Self-humidifying ion-exchange composite membrane and method for fabricating the same

Patent metadata

Field	Value
Publication number	US-2020102435-A1
Application number	US-201716303198-A
Country	US
Kind code	A1
Filing date	May 23, 2017
Priority date	May 24, 2016
Publication date	Apr 2, 2020
Grant date	—

Abstract

The present invention relates to a self-humidifying ion-exchange composite membrane including an aromatic hydrocarbon polymer ion-exchange membrane formed on the surface of a porous polymer support and a thin hydrophobic coating layer having a nanocracked morphology pattern on the surface of the ion-exchange membrane. The self-humidifying ion-exchange composite membrane of the present invention has good thermal/chemical stability, high mechanical strength, high ion-exchange capacity, and good long-term operational stability. Particularly, the self-humidifying ion-exchange composite membrane of the present invention is able to self-hydrate even under high-temperature and low-humidity conditions. Due to these advantages, it is expected that the self-humidifying ion-exchange composite membrane of the present invention will be commercialized as an electrolyte membrane for a fuel cell or a membrane for water treatment.

First claim

1 . A self-humidifying ion-exchange composite membrane comprising a) a porous polymer support, b) an aromatic hydrocarbon polymer ion-exchange membrane formed on the surface of the support, and c) a thin hydrophobic coating layer having a nanocracked morphology pattern on the surface of the ion-exchange membrane.

2 . The self-humidifying ion-exchange composite membrane according to claim 1 , wherein the porous polymer support is made of a polymer selected from the group consisting of polytetrafluoroethylene, thermally rearranged poly(benzoxazole-co-imide), thermally rearranged poly(benzothiazole-co-imide), thermally rearranged poly(pyrrolone-co-imide), polyethylene terephthalate, and a polyarylene ether sulfone copolymer.

3 . The self-humidifying ion-exchange composite membrane according to claim 2 , wherein the thermally rearranged poly(benzoxazole-co-imide) has a repeating unit represented by Formula 1:

wherein each Ar 1 is an aromatic cyclic group selected from substituted or unsubstituted tetravalent C 6 -C 24 arylene groups and substituted or unsubstituted tetravalent C 4 -C 24 heterocyclic groups, with the proviso that the aromatic cyclic group exists alone or in plurality and that the aromatic cyclic groups together form a fused ring or are linked to each other via a single bond, O, S, CO, SO 2 , Si(CH 3 ) 2 , (CH 2 ) p (1≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 or CO—NH, Ar 2 is an aromatic cyclic group selected from substituted or unsubstituted divalent C 6 -C 24 arylene groups and substituted or unsubstituted divalent C 4 -C 24 heterocyclic groups, with the proviso that the aromatic cyclic group exists alone or in plurality and that the aromatic cyclic groups together form a fused ring or are linked to each other via a single bond, O, S, CO, SO 2 , Si(CH 3 ) 2 , (CH 2 ) p (1≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 or CO—NH, Q is a single bond, O, S, CO, SO 2 , Si(CH 3 ) 2 , (CH 2 ) p (1≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 , CO—NH, C(CH 3 )(CF 3 ) or a substituted or unsubstituted phenylene group, and x and y representing the mole fractions of the corresponding structural units satisfy 0.1≤x≤0.9, 0.1≤y≤0.9, and x+y=1.

4 . The self-humidifying ion-exchange composite membrane according to claim 2 , wherein the polyarylene ether sulfone copolymer has a cross-linked repeating unit represented by Formula 2:

wherein each Q is a single bond, O, S, C(═O), C(═O)NH, Si(CH 3 ) 2 , (CH 2 ) p (1≤p≤10), (CF 2 ) q (1≤q≤10), C(CH 3 ) 2 , C(CF 3 ) 2 or C(CH 3 )(CF 3 ) and n representing the molar ratio of the corresponding structural units satisfies 0<n<1.

5 . The self-humidifying ion-exchange composite membrane according to claim 1 , wherein the porous polymer support is an electrospun film or non-woven fabric.

6 . The self-humidifying ion-exchange composite membrane according to claim 1 , wherein the aromatic hydrocarbon polymer is selected from the group consisting of polybenzimidazole, polybenzoxazole, polyimide, polyetherimide, polyphenylene sulfide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylquinoxaline, copolymers thereof, and combinations thereof.

