Method for preparing butene oligomer

Patent metadata

Field	Value
Publication number	US-11370855-B2
Application number	US-201916644703-A
Country	US
Kind code	B2
Filing date	Jul 26, 2019
Priority date	Jul 27, 2018
Publication date	Jun 28, 2022
Grant date	Jun 28, 2022

Abstract

The present invention provides a method for preparing a butene oligomer including a step of oligomerizing a polymerization solution including a halogenated hydrocarbon solvent, a nonpolar hydrocarbon solvent and an isobutene monomer in the presence of an organometal catalyst.

First claim

The invention claimed is:

1. A method for preparing a butene oligomer, the method comprising:
a step of oligomerizing a polymerization solution comprising a halogenated hydrocarbon solvent, a nonpolar hydrocarbon solvent and an isobutene monomer, in the presence of an organometal catalyst represented by the following Formula 1:

in Formula 1,
M is selected from the group consisting of metals in group 13 and lanthanide series,
L is each independently a coordinating solvent molecule comprising a functional group selected from the group consisting of a cyanide group, an isocyanide group, an ether group, a pyridine group, an amide group, a sulfoxide group and a nitro group,
R 1 to R 4 are each independently hydrogen, a halogen group, or a substituted or unsubstituted C1-C20 alkyl group,
R 5 and R 6 are each independently hydrogen, a C1-C20 alkyl group, a C6-C20 aryl group, or an allyl group,
a, b, c and a+b+c are each independently an integer of 0 to 3,
d and a+b+c+d are each independently an integer of 1 to 10,
o, p, q and r are each independently an integer of 1 to 5, and
x and y are an integer of 1 to 4 and are the same.

2. The method for preparing a butene oligomer according to claim 1 , wherein a volume ratio of the halogenated hydrocarbon solvent and the nonpolar hydrocarbon solvent is 25:75 to 99:1.

3. The method for preparing a butene oligomer according to claim 1 , wherein the halogenated hydrocarbon solvent is one or more selected from the group consisting of chloromethane, dichloromethane, trichloromethane, 1-chlorobutane and chlorobenzene.

4. The method for preparing a butene oligomer according to claim 1 , wherein the nonpolar hydrocarbon solvent is one or more selected from the group consisting of butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane, benzene, toluene, xylene, and ethylbenzene.

5. The method for preparing a butene oligomer according to claim 1 , wherein the step of oligomerizing is performed by a batch type or continuous type process.

6. The method for preparing a butene oligomer according to claim 1 , further comprising a step of removing the organometal catalyst by filtering an oligomerized product.

7. The method for preparing a butene oligomer according to claim 6 , wherein the filtering is performing using a filter comprising one or more selected from the group consisting of celite, silica, zeolite and alumina.

8. The method for preparing a butene oligomer according to claim 6 , wherein a step of drying the halogenated hydrocarbon solvent is not performed after the step of oligomerizing and prior to filtering.

9. The method for preparing a butene oligomer according to claim 1 , wherein a step of washing an oligomerized product to remove the organometal catalyst is not performed.

10. The method for preparing a butene oligomer according to claim 1 , wherein
M is one or more selected from the group consisting of Al, Ga, In, Tl, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
L is one or more selected from the group consisting of acetonitrile, propionitrile, 2-methylpropanenitrile, trimethylacetonitrile, benzonitrile, dialkyl ether, pyridine, dimethylformamide, dimethyl sulfoxide, nitromethane, nitrobenzene and the derivatives thereof, and a coordinating solvent molecule in which an unshared electron pair of oxygen, nitrogen or carbon makes a coordination bond with M;
R 1 to R 4 are each independently hydrogen, a halogen group, or a halogen-substituted C1-C12 alkyl group, and
R 5 and R 6 are each independently hydrogen, a C1-C12 alkyl group, a C6-C12 aryl group, or an allyl group.

11. The method for preparing a butene oligomer according to claim 1 , wherein the organometal catalyst does not comprise a halogen salt of one or more metals selected from the group consisting of metals of group 1, group 2 and group 11.

12. The method for preparing a butene oligomer according to claim 11 , wherein the halogen salt is one or more selected from the group consisting of silver chloride (AgCl), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), magnesium chloride (MgCl 2 ), silver bromide (AgBr), lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), magnesium bromide (MgBr 2 ), silver iodide (AgI), lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI) and magnesium iodide (MgI 2 ).

13. The method for preparing a butene oligomer according to claim 1 , wherein the borate-based bulky anion of the organometal catalyst represented by Formula 1 is one or more selected from the group consisting of tetrakis(phenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis [3,5-bis(trifluoromethyl)phenyl]borate, and the derivatives thereof.

14. The method for preparing a butene oligomer according to claim 1 , wherein the butene oligomer produced by the oligomerization has a number average molecular weight of 500 to 5,500.

15. The method for preparing a butene oligomer according to claim 1 , wherein the isobutene monomer is included in an amount of 1 to 50 wt % based on the total weight of the polymerization solution.

16. The method for preparing a butene oligomer according to claim 1 , wherein the butene oligomer produced by the oligomerization has a polydispersity (PDI) of 1.5 to 3, and an exo-content of 50% to 99%.

Assignees

• Lg Chemical Ltd

Inventors

• Lee Jin
• Jo Dong Hyun
• Kim Won Hee
• Choi Gyeong Shin

Classifications

• C08F6/02 Primary

  Neutralisation of the polymerisation mass, e.g. killing the catalyst (short-stopping C08F2/42 ){also removal of catalyst residues} · CPC title

• C08F4/52

  selected from boron, aluminium, gallium, indium, thallium or rare earths (C08F4/14 takes precedence) · CPC title

• C07C2/32

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

• B01J2231/20

  Olefin oligomerisation or telomerisation · CPC title

• C08F10/10 Primary

  Isobutene · CPC title