# US 11,306,040 B2 · Halogen-containing compound and use thereof, catalyst composition, and ethylene oligomerization, trimerization and tetramerization methods

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,306,040 B2
- Document ID: US11306040B2
- Status: Granted
- Kind: B2
- Application number: 17/310,069
- Filed: 2019-10-30
- Published: 2022-03-03
- Granted: 2022-04-19
- Earliest claimed: 2019-01-15
- Assignees: China Petroleum & Chemical Corporation; Beijing Research Institute of Chemical Industry, China Petroleum & Chemical Corporation
- Applicants: China Petroleum & Chemical Corporation; Beijing Research Institute of Chemical Industry, China Petroleum & Chemical Corporation
- Inventors: Hongfei Wu; Mingfang Zheng; Songshuang Hu; Tonglin Li; Jun Liu; Ke Xu; Xiaoqing Wang; Feng Pan
- Web page: https://patentgrep.com/patent/US11306040B2

## CPC

- C07C 2/36: as phosphines, arsines, stilbines or bismuthines
- C07F 9/5027: {Polyphosphines}
- B01J 31/143: {of aluminium}
- B01J 31/2213: {At least two complexing oxygen atoms present in an at least bidentate or bridging ligand}
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- C07F 9/5045: {Complexes or chelates of phosphines with metallic compounds or metals}
- C07F 11/00: Compounds containing elements of Groups 6 or 16 of the Periodic Table
- B01J 31/2291: {Olefins}
- B01J 2231/20: Olefin oligomerisation or telomerisation
- B01J 2531/62: Chromium
- B01J 2540/22: comprising fluorine, e.g. trifluoroacetate
- C07C 2531/14: of aluminium or boron
- C07C 2531/24: Phosphines
- Y02P 20/52: using catalysts, e.g. selective catalysts
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A halogen-containing compound as shown in a formula I can be used as a ligand for an ethylene oligomerization catalyst composition. The ethylene oligomerization catalyst composition containing the halogen-containing compound can be used to catalyze ethylene oligomerization, trimerization and tetramerization reactions. As a ligand of a catalyst for ethylene oligomerization, a fluoropolymer can effectively improve the catalytic performance of a catalyst system, and particularly exhibits improved activity and selectivity in an ethylene oligomerization reaction.

## Claims

### Claim 1

A halogen-containing compound, represented by a formula I,
wherein in the formula I, R1, R2, R3, and R4 are the same or different, and each independently is halogen; R5 and R6 are the same or different, and each independently is hydrogen, C1-C12 alkyl, C3-C12 cycloalkyl, or C6-C20 aryl.

### Claim 2 (depends on 1)

The halogen-containing compound according to claim 1, wherein in the formula I, both R5 and R6 are hydrogen.

### Claim 3 (depends on 1)

The halogen-containing compound according to claim 1, wherein in the formula I, R5 and R6 are the same or different, and each independently is C1-C12 alkyl, C3-C12 cycloalkyl, or C6-C20 aryl;
or, in the formula I, R5 and R6 are the same or different, and each independently is C1-C8 alkyl, C3-C8 cycloalkyl, or C6-C16 aryl;
or, in the formula I, R5 and R6 are the same or different, and each independently is C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C12 aryl;
or, in the formula I, R5 and R6 are the same or different, and each independently is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl, chlorophenyl, or naphthyl;
or, in the formula I, R5 and R6 are the same or different, and each independently is tert-butyl, cyclohexyl, phenyl, isopropyl, or methyl;
or, in the formula I, R5 and R6 are the same or different, and each independently is tert-butyl, cyclohexyl, or methyl.

### Claim 4 (depends on 1)

The halogen-containing compound according to claim 1, wherein in the formula I, R5 is hydrogen, and R6 is C1-C12 alkyl, C3-C12 cycloalkyl, or C6-C20 aryl;
or, in the formula I, R5 is hydrogen, and R6 is C1-C8 alkyl, C3-C8 cycloalkyl, or C6-C16 aryl;
or, in the formula I, R5 is hydrogen, and R6 is C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C12 aryl;
or, in the formula I, R5 is hydrogen, and R6 is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl, chlorophenyl, or naphthyl;
or, in the formula I, R5 is hydrogen, and R6 is tert-butyl, cyclohexyl, phenyl, isopropyl, or ethyl;
or, in the formula I, R5 is hydrogen, and R6 is tert-butyl, cyclohexyl, or phenyl.

### Claim 5 (depends on 1)

The halogen-containing compound according to claim 1, wherein R1, R2, R3 and R4 are the same or different, and each independently is chlorine or fluorine;
or, R1, R2, R3 and R4 are fluorine.

### Claim 6 (depends on 1)

The halogen-containing compound according to claim 1, wherein at least one of R1, R2, R3, and R4 is an ortho-substituent;
or, all of R1, R2, R3 and R4 are an ortho-substituent.

### Claim 7 (depends on 1)

The halogen-containing compound according to claim 1, wherein the halogen-containing compound is selected from compounds represented by formulae II and compounds represented by formulae III,
in the formula II, R7 is C1-C12 alkyl, C3-C12 cycloalkyl, or C6-C20 aryl;
in the formula III, R8 and R9 are the same or different, each independently is C1-C12 alkyl, C3-C12 cycloalkyl, or C6-C20 aryl.

