# US 11,298,693 B2 · Method and catalyst for selective oligomerization of ethylene

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- Number: US 11,298,693 B2
- Document ID: US11298693B2
- Status: Granted
- Kind: B2
- Application number: 16/446,454
- Filed: 2019-06-19
- Published: 2019-12-26
- Granted: 2022-04-12
- Earliest claimed: 2018-06-22
- Assignees: PetroChina Company Limited
- Applicants: Petrochina Company Limited
- Inventors: Buwei Yu; Tao Jiang; Sihan Wang; Hongling Chu; Yan Jiang; Hongliang Huo; Xianming Xu; Libo Wang; Huaiqi Shao; Yali Wang; Yuanyuan Cao; Tong Liu; Kecun Ma; Fuling Huang; Xiuhui Wang; Enhao Sun; Yulong Wang
- Web page: https://patentgrep.com/patent/US11298693B2

## CPC

- B01J 31/181: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine}
- B01J 31/121: {Metal hydrides}
- B01J 31/122: {Metal aryl or alkyl compounds}
- B01J 31/143: {of aluminium}
- B01J 31/146: {of boron}
- B01J 31/34: of chromium, molybdenum or tungsten
- B01J 31/36: of vanadium, niobium or tantalum
- B01J 31/38: of titanium, zirconium or hafnium
- C07C 2/32: as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)}
- C07D 487/18: Bridged systems
- C07F 11/00: Compounds containing elements of Groups 6 or 16 of the Periodic Table
- B01J 2231/12: Olefin polymerisation or copolymerisation
- B01J 2231/20: Olefin oligomerisation or telomerisation
- B01J 2531/62: Chromium
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The present disclosure provides a method and a catalyst for selective oligomerization of ethylene. The raw material for the catalyst consists of a dehydropyridine annulene-type ligand, a transition metal compound, and an organometallic compound in a molar ratio of 1:0.5-100:0.1-5000. The present disclosure also provides a method for selective oligomerization of ethylene accomplished by using the above-mentioned catalyst. The catalyst for selective oligomerization of ethylene has high catalytic activity, high selectivity for the target products 1-hexene and 1-octene, and low selectivity for 1-butene and 1-C10+.

## Claims

### Claim 1

A catalyst for selective oligomerization of ethylene, wherein the raw material for the catalyst consists of: a dehydropyridine annulene ligand, a transition metal compound, and an organometallic compound in a molar ratio of 1:0.5-100:0.1-5000; wherein the dehydropyridine annulene ligand has a structural formula as shown in Formula I:
with R1, R2, R3 each independently selected from an alkyl group or an aryl group, wherein the transition metal compound is a compound of a metal from Group IVB-VIIIB, and wherein the organometallic compound is a compound containing a Group IIIA metal.

### Claim 2 (depends on 1)

The catalyst according to claim 1, wherein R1, R2, R3 are independently selected from methyl, ethyl, isopropyl, cyclopentyl, cyclohexyl, phenyl, o-methylphenyl, o-ethylphenyl, o-isopropylphenyl, 2,4-dimethylphenyl, 2,4-diethylphenyl, 2,4-diisopropylphenyl, 2,4-dibutylphenyl, 2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-dibutylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 2,4,6-triisopropylphenyl, naphthyl, anthryl, and biphenyl.

### Claim 3 (depends on 1)

The catalyst according to claim 1, wherein the dehydropyridine annulene ligand consists of a plurality of the compounds of Formula I.

### Claim 4 (depends on 1)

The catalyst according to claim 1, wherein the transition metal compound is a compound of at least one or more of chromium, molybdenum, tungsten, titanium, cobalt, tantalum, vanadium, zirconium, iron, nickel, or palladium.

### Claim 5 (depends on 4)

The catalyst according to claim 4, wherein the compound of chromium has a general formula of CrRnm, wherein Rn is an organic anion or a neutral molecule, Rn contains 1-10 carbon atoms, and n is an integer of 1-6.

### Claim 6 (depends on 5)

The catalyst according to claim 5, wherein the compound of chromium includes one or more of chromium acetate, chromium isooctanoate, chromium n-octanoate, chromium acetylacetonate, chromium diisoprene, diphenyl chromium, CrCl3(THF)3, CrCl2(THF)2, (phenyl)tricarbonylchromium, or hexacarbonylchromium.

### Claim 7 (depends on 1)

The catalyst according to claim 1, wherein the organometallic compound includes one or more of an alkyl aluminum compound, an aluminoxane compound, an organoboron compound, and an organic salt.

### Claim 8 (depends on 7)

The catalyst according to claim 7, wherein the alkyl aluminum compound includes an alkyl aluminum compound and an aluminoxane compound;
wherein the aluminoxane compound is methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and modified aluminoxane; wherein the molar ratio of the aluminoxane compound to the alkyl aluminum compound is 100-0.01:1.

### Claim 9 (depends on 7)

The catalyst according to claim 7, wherein the alkyl aluminum compound is one or more of alkyl aluminum halide, alkyl aluminum hydride, or alkyl aluminum sesquichloride.

### Claim 10 (depends on 7)

The catalyst according to claim 7, wherein the organic salt is methyl lithium or methyl magnesium bromide; the inorganic acid is a tetrafluoroboric acid ether complex; the inorganic salt is tetrafluoroborate or hexafluoroantimonate; the organoboron compound includes one or more of boroxine, sodium borohydride, triethylborane, tris(pentafluorophenyl)boron, or tributylborate.