Block copolymer, ion-exchange membrane and method of preparing block copolymer

Patent metadata

Field	Value
Publication number	US-10717835-B2
Application number	US-201715490159-A
Country	US
Kind code	B2
Filing date	Apr 18, 2017
Priority date	Nov 16, 2016
Publication date	Jul 21, 2020
Grant date	Jul 21, 2020

Abstract

A block copolymer, an ion-exchange membrane including the block copolymer and a method of preparing the block copolymer are provided. The block copolymer may include a hydrophobic repeating unit and a hydrophilic repeating unit.

First claim

What is claimed is:

1. A block copolymer comprising:
a hydrophobic repeating unit represented by Formula 1 below; and
a hydrophilic repeating unit represented by Formula 2 below:

wherein in Formulae 1 and 2,
n and m are each independently an integer of 1 to 1000,
Ar 1 is an aromatic group including a single benzene ring or at least two benzene rings, the at least two benzene rings are directly connected to each other or are bonded to each other through a linking group selected from —O—,—S—, —S(O 2 )—, —(C(O))—, —(CF 2 ) n —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, an imide bond, an ether imide bond, phosphine, imidazole, or —(CH 2 ) n — in which n is an integer of 1 to 10, each of the benzene rings is unsubstituted or substituted with —COR 1 or —CN, and R 1 is an aromatic group including at least one benzene ring;
Ar 2 is a benzene ring substituted with —COR 2 or —(CH 2 ) n CH 3 in which n is an integer of 0 to 6, and R 2 is an aromatic group including at least one benzene ring that is unsubstituted or substituted with —(CH 2 ) n CH 3 in which n is an integer of 0 to 6;
Ar 3 and Ar′ 3 are each independently an aromatic group including a single benzene ring or at least two benzene rings, the at least two benzene rings are directly connected to each other or are bonded to each other through a linking group selected from —O—, —S—, —S(O 2 )—, —(C(O))—, —C(CH 3 ) 2 —, —(CH 2 ) n —, —C(CF 3 ) 2 —, or —(CF 2 ) n — in which n is an integer of 1 to 10, and each of the benzene rings is unsubstituted or substituted with a halogen ion, hydroxy, acetylene, or —(CH 2 ) n CH 3 in which n is an integer of 0 to 6;
Ar 4 and Ar′ 4 are the same as Ar 1 and Ar 2 , or are

wherein n is an integer of 1 or 2, two of R a through R d are connected to a main chain of the block copolymer, and the rest are the same as or different from each other and are hydrogen, benzene or alkyl;
A is —O—, —S—, or —S(O 2 )—;
z is an integer of 0 or 1; and
x and y are each independently an integer of 1 to 100.

2. The block copolymer of claim 1 , wherein Ar 1 is selected from the group consisting of:

3. The block copolymer of claim 1 , wherein Ar 1 is selected from the group consisting of:

wherein a and b are each independently an integer of 1 to 100.

4. The block copolymer of claim 1 , wherein R 1 is selected from the group consisting of:

5. The block copolymer of claim 1 , wherein Ar 2 is selected from the group consisting of:

6. The block copolymer of claim 1 , wherein Ar 2 is selected from the group consisting of:

wherein a and b are each independently an integer of 1 to 100.

7. The block copolymer of claim 1 , wherein R 2 is selected from the group consisting of:

8. The block copolymer of claim 1 , wherein Ar3 and Ar′3 are each independently an aromatic group represented by Formulae 3a through 3d below:

wherein R 3 is fluorine (F), chlorine (Cl), hydroxy, acetylene, or —(CH 2 ) n CH 3 in which n is an integer of 0 to 10, W is —O—, —S—, —S(O 2 )—, —(C(O))—, —C(CH 3 ) 2 —, —(CH 2 ) n —, —C(CF 3 ) 2 —, or —(CF 2 ) n —in which n is an integer of 1 to 10, c is an integer of 0 to 4, and d is an integer of 0 to 100.

