Method for preparing polybutene oligomer

Patent metadata

Field	Value
Publication number	US-11746165-B2
Application number	US-201916960696-A
Country	US
Kind code	B2
Filing date	Oct 30, 2019
Priority date	Nov 23, 2018
Publication date	Sep 5, 2023
Grant date	Sep 5, 2023

Abstract

The present invention provides a method for preparing a polybutene 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 polybutene 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 1 and M 2 are each independently selected from transition metals in period 5 of groups 6 to 10 and transition metals in period 6 of groups 6 to 10, where a bond between M 1 and M 2 is any one among single to quadruple bonds according to an oxidation number of a metal,
S 1 and S 2 are each independently a substituent which includes any one among oxygen, nitrogen, carbon and halogen atoms having one or more unshared electron pairs, where the unshared electron pairs of S 1 and S 2 make coordination bonds with M 1 and M 2 , respectively,
Y and Z are each independently selected from the group consisting of O, S, N(R m ) and P, where R m is hydrogen, or a substituted or unsubstituted alkyl group of 1 to 10 carbon atoms,
L is C(R n ), where R n is hydrogen, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, or a substituted or unsubstituted amine group,
R m and R n are optionally combined with each other to form a heteroaryl group of 4 to 20 carbon atoms,
R 1 to R 4 are each independently hydrogen, a halogen group, or a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms,
a is an integer of 0 to 3,
b is an integer of 1 to 5,
a+b is 4 or 5,
o, p, q and r are each independently an integer of 1 to 5, and
x and y are the same and an integer of 1 to 4.

2. The method for preparing a polybutene oligomer according to claim 1 , wherein a weight ratio of the nonpolar hydrocarbon solvent and the halogenated hydrocarbon solvent is 85:15 to 15:85.

3. The method for preparing a polybutene 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 polybutene 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 polybutene 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 polybutene 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 polybutene oligomer according to claim 6 , wherein the filtering is performed with a filter comprising one or more selected from the group consisting of celite, silica, zeolite and alumina.

8. The method for preparing a polybutene 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 the filtering.

9. The method for preparing a polybutene 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 polybutene oligomer according to claim 1 , wherein
M 1 and M 2 are each independently selected from the group consisting of Mo, W, Re, Ru, Os, Rh, Pd and Pt,
S 1 and S 2 are each independently a halogen group; or a coordination solvent molecule comprising a functional group selected from the group consisting of a cyano group, an isocyano 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 alkyl group of C1-C12 with a halogen group,
R n is hydrogen, a substituted or unsubstituted alkyl group of 1 to 12 carbon atoms, an aryl group of 6 to 12 carbon atoms, or a substituted or unsubstituted amine group, and
R m and R n are optionally combined with each other to form a heteroaryl group of 4 to 12 carbon atoms.

11. The method for preparing a polybutene 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.

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

13. The method for preparing a polybutene oligomer according to claim 1 , wherein the step of oligomerizing is performed by a continuous type process, and the nonpolar hydrocarbon solvent is an aromatic hydrocarbon solvent.

14. The method for preparing a polybutene oligomer according to claim 1 , wherein the isobutene monomer is included in an amount of 1 to 50 wt %, and the organometal catalyst is included in an amount of 0.005 to 1 wt %, based on the total weight of the polymerization solution.

15. The method for preparing a polybutene oligomer according to claim 1 , wherein S 1 and S 2 are each independently a halogen group; or one or more selected from the group consisting of acetonitrile, propionitrile, 2-methylpropanenitrile, trimethylacetonitrile, benzonitrile, dialkyl ether, for example, diethyl ether and diallyl ether, pyridine, dimethylformamide, dimethyl sulfoxide, nitromethane, nitrobenzene and the derivatives thereof.

16. The method for preparing a polybutene oligomer according to claim 1 , wherein the organometal catalyst is one or more selected from the group consisting of the compounds represented by the formulae below:

17. The method for preparing a polybutene oligomer according to claim 1 , wherein the polybutene oligomer produced by the oligomerization has a polydispersity (PDI) of 1.5 to 3.0.

18. The method for preparing a polybutene oligomer according to claim 1 , wherein the polybutene oligomer produced by the oligomerization has an exo-content of 50 to 99%.

Assignees

• Lg Chemical Ltd

Inventors

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

Classifications

• C08F110/10 Primary

  Isobutene · CPC title

• C07F5/027

  Organoboranes and organoborohydrides · CPC title

• C08F6/00

  Post-polymerisation treatments (C08F8/00 takes precedence; of conjugated diene rubbers C08C) · CPC title

• C08F6/02

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