Catalyst composition for polymerization of α-olefin and preparation and use thereof

Patent metadata

Field	Value
Publication number	US-12503523-B2
Application number	US-202218248198-A
Country	US
Kind code	B2
Filing date	Jan 7, 2022
Priority date	Apr 15, 2021
Publication date	Dec 23, 2025
Grant date	Dec 23, 2025

Abstract

The present disclosure discloses a catalyst composition for polymerization of an α-olefin and preparation and use thereof. The catalyst composition comprises boron trifluoride and at least one protic cocatalyst; the protic cocatalyst has a structural formula of X—(CH2)n—OH, where n is an integer selected from 1 to 10; X is selected from nitro, halogen, cyano, sulfonic acid group, aldehyde group, acyl, carboxyl and amino. The catalyst can be used in production of a poly(α-olefin) synthetic base oil, and is particularly suitable for a low viscosity poly(α-olefin) synthetic base oil with high selectivity of the target product.

First claim

The invention claimed is:

1 . A catalyst composition for polymerization of an α-olefin, comprising boron trifluoride and at least one protic cocatalyst;
wherein the protic cocatalyst has a structural formula of:
X—(CH 2 ) n —OH

where n is an integer selected from 1 to 10;
X is selected from nitro, halogen, cyano, sulfonic acid, and carboxyl groups;
the catalyst composition is a complex of boron trifluoride and the protic cocatalyst, and the molar ratio of boron trifluoride to the protic cocatalyst is from 0.1 to 3.0.

2 . The catalyst composition according to claim 1 , wherein the protic cocatalyst is one or a combination of two or more selected from 2-nitroethanol, 3-nitropropanol, 2-chloroethanol, 3-chloro-1-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 7-chloro-1-heptanol, 8-chloro-1-octanol, 9-chloro-1-nonanol, 10-chloro-1-decanol, 2-fluoroethanol, 3-fluoro-1-propanol, 4-fluoro-1-butanol, 5-fluoro-1-pentanol, 6-fluoro-1-hexanol, 7-fluoro-1-heptanol, 8-fluoro-1-octanol, 9-fluoro-1-nonanol, 10-fluoro-1-decanol, 2-bromoethanol, 3-bromo-1-propanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-1-hexanol, 7-bromo-1-heptanol, 8-bromo-1-octanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 2-iodoethanol, 3-iodo-1-propanol, 4-iodo-1-butanol, 5-iodo-1-pentanol, 6-iodo-1-hexanol, 7-iodo-1-heptanol, 8-iodo-1-octanol, 9-iodo-1-nonanol, 10-iodo-1-decanol, 3-hydroxypropionitrile, 4-hydroxybutyronitrile, 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, 4-hydroxybutanesulfonic acid, hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, and 10-hydroxydecanoic acid.

3 . The catalyst composition according to claim 1 , wherein the protic cocatalyst is one or a combination of two or more selected from 4-fluoro-1-butanol, 3-chloro-1-propanol, 3-iodo-1-propanol, 4-bromo-1-butanol, 6-hydroxyhexanoic acid, 3-nitropropanol, 2-hydroxyethanesulfonic acid, 4-hydroxybutanesulfonic acid, 8-hydroxyoctanoic acid and 10-hydroxydecanoic acid.

4 . The catalyst composition according to claim 1 , wherein X is selected from halogen and carboxyl.

5 . The catalyst composition according to claim 4 , wherein the protic cocatalyst is one or a combination of two or more selected from 4-fluoro-1-butanol, 4-bromo-1-butanol and 8-hydroxyoctanoic acid.

6 . The catalyst composition according to claim 1 , wherein a molar ratio of boron trifluoride to the protic cocatalyst is from 0.5 to 2.0.

7 . The catalyst composition according to claim 1 , wherein a molar ratio of boron trifluoride to the protic cocatalyst is from 0.8 to 1.5.

8 . The catalyst composition according to claim 1 , wherein the protic cocatalyst is one or a combination of two or more selected from 4-fluoro-1-butanol, 4-bromo-1-butanol and 8-hydroxyoctanoic acid, and a molar ratio of boron trifluoride to the protic cocatalyst is from 1 to 1.2.

9 . A method for preparing a catalyst composition according to claim 1 , comprising: mixing the protic cocatalyst with boron trifluoride and carrying out a reaction at a predetermined temperature for a predetermined time to obtain the catalyst composition.

10 . The method according to claim 9 , wherein the mixing the protic cocatalyst with boron trifluoride comprises: thermally purging with nitrogen a reactor for preparing a catalyst; after purging with nitrogen, adding the protic cocatalyst while turning on stirring; raising the temperature to a predetermined temperature; and adding boron trifluoride in proportion.

11 . The method according to claim 9 , wherein the predetermined temperature is −30° C. to 50° C.

12 . The method according to claim 9 , wherein the predetermined time is 0.5 h to 4.0 h.

13 . The method according to claim 9 , wherein the protic cocatalyst has been subjected to a refining treatment.

14 . The method according to claim 13 , wherein the refining treatment includes distillation and/or adsorbent removal method, and the water content of the protic cocatalyst after the refining treatment is less than 100 ppm.

15 . The method according to claim 9 , comprising: thermally purging with nitrogen a reactor for preparing a catalyst for 5 min to 10 min; after purging with nitrogen, adding the refined protic cocatalyst while turning on stirring; controlling the temperature at −30° C. to 50° C.; adding boron trifluoride in proportion; and reacting for 0.5 h to 4.0 h to obtain the catalyst composition.

16 . A method of using the catalyst composition according to claim 1 in synthesis of a poly (α-olefin) synthetic base oil, comprising the following steps:
adding a raw material α-olefin to a tank polymerization reactor; adding the catalyst composition continuously to the tank polymerization reactor; controlling the reaction temperature at 20° C. to 50° C. with a residence time of 20 min to 100 min; after the reaction, separating the catalyst, and carrying out hydrogenation to obtain the poly (α-olefin) synthetic base oil.

17 . The method according to 16 , wherein the catalyst composition is added in an amount of 0.1% to 2.0% by mass of the raw material α-olefin.

18 . The method according to claim 9 , wherein the predetermined temperature is −10° C. to 30° C.

19 . The method according to claim 9 , wherein the predetermined time is 0.5 h to 3.0 h.

Assignees

• Petrochina Co Ltd

Inventors

• Cao Yuanyuan
• Liu Tong
• Chu Hongling
• Wang Libo
• Wang Yulong
• Xu Xianming
• Wang Xiuhui
• Gao Han
• Sun Wei
• Li Hongpeng

Classifications

• C08F2410/04

  Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene · CPC title

• C08F110/14 Primary

  Monomers containing five or more carbon atoms · CPC title

• C08F4/32

  Organic compounds · CPC title

• C08F10/14

  Monomers containing five or more carbon atoms · CPC title

• C10G69/12

  including at least one polymerisation or alkylation step · CPC title