9. The block copolymer of claim 1 , wherein Ar 3 and Ar′ 3 are selected from the group consisting of:

wherein n is an integer of 1 or 2.

10. The block copolymer of claim 1 , wherein a repeating unit represented by Formula 1 is present in an amount of 50% by moles (mol %) to 95 mol %, and a repeating unit represented by Formula 2 is present in an amount of 5 mol % to 50 mol %, based on a total mole number of repeating units included in a polymer chain of the block copolymer.

11. A method of preparing the block copolymer of claim 1 , the method comprising:
performing polymerization by adding a hydrophobic oligomer represented by Formula 4 below, a hydrophilic oligomer represented by Formula 5 below, and a chain extender, to prepare a block copolymer represented by Formula 7 below:

wherein R and R′ are each independently a hydroxyl group (OH), fluorine (F), chlorine (Cl), bromine (Br), iodine (I), or

one of R a through R d is connected to Ar 4 or Ar′ 4 , respectively, and the rest are the same as or different from each other and are hydrogen, benzene or alkyl, and wherein in Formulae 4, 5, and 7,
n and m are each independently an integer of 1 to 1000,
Ar 1 is an aromatic group including a single benzene ring or at least two benzene rings, the at least two benzene rings are directly connected to each other or are bonded to each other through a linking group selected from —O—, —S—, —S(O 2 )—, —(C(O))—, —(CF 2 ) n —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, an imide bond, an ether imide bond, phosphine, imidazole, or —(CH 2 ) n — in which n is an integer of 1 to 10, each of the benzene rings is unsubstituted or substituted with —COR 1 or —CN, and R 1 is an aromatic group including at least one benzene ring;
Ar 2 is a benzene ring substituted with —COR 2 or —(CH 2 ) n CH 3 in which n is an integer of 0 to 6, and R 2 is an aromatic group including at least one benzene ring that is unsubstituted or substituted with —(CH 2 ) n CH 3 in which n is an integer of 0 to 6;
Ar 3 and Ar′ 3 are each independently an aromatic group including a single benzene ring or at least two benzene rings, the at least two benzene rings are directly connected to each other or are bonded to each other through a linking group selected from —O—, —S—, —S(O 2 )—, —(C(O))—, —C(CH 3 ) 2 —, —(CH 2 ) n —, —C(CF 3 ) 2 —, or —(CF 2 ) n — in which n is an integer of 1 to 10, and each of the benzene rings is unsubstituted or substituted with a halogen ion, hydroxy, acetylene, or —(CH 2 ) n CH 3 in which n is an integer of 0 to 6;
Ar 4 and Ar′ 4 are the same as Ar 1 , and Ar 2 or are

wherein n is an integer of 1 or 2, two of R a through R d are connected to a main chain of the block copolymer, and the rest are the same as or different from each other and are hydrogen, benzene or alkyl;
A is —O—, —S—, or —S(O 2 )—;
z is an integer of 0 or 1; and
x and y are each independently an integer of 1 to 100.

12. Th

Assignees

• Korea Inst Energy Res

Inventors

• Bae Byungchan
• Yim Sung-Dae
• Kim Chang-Soo
• Lee Won-Yong
• Park Gu-Gon
• Yang Tae-Hyun
• Park Seok-Hee
• Kim Minjin
• Sohn Young-Jun
• Kim Seung-Gon
• Shin Dong Won
• Nugraha Adam Febriy-Anto

Classifications

• Y02E60/50

  Fuel cells · CPC title

• C08G65/4025

  (I) or (II) containing fluorine other than as leaving group (X) · CPC title

• B01J47/12

  characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes (electrodialysis or electro-osmosis B01D61/42) · CPC title

• C08J5/2262 Primary

  containing fluorine · CPC title

• C08J5/2225

  containing fluorine · CPC title