Block polymer and polymer electrolyte membrane including same

Patent metadata

Field	Value
Publication number	US-10899874-B2
Application number	US-201615753095-A
Country	US
Kind code	B2
Filing date	Sep 22, 2016
Priority date	Sep 22, 2015
Publication date	Jan 26, 2021
Grant date	Jan 26, 2021

Abstract

The present specification relates to a block polymer and a polymer electrolyte membrane comprising the same, a membrane-electrode assembly comprising the polymer electrolyte membrane, a fuel cell comprising the membrane-electrode assembly, and a redox flow battery comprising the polymer electrolyte membrane.

First claim

The invention claimed is:

1. A block polymer comprising:
a hydrophobic block; and
a hydrophilic block,
wherein the hydrophobic block comprises at least one cationic side chain, and
the hydrophilic block comprises a unit derived from a compound represented by the following Chemical Formula 1:

wherein, in Chemical Formula 1,
A is —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− 2M + , —O(CF 2 ) m SO 3 H, —O(CF 2 ) m SO 3 − M + , —O(CF 2 ) m COOH, —O(CF 2 ) m COO − M + , —O(CF 2 ) m PO 3 H 2 , —O(CF 2 ) m PO 3 H − M + or —O(CF 2 ) m PO 3 2− 2M + ;
m is an integer of 2 to 6;
M is a group 1 element;
R1 to R5 are the same as or different from each other, and each independently hydrogen; a halogen group; or a hydroxyl group;
at least two of R1 to R5 are a halogen group; or a hydroxyl group;
R6 and R7 are the same as or different from each other, and each independently a halogen group;
L(a) is a direct bond; S; O; NRa; SO 2 ; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
Ra is hydrogen; or a substituted or unsubstituted alkyl group; and
n is an integer of 2 to 10, and structures in the 2 to 10 parentheses are the same as or different from each other,
wherein the hydrophobic block comprises a unit represented by the following Chemical Formula 2 or Chemical Formula 3:

wherein, in Chemical Formula 2 and Chemical Formula 3,
S1 to S4 are the same as or different from each other, and each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; -(L)o-N + RR′R″; -(L)o-P + RR′R″; or the following Chemical Formula 1-A;

L is a direct bond; O; NR′″; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
o is an integer of 1 to 10;
when o is 2 or greater, two or more Ls are the same as or different from each other;
R, R′, R″, R′ and Rb are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms:
a, a′, b and b′ are each an integer of 1 to 4; and
when a, a′, b and b′ are each an integer of 2 or greater, structures in the two or more parentheses are the same as or different from each other.

2. The block polymer of claim 1 , wherein the cationic side chain is -(L)o-N + RR′R″; -(L)o-P + RR′R″; or the following Chemical Formula 1-A:

L is a direct bond; 0; NR′″; S; SO 2 ; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
o is an integer of 1 to 10;
when o is 2 or greater, two or more Ls are the same as or different from each other; and
R, R′, R″, R′″ and Rb are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

3. The block polymer of claim 1 , wherein the hydrophobic block or the hydrophilic block further comprises a unit derived from a compound represented by the following Chemical Formula 4:

wherein, in Chemical Formula 4,
E1 and E2 are a hydroxyl group or a thiol group;
S5 is hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; -(L)o-N + RR′R″; -(L)o-P + RR′R″; or the following Chemical Formula 1-A;

L is a direct bond; O; NR′″; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
o is an integer of 1 to 10;
when o is 2 or greater, two or more Ls are the same as or different from each other;
R, R′, R″, R′ and Rb are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
c is an integer of 1 to 4;
c′ is an integer of 1 to 3; and
when c and c′ are each an integer of 2 or greater, structures in the two or more parentheses are the same as or different from each other.

4. The block polymer of claim 1 , wherein the hydrophobic block further comprises a unit derived from a compound represented by the following Chemical Formula 4:

in Chemical Formulae 2 to 4,
E1 and E2 are a hydroxyl group or a thiol group;
each S5 is the same as or different from each other, and each independently hydrogen; deuterium; a halogen group; a cyano group; a nitrile group; a nitro group; a hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; -(L)o-N + RR′R″; -(L)o-P + RR′R″; or the following Chemical Formula 1-A;

L is a direct bond; 0; NR′″; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
o is an integer of 1 to 10;
when o is 2 or greater, two or more Ls are the same as or different from each other;
R, R′, R″, R′″ and Rb are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
a, a′, b, b′ and c are each an integer of 1 to 4;
c′ is an integer of 1 to 3; and
when a, a′, b, b′, c and c′ are each an integer of 2 or greater, structures in the two or more parentheses are the same as or different from each other.

5. The block polymer of claim 1 , wherein the unit derived from the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulae 1-1 to 1-18:

6. The block polymer of claim 1 , wherein the unit derived from the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulae 1-19 to 1-36:

Assignees

• Lg Chemical Ltd

Inventors

• Jang Yong Jin
• Han Joong Jin
• Kang Esder
• Yu Yunah
• Kim Youngjea

Classifications

• C08J2365/00

  Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08J2307/00 - C08J2357/00, C08J2361/00 take precedence); Derivatives of such polymers · CPC title

• Y02E60/50

  Fuel cells · CPC title

• B01D71/32

  containing fluorine atoms · CPC title

• B01D71/62

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain · CPC title

• C08G2261/3444

  Polyethersulfones · CPC title