Block polymer and polymer electrolyte membrane comprising same

Patent metadata

Field	Value
Publication number	US-10947338-B2
Application number	US-201716087512-A
Country	US
Kind code	B2
Filing date	Mar 21, 2017
Priority date	Mar 29, 2016
Publication date	Mar 16, 2021
Grant date	Mar 16, 2021

Abstract

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

First claim

The invention claimed is:

1. A block polymer comprising:
a hydrophobic block; and
a hydrophilic block,
wherein the hydrophilic block includes a unit derived from a compound represented by the following Chemical Formula 1, and
the hydrophobic block includes a cationic group and a halogen group:

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;
R 1 to R 5 are the same as or different from each other, and each independently hydrogen;
a halogen group; or a hydroxyl group;
at least two of R 1 to R 5 are a halogen group; or a hydroxyl group;
R 6 and R 7 are the same as or different from each other, and each independently a halogen group;
L 1 is a direct bond; —S—; —O—; —N(R)—; —SO 2 —; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
a is an integer of 0 to 2, and when a is 2, structures in the parentheses are the same as or different from each other;
R is hydrogen; or a substituted or unsubstituted alkyl group;
n is an integer of 2 to 10, and when n is 2 or greater, structures in the parentheses are the same as or different from each other,
wherein the hydrophobic block includes a unit derived from one or more types of a compound represented by the following Chemical Formula 3, a compound represented by the following Chemical Formula 4, and a compound represented by the following Chemical Formula 5:

in Chemical Formula 3 and Chemical Formula 4:
A 1 and A 2 are the same as or different from each other, and each independently a hydroxyl group; a thiol group; or a halogen group;
S 1 and S 2 are the same as or different from each other, and each independently hydrogen; deuterium; a halogen 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 2 ) b -N + R 11 R 12 R 13 ; -(L 2 ) b -P + R 11 R 12 R 13 ; or a structure represented by the following Chemical Formula 2;
c and d are each an integer of 1 to 4;
when c and d are each an integer of 2 or greater, structures in the two or more parentheses are the same as or different from each other;
S 3 and S 4 are the same as or different from each other, and each independently hydrogen; a halogen group; an alkyl group; or a haloalkyl group;
E 1 and E 2 are the same as or different from each other, and each independently a hydroxyl group; a thiol group; or a halogen group;
e is an integer of 1 to 4;
f is an integer of 1 to 3;
when e and f are each an integer of 2 or greater, structures in the parentheses are the same as or different from each other;
S 5 is hydrogen; deuterium; a halogen 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 2 ) b -N + R 11 R 12 R 13 : -(L 2 ) b -P + R 11 R 12 R 13 ; or a structure represented by the following Chemical Formula 2;
S 3 and S 4 are each independently a halogen group or a haloalkyl group, or S 5 is a halogen group or a haloalkyl group; and
the hydrophobic block includes one, two or more of -(L 2 ) b -N + R 11 R 12 R 13 ; -(L 2 ) b -P + R 11 R 12 R 13 ; and a structure represented by the following Chemical Formula 2,
in Chemical Formula 5:
X 1 is a direct bond; —CO—; —SO 2 —; or an alkylene group substituted with a halogen group;
X 2 is —O—; or —S—;
X 3 is a direct bond or an alkylene group substituted with a halogen group;
k is 0 or 1;
p, q, r and s are each independently an integer of 0 to 4;
t, u, v and w are each independently 0 or 1;
a sum of t, u, v and w is 1 or greater;
a sum of p and t, a sum of q and u, a sum of r and v and a sum of s and w are each 4;
when p, q, r and s are each 2 or greater, substituents in the parentheses are the same as or different from each other;
R 21 to R 24 are the same as or different from each other, and each independently hydrogen or a halogen group;
at least one of X 1 and X 3 is an alkylene group substituted with a halogen group, and at least one of R 21 to R 24 is a halogen group;
R 31 to R 34 are hydrogen; -(L 2 ) b -N + R 11 R 12 R 13 ; -(L 2 ) b -P + R 11 R 12 R 13 ; or a cationic group represented by the Chemical Formula 2; and
at least one of R 31 to R 34 is -(L 2 ) b -N + R 11 R 12 R 13 ; -(L 2 ) b -P + R 11 R 12 R 13 ; or a cationic group represented by the Chemical Formula 2;

in Chemical Formula 2,
L 2 is a direct bond: —O—; —N(R 14 )—; —S—; —SO 2 —; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms;
b is an integer of 1 to 10;
when b is 2 or greater, the two or more L 2 s are the same as or different from each other; and
R 11 to R 15 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.

2. The block polymer of claim 1 , wherein Chemical Formula 3 is represented by the following Chemical Formula 3-1; and
Chemical Formula 4 is represented by the following Chemical Formula 4-1:

in Chemical Formula 3-1 and Chemical Formula 4-1,
S 1 , S 2 , c, d and f have the same definitions as in Chemical Formula 3 or Chemical Formula 4.

3. 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 1-9:

4. The block polymer of claim 1 , wherein the hydrophilic block and the hydrophobic block are included in a mole ratio of 1:0.001 to 1:100 in the block polymer.

5. The block polymer of claim 1 , further comprising a brancher.

6. The block polymer of claim 1 , which has a weight average molecular weight of 500 g/mol to 5,000,000 g/mol.

7. A polymer electrolyte membrane comprising the block polymer of claim 1 .

8. The polymer electrolyte membrane of claim 7 , which has ion conductivity of 0.01 S/cm to 0.5 S/cm.

9. The polymer electrolyte membrane of claim 7 , which h

Assignees

• Lg Chemical Ltd

Inventors

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

Classifications

• H01M8/1025 Primary

  having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters · CPC title

• H01M8/1027

  having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES] · CPC title

• H01M8/188

  by recharging of redox couples containing fluids; Redox flow type batteries · CPC title

• C08G65/4056

  (I) or (II) containing sulfur (as the sulfone group C08G75/23) · CPC title

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title