# US 10,441,946 B2 · Linear alpha-olefin catalysts and preparation and use thereof

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- Number: US 10,441,946 B2
- Document ID: US10441946B2
- Status: Granted
- Kind: B2
- Application number: 15/731,880
- Filed: 2016-04-01
- Published: 2018-05-31
- Granted: 2019-10-15
- Earliest claimed: 2016-03-22
- Assignees: Apalene Technology Co., Ltd. (Hangzhou)
- Applicants: Apalene Technology Co., Ltd. (Jiaxing)
- Inventors: Dongchu Wei; Bing Li
- Web page: https://patentgrep.com/patent/US10441946B2

## CPC

- B01J 31/184: {mixed aromatic/aliphatic ring systems, e.g. indoline}
- B01J 31/143: {of aluminium}
- B01J 31/1815: {with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine}
- B01J 31/183: {with more than one complexing nitrogen atom, e.g. phenanthroline}
- B01J 31/22: Organic complexes
- B01J 31/26: containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- C07C 2/32: as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)}
- B01J 2231/20: Olefin oligomerisation or telomerisation
- B01J 2531/0238: Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J 2531/842: Iron
- C07C 2523/745: Iron
- C07C 2531/14: of aluminium or boron
- C07C 2531/22: Organic complexes
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to a novel linear α-olefin catalyst composition, and preparation and use thereof. The catalyst composition includes a main catalyst and a co-catalyst, wherein the main catalyst is an imino-based iron coordination compound, and the co-catalyst is a mixture of methylaluminoxane, triisobutylaluminum, and borane or GaCl3. The catalyst composition can be used to catalyze ethylene oligomerization to produce linear α-olefins having a selectivity of greater than 96%, carbon distribution between C4-C28 with the component of C6-C20 being greater than 75%. The catalyst of the invention is stable in structure and can be used for ethylene oligomerization with high catalytic efficiency. The method of the invention has the advantages of relatively convenient in operation, readily available of raw materials, high yield, low costs, less pollution and easy for industrial production.

## Claims

### Claim 1

A linear poly-α-olefin catalyst, comprising a main catalyst and a co-catalyst,
wherein the main catalyst has a structure of formula (IA), (IB) or (IC) below:
wherein R1 to R10 are each independently selected from hydrogen, C1-C6 alkyl, halogen and C1-C6 alkoxy; R11 is C1-C6 alkyl, isopropyl or trifluoromethyl;
wherein R1 to R10 are each independently selected from hydrogen, C1-C6 alkyl, halogen and C1-C6 alkoxy; R11 is C1-C6 alkyl, isopropyl or trifluoromethyl; R12 is C1-C6 alkyl, isopropyl or trifluoromethyl;
wherein, R1 to R5 are each independently selected from hydrogen, C1-C6 alkyl, halogen and C1-C6 alkoxy.

### Claim 2 (depends on 1)

The catalyst of claim 1, wherein the main catalyst has formula (IA), and is obtained by reacting 2,6-diacetyl-pyridine phenalene with substituted aniline.

### Claim 3 (depends on 1)

The catalyst of claim 1, wherein the main catalyst has formula (IB), and is obtained by reacting 2-acetyl-6-methylamino with substituted aniline.

### Claim 4 (depends on 1)

The catalyst of claim 1, wherein the main catalyst has formula (IC), and is obtained by reacting 9,10-dihydrobenzo[b][1,10]phenanthroline-11(8H)-one with substituted aniline, wherein the 9,10-dihydrobenzo[b][1,10]phenanthroline-11 (8H)-one is prepared from [1,10] phenanthroline.

### Claim 5 (depends on 1)

The catalyst of claim 1, wherein any one of the terminal phenyl end-groups is mono-, di- or tri-substituted by C1-C4 alkyl, and is selected from the group consisting of 2-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-propylphenyl, 4-propylphenyl, 2,4-dipropylphenyl, 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2,4-diisopropylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2,4-dibutylphenyl, 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-tert-butylphenyl, 4-tert-butylphenyl, 2,4-di-tert-butylphenyl, 2,6-di-, 6-tri-tert-butylphenyl, 2-tert-butylphenyl, 4-tert-butylphenyl, 2,4-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, and 2,4,6-tri-tert-butylphenyl.

### Claim 6 (depends on 1)

The catalyst of claim 1, wherein any one of the terminal phenyl end-groups is mono-, di- or tri-substituted with by halogen, and is selected from the group consisting of 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-bromophenyl, 4-bromophenyl, 2,4-dibromophenyl, 2,4,6-tribromophenyl, 2-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, and 2,4,6-trifluorophenyl.

### Claim 7 (depends on 1)

The catalyst of claim 1, wherein any one of the terminal phenyl end-groups is mono-, di- or tri-substituted by halogen and/or C1-C4 alkyl, and is selected from the group consisting of 2-bromo-4-methylphenyl, 2-bromo-6-methyl phenyl, 2,6-dibromo-4-methylphenyl, 4-bromo-2,6-dimethylphenyl, 2-chloro-4-methylphenyl, 2-chloro-6-methylphenyl, 2,6-dichloro-4-methylphenyl, and 4-chloro-2,6-dimethylphenyl.

### Claim 8 (depends on 1)

The catalyst of claim 1, wherein the co-catalyst is a mixture comprising methylaluminoxane, triisobutylaluminum, and borane or GaCl3.

### Claim 9 (depends on 8)

A method for ethylene oligomerization to linear α-olefins, the method comprising:
adding sequentially an organic solvent, a solution of the co-catalyst of claim 8 and a solution of the main catalyst of claim 8;
contacting the co-catalyst and the main catalyst with ethylene under anhydrous and oxygen-free conditions under ethylene pressure of 0.1-20 MPa and a reaction temperature of 0-100° C. for a duration of 5-60 minutes to produce an oligomerization effluent having linear α-olefin selectivity of >97 and a C6-C20 oligomers distribution being greater than 80% in weight among C4-C28 oligomers;
cooling the oligomerization effluent to −10° C.-0° C. to produce a cooled effluent,
adding methanol to the cooled effluent to terminate the reaction to produce a terminated reaction product, and
distilling the terminated reaction product to separate the linear α-olefin.

### Claim 10 (depends on 9)

The method of claim 9, wherein the organic solvent is petroleum ether, toluene or xylene, solvent of the solution of the main catalyst is 1,2-dichloroethane, dichloromethane, trichloride methane, o-dichlorobenzene, hexane or cyclohexane, and molar ratio of the co-catalyst to the main catalyst on the basis of Al/Fe is 5,000:1 to 500:1.