7 . The self-humidifying ion-exchange composite membrane according to claim 1 , wherein the aromatic hydrocarbon polymer ion-exchange membrane comprises: an aromatic hydrocarbon polymer comprising a first repeating unit represented by Formula 3:

wherein X 1 , X 2 , and X 3 are identical to or different from each other and are each independently SO 2 or O, Y 1 and Y 2 are each independently SO 3 H or SO 3 Na, and n1 is an integer from 30 to 70, and
a second repeating unit represented by Formula 4:

wherein X 4 , X 5 , and X 6 are identical to or different from each other and are each independently SO 2 or O, n2 is 100-n1, and n1 is an integer from 30 to 70; and/or
an aromatic hydrocarbon polymer represented by Formula 5, 6 or 7:

wherein X 7 , X 8 , X 9 , X 10 , X 19 , X 20 , X 21 , X 22 , and X 31 are identical to or different from each other and are each independently sulfide (S), ether (O) or sulfone (SO 2 ), T 1 , T 2 , T 3 , T 4 , T 5 , T 6 , T 7 , T 8 , T 20 , T 21 , T 22 , T 23 , T 24 , T 25 , T 26 , T 27 , T 39 , T 40 , T 41 , T 42 , T 43 , T 44 , and T 45 are identical to or different from each other and are each independently fluoro (F), cyano (CN) or sulfo (SO 3 H), Q1 is represented by Formula 5a:

wherein X 30 , X 32 , X 33 , X 34 , X 35 , X 36 , X 37 , X 39 , X 40 , X 41 , and X 42 are identical to or different from each other and are each independently sulfide (S), ether (O) or sulfone (SO 2 ), X 38 is sulfone (SO 2 ), T 50 , T 51 , T 52 , T 53 , T 54 , T 55 , T 56 , and T 57 are identical to or different from each other and are each independently fluoro (F), cyano (CN) or sulfo (SO 3 H), each of T 48 and T 49 is sulfo (SO 3 H), T 47 is cyano (CN), and k5 representing the mole fraction of the corresponding hydrophilic moiety is a real number from 0.4 to 0.6, and k6 representing the mole fraction of the corresponding hydrophobic moiety is a real number from 0.6 to 0.4 satisfying 1-k5, Q2 is represented by Formula 5b:

wherein X 12 , X 13 , X 14 , X 15 , X 16 , X 17 , and X 18 are identical to or different from each other and are each independently sulfide (S), ether (O) or sulfone (SO 2 ), X II is sulfone (SO 2 ), T 12 , T 13 , T 14 , T 15 , T 16 , T 17 , T 18 , and T 19 are identical to or different from each other and are each independently fluoro (F), cyano (CN) or sulfo (SO 3 H), each of T 9 and T 10 are sulfo (SO 3 H), T 11 is cyano (CN), k1 representing the mole fraction of the corresponding hydrophilic moiety is a real number from 0.4 to 0.6, and k2 representing the mole fraction of the corresponding hydrophobic moiety is a real number from 0.6 to 0.4 satisfying 1-k1, and Q3 is represented by Formula 5c:

wherein X 22 , X 24 , X 25 , X 26 , X 27 , X 28 , X 29 , and X 30 are identical to or different from each other and are each independently sulfide (S), ether (O) or sulfone (SO 2 ), X 23 is sulfone (SO 2 ), T 31 , T 32 , T 33 , T 34 , T 35 , T 36 , T 37 , and T 38 are identical to or different from each other and are each independently fluoro (F), cyano (CN) or sulfo (SO 3 H), T 28 and T 29 are each independently sulfo (SO 3 H), T 30 is cyano (CN), k3 representing the mole fraction of the corresponding hydrophilic moiety is a real number from 0.4 to 0.6, and k4 representing the mole fraction of the corresponding hydrophobic moiety is a real number from 0.6 to 0.4 satisfying 1-k3,

wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 are identical to or different from each other and are each independently SO 2 or 0, Y 1 and Y 2 are each independently SO 3 H or SO 3 Na, each of Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y

Assignees

• Univ Hanyang Ind Univ Coop Found

Inventors

• Lee Young Moo
• Park Sang Hyun
• Moon Sun-Ju
• Park Hyun Jin

Classifications

• C08J5/2225 Primary

  containing fluorine · CPC title

• C08J2379/06

  Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles · CPC title

• C08J7/18

  using wave energy or particle radiation · CPC title

• C08J2381/06

  Polysulfones; Polyethersulfones · CPC title

• C08J5/2262

  containing fluorine · CPC title