Polymer electrolyte membrane

Patent metadata

Field	Value
Publication number	US-2018261868-A1
Application number	US-201515531584-A
Country	US
Kind code	A1
Filing date	Dec 4, 2015
Priority date	Dec 4, 2014
Publication date	Sep 13, 2018
Grant date	—

Abstract

The present specification relates to a polymer electrolyte membrane including two types of polymers.

First claim

1 . A polymer electrolyte membrane comprising:
a polymer including a unit represented by the following Chemical Formula 1; and a polymer including at least one cationic side chain:

wherein, 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 1 to 6;
M is a group 1 element;
R1 and R2 are the same as or different from each other, and each independently a halogen group;
n is an integer of 1 to 10; and
when m and n are 2 or greater, two or more structures in the parentheses are the same as or different from each other.

2 . The polymer electrolyte membrane 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:

wherein, L is a direct bond; O; 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 Ra 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 polymer electrolyte membrane of claim 1 , wherein the polymer including at least one cationic side chain includes a unit represented by the following Chemical Formula 2:

in Chemical Formula 2,
La is CO; SO 2 ; or C(CF 3 ) 2 ;
S1 and S2 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)o-N + RR′R″; -(L)o-P + RR′R″; or the following Chemical Formula 1-A;

in Chemical Formula 1-A,
L is a direct bond; O; 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;
R, R′, R″, R′″ and Ra 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 and a′ are each an integer of 1 to 4; and
when a and a′ are each an integer of 2 or greater, two or more structures in the parentheses are the same as or different from each other.

4 . The polymer electrolyte membrane of claim 1 , wherein the polymer including at least one cationic side chain further includes a unit derived from a compound represented by the following Chemical Formula 3:

in Chemical Formula 3,
E1 and E2 are a hydroxyl group or a thiol group;
S5 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)o-N + RR′R″; -(L)o-P + RR′R″; or the following Chemical Formula 1-A;

in 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;
R, R′, R″, R′″ and Ra 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;
b is an integer of 1 to 4;
c is an integer of 1 to 3; and
when b and c are each an integer of 2 or greater, two or more structures in the parentheses are the same as or different from each other.

5 . The polymer electrolyte membrane of claim 1 , wherein a first unit represented by Chemical Formula 1 is represented by any one of the following Chemical Formulae 1-1 to 1-9:

6 . The polymer electrolyte membrane of claim 1 , wherein the polymer including a unit represented by Chemical Formula 1 includes the unit represented by Chemical Formula 1 in 1 mol % to 100 mol %.

7 . The polymer electrolyte membrane of claim 1 , wherein the polymer including a unit represented by Chemical Formula 1 is a random polymer.

8 . The polymer electrolyte membrane of claim 1 , wherein the polymer including a unit represented by Chemical Formula 1 is a block polymer including a hydrophilic block; and a hydrophobic block, and the hydrophilic block includes the unit represented by Chemical Formula 1.

9 . The polymer electrolyte membrane of claim 8 , wherein the polymer including a unit represented by Chemical Formula 1 includes the hydrophilic block and the hydrophobic block in a molar ratio of 1:0.1 to 1:10.

10 . The polymer electrolyte membrane of claim 1 , wherein the polymer including a unit represented by Chemical Formula 1 further includes a brancher derived from a compound represented by the following Chemical Formula 4; or
a brancher represented by the following Chemical Formula 5:

in Chemical Formulae 4 and 5,
X is S; O; CO; SO; SO 2 ; NR″″; a hydrocarbon-based or fluorine-based assembly;
1 is an integer of 0 to 10;
when 1 is 2 or greater, two or more Xs are the same as or different from each other;
Y1 and Y2 are the same as or different from each other, and each independently NR″″R″″; an aromatic ring in which one or two or more are substituted with substituents selected from the group consisting of a hydroxyl group and a halogen group; or an aliphatic ring in which one or two or more are substituted with substituents selected from the group consisting of a hydroxyl group and a halogen group;
R″″ is hydrogen; an aromatic ring substituted with a halogen group; or an aliphatic ring substituted with a halogen group; and
Z is a trivalent organic group.

11 . The polymer electrolyte membrane of claim 1 , comprising the polymer including a unit represented by Chemical Formula 1 and the polymer including at least one cationic side chain in a weight ratio of 1:1 to 1:50.

Assignees

• Lg Chemical Ltd

Inventors

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

Classifications

• C08J5/22

  Films, membranes or diaphragms · CPC title

• H01M8/1006

  Corrugated, curved or wave-shaped MEA · CPC title

• C08G75/02

  Polythioethers · CPC title

• H01M8/1039

  halogenated, e.g. sulfonated polyvinylidene fluorides · CPC title

• C08G81/00 Primary

  Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers (involving only carbon-to-carbon unsaturated bond reactions C08F299/00 {; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42}) · CPC title