Fluorine-containing graft copolymer, and preparation method and use thereof

Patent metadata

Field	Value
Publication number	US-12441825-B2
Application number	US-202117801304-A
Country	US
Kind code	B2
Filing date	Jul 16, 2021
Priority date	Jun 28, 2021
Publication date	Oct 14, 2025
Grant date	Oct 14, 2025

Abstract

The invention provides a fluorine-containing graft copolymer, and a preparation method and use thereof. The method includes the following steps: under a protective atmosphere, reacting a compound of Formula (I) and a compound of Formula (II) in a first organic solvent in the presence of a catalyst and a ligand at 20-30° C., to obtain the fluorine-containing graft copolymers of Formula (III) after complete reaction. The compounds of Formulas (I) and (II), and the fluorine-containing graft copolymer of Formula (III) have a structural formula shown below:and the compound of Formula (II) comprises a polyethylene glycol segment and a terminal alkynyl group, wherein a=4-8; b=6-8; n=1-20; and m=3-22. In the present invention, a graft copolymer of a main-chain-type “semi-fluorinated” alternating copolymer is obtained for the first time by post-polymerization modification using a reactive functional group contained in the main-chain-type “semi-fluorinated” alternating copolymers.

First claim

What is claimed is:

1. A method for preparing a fluorine-containing graft copolymer, comprising steps of: under a protective atmosphere, reacting a compound of Formula (I) and a compound of Formula (II) in a first organic solvent in the presence of a catalyst and a ligand at 20-30° C., to obtain the fluorine-containing graft copolymer of Formula (III), wherein the compounds of Formulas (I) and (II), and the fluorine-containing graft copolymers of Formula (III) have a structural formula shown below:

wherein a=4-8; b=6-8; n=1-20; and m=3-22.

2. The preparation method according to claim 1 , wherein the compound of Formula (I) is prepared by a process comprising:
under a protective atmosphere, reacting a compound of Formula (A) with an azide in a second organic solvent, in the presence of a phase catalyst at 50-55° C., to obtain the compound of Formula (I),
wherein the compound of Formula (A) has a structural formula of:

wherein a=4-8; b=6-8; and n=1-20.

3. The preparation method according to claim 2 , wherein the phase catalyst comprises a crown ether compound; and the second organic solvent is selected from the group consisting of chloroform, N, N-dimethyl formamide, dimethyl sulfoxide and any combination thereof.

4. The preparation method according to claim 2 , wherein the molar ratio of the compound of Formula (A) to the azide is 1:1-1:40; and the molar ratio of the compound of Formula (A) to the phase catalyst is 1:2-1:80.

5. The preparation method according to claim 1 , wherein the molar ratio of the compound of Formula (I) to the compound of Formula (II) is 1:20-1:80.

6. The preparation method according to claim 1 , wherein the catalyst is selected from the group consisting of cuprous bromide, cuprous chloride, cupric sulfate pentahydrate and any combination thereof; and the ligand comprises pentamethyl diethylenetriamine and/or ascorbic acid.

7. The preparation method according to claim 1 or 6 , wherein the molar ratio of the compound of Formula (I) to the catalyst is 1:1-1:4; and the molar ratio of the compound of Formula (I) to the ligand is 1:2-1:20.

8. The preparation method according to claim 1 , wherein the first organic solvent is selected from the group consisting of toluene, N, N-dimethyl formamide, and tetrahydrofuran and any combination thereof.

9. A fluorine-containing graft copolymer prepared by the method according to claim 1 , wherein the fluorine-containing graft copolymer comprises a lipophilic chain having a fluorine-containing segment and a hydrophilic chain having a polyethylene glycol segment, the polyethylene glycol segment is a side chain; and the fluorine-containing graft copolymer has a structural formula (III):

wherein a=4-8; b=6-8; n=1-20; and m=3-22.

10. A method for preparation of a surfactant comprising providing the fluorine-containing graft copolymer according to claim 9 and utilizing the fluorine-containing graft copolymer to form the surfactant.

Assignees

• Univ Soochow

Inventors

• Zhang Lifen
• Cheng Jiannan
• Cheng Zhenping
• Wang Jinying
• Zhu Xiulin

Classifications

• C07D249/04 Primary

  1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles · CPC title

• C08G81/025

  containing polyether sequences · CPC title

• Y02E60/50

  Fuel cells · CPC title

• C08G65/337

  containing other elements (organic compounds containing halogens only as halides of a carboxyl group C08G65/332) · CPC title

• C08F259/08 Primary

  on to polymers containing fluorine · CPC title