group thereof; or a C7-C20 alkylaryl group, a C7-C20 heteroalkylaryl group, or a C7-C20 heteryl group thereof; and

R7 to R9 are each independently hydrogen; a C1-C20 alkyl group, a C1-C20 alkenyl group, a C1-C20 arylalkyl group, or a C1-C20 arylalkenyl group; a C3-C20 cycloalkyl group, a C3-C20 cycloalkenyl group, a C3-C20 arylcycloalkyl group, or a C3-C20 arylcycloalkenyl group; a C6-C20 aryl group; or a C7-C20 alkylaryl group.

13. The method for oligomerizing an olefin of claim 12 , wherein R7 to R9 of Formula 3 are hydrogen.

14. The method for oligomerizing an olefin of claim 1 , wherein the organic chromium compound is 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-heptanedionate), chromium(III) benzoyl acetonate, chromium(III) hexafluoro-2,4-pentanedionate, and chromium(III) acetate hydroxide.

15. The method for oligomerizing an olefin 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 the above Formula 4, each R5 is the same or different and is independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a halogen substituted hydrocarbyl radical having 1 to 20 carbon atoms, and c is an integer of at least 2;

D(R 6 ) 3   [Formula 5]

wherein in the above Formula 5, D is aluminum or boron, each R 6 is the same or different and is independently a hydrogen, 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 the above Formula 6, L is a neutral Lewis base, [L-H] + is a Brönsted 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 C1-C20 hydrocarbyl group, an alkoxy functional group or a phenoxy functional group.

16. The method for oligomerizing an olefin of claim 1 , wherein a pressure of the multimerization reaction is 1 to 300 bar.