### Claim 8 (depends on 7)

The halogen-containing compound according to claim 7, wherein in the formulae II and III, R7, R8 and R9 each independently is C1-C8 alkyl, C3-C8 cycloalkyl, or C6-C16 aryl;
or, in the formulae II and III, R7, R8 and R9 each independently is C1-C6 alkyl, C3-C6 cycloalkyl, or C6-C12 aryl;
or, in the formulae II and III, R7, R8 and R9 each independently is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, tert-pentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, ethylphenyl, chlorophenyl, or naphthyl;
or, in the formulae II and III, R7, R8 and R9 each independently is tert-butyl, cyclohexyl, phenyl, isopropyl, or ethyl;
or, in the formula II, R7 is tert-butyl, cyclohexyl, or phenyl;
or, in the formula III, R8 and R9 each independently is tert-butyl, cyclohexyl, or methyl.

### Claim 9 (depends on 1)

An ethylene oligomerization catalyst composition, comprising at least one halogen-containing compound of claim 1, at least one transition metal compound, and at least one cocatalyst.

### Claim 10 (depends on 9)

The composition according to claim 9, wherein a molar ratio of the halogen-containing compound to the transition metal compound is 1:0.1-10, or 1:025-2, or 1:0.5-2, and a molar ratio of the halogen-containing compound to the co-catalyst is 1:1-1000, or 1:10-700, or 1:100-500.

### Claim 11 (depends on 9)

The composition according to claim 9, wherein the transition metal compound is at least one selected from the group consisting of a chromium compound, a molybdenum compound, an iron compound, a titanium compound, a zirconium compound, and a nickel compound, or at least one selected from the group consisting of chromium acetylacetonate, chromium isooctanoate, tris(tetrahydrofuran)chromium trichloride, and bis(tetrahydrofuran)chromium dichloride, the co-catalyst is an aluminum-containing co-catalyst;
or, the co-catalyst is an organoaluminum compound;
or, the co-catalyst is at least one selected from the group consisting of alkyl aluminum, alkoxy aluminum and alkyl aluminum halide;
or, the co-catalyst is at least one selected from the group consisting of methylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, aluminium diethyl monochloride, aluminium ethyl dichloride, ethylaluminoxane, and modified methylaluminoxane;
or, the co-catalyst is at least one selected from the group consisting of modified methylaluminoxane, methylaluminoxane, and triethylaluminum.

### Claim 12 (depends on 9)

An ethylene oligomerization method, comprising a step of contacting ethylene with the catalyst composition according to claim 9.

### Claim 13 (depends on 12)

The method according to claim 12, wherein the contacting is carried out in at least one organic solvent, the organic solvent is at least one selected from the group consisting of C6-C12 alkane, C6-C12 cycloalkane, and C6-C12 aromatic hydrocarbon,
Or, the organic solvent is at least one selected from the group consisting of methylcyclohexane, heptane, cyclohexane, toluene, and xylene, and wherein the organic solvent is used in an amount that the concentration of the catalyst composition, in terms of a transition metal element in the transition metal compound, is 1-20 μmol/L.

### Claim 14 (depends on 12)

The method according to claim 12, wherein the contacting is carried out at a temperature of 0-200° C., or 0-100° C., or 30-90° C., and the pressure of the ethylene is 0.1-20 MPa, or 0.5-10 MPa, or 2-8 MPa.

### Claim 15 (depends on 9)

An ethylene trimerization method, comprising a step of contacting ethylene with the catalyst composition according to claim 9 at a temperature of 60° C. or above.

### Claim 16 (depends on 15)

The trimerization method according to claim 15, wherein the contacting is carried out in at least one organic solvent, and the organic solvent is at least one selected from the group consisting of C6-C12 alkane, C6-C12 cycloalkane and C6-C12 aromatic hydrocarbon;
or, the organic solvent is at least one selected from the group consisting of methylcyclohexane, heptane, cyclohexane, toluene and xylene, wherein the organic solvent is used in an amount such that the concentration of the catalyst composition in the solvent, in terms of a transition metal element in the transition metal compound, is 1-20 μmol/L, and wherein the pressure of the ethylene is 0.1-20 MPa, or 0.5-5 MPa, or 1-4 MPa, or 2-3 MPa.

### Claim 17 (depends on 15)

The trimerization method according to claim 15, wherein the contacting is carried out at a temperature of 60-90° C.

### Claim 18 (depends on 9)

An ethylene tetramerization method, comprising a step of contacting ethylene with the catalyst composition according to claim 9 at a temperature of lower than 60° C.

### Claim 19 (depends on 18)

The tetramerization method according to claim 18, wherein the contacting is carried out in at least one organic solvent, the organic solvent is at least one selected from the group consisting of C6-C12 alkane, C6-C12 cycloalkane, and C6-C12 aromatic hydrocarbon;
or, the organic solvent is at least one selected from methylcyclohexane, heptane, cyclohexane, toluene and xylene, wherein the organic solvent is used in an amount that the concentration of the catalyst composition in the solvent, in terms of a transition metal element in the transition metal compound, k 1-20 μmol/L, and wherein the pressure of the ethylene is 0.1-20 MPa, or 0.5-8 MPa, or 3-6 MPa, or 4-5 MPa.

### Claim 20 (depends on 18)

The tetramerization method according to claim 18, wherein the contacting is carried out at a temperature of 30-50° C.