Method for producing ionic polymer membrane
View Patent ↗To provide a simple method whereby an ionic polymer membrane having a high ion exchange capacity and a low water uptake can be produced by converting a —SO 2 F group in a polymer to a pendant group having multiple ion exchange groups, while preventing a cross-linking reaction. At the time of obtaining an ionic polymer membrane by converting —SO 2 F (group (1)) in a polymer sequentially to —SO 2 NZ 1 Z 2 (group (2)), —SO 2 N − (M α + )SO 2 (CF 2 ) 2 SO 2 F (group (3)), —SO 2 N − (H + )SO 2 (CF 2 ) 2 SO 2 F (group (4)) and —SO 2 N − (M β + )SO 2 (CF 2 ) 2 SO 3 − M β + (group (5)), the polymer is formed into a polymer membrane in the state of any one of the groups (1) to (4), and the polymer membrane is thermally treated in the state of group (4). Here, Z 1 and Z 2 are hydrogen atoms, etc., M α + is a monovalent cation, and M β + is a hydrogen ion or a monovalent cation.
1. A method for producing an ionic polymer membrane comprising the following steps (A) to (F):
(A) a step of converting a group represented by the following formula (1) in a polymer (i) having a constituent unit having the group represented by the formula (1), to a group represented by the following formula (2) to form a polymer (ii),
(B) a step of reacting the polymer (ii) with a compound represented by the following formula (a) to convert the group represented by the formula (2) in the polymer (ii) to a group represented by the following formula (3) to form a polymer (iii),
(C) a step of converting the group represented by the formula (3) in the polymer (iii) to a group represented by the following formula (4) to form a polymer (iv),
(D) a step of forming a polymer membrane which contains the polymer (i), prior to the step (A), or
forming a polymer membrane which contains the polymer (ii), between the step (A) and the step (B), or
forming a polymer membrane which contains the polymer (iii), between the step (B) and the step (C), or
forming a polymer membrane which contains the polymer (iv), between the step (C) and the following step (E),
(E) a step of thermally treating the polymer membrane containing the polymer (iv), subsequent to the step (C) and between the step (D) and the following step (F),
(F) a step of converting the group represented by the formula (4) in the polymer (iv) to a group represented by the following formula (5) to form a polymer (v), thereby to obtain an ionic polymer membrane which contains the polymer (v);
—SO 2 F (1)
—SO 2 NZ 1 Z 2 (2)
FSO 2 (CF 2 ) 2 SO 2 F (a)
—SO 2 N − (M α + )SO 2 (CF 2 ) 2 SO 2 F (3)
—SO 2 N − (H + )SO 2 (CF 2 ) 2 SO 2 F (4)
—SO 2 N − (M β + )SO 2 (CF 2 ) 2 SO 3 − M β + (5)
wherein each of Z 1 and Z 2 which are independent of each other, is a group selected from the group consisting of a hydrogen atom, a monovalent metal element and Si(R) 3 ,
R is a hydrogen atom, or a C 1-12 monovalent organic group which may have an etheric oxygen atom, and three R may be the same or different groups one another,
M α + is a monovalent metal cation, or a monovalent cation derived from an organic amine, and
M β + is an hydrogen ion, a monovalent metal cation, or a monovalent cation derived from an organic amine.
2. The method for producing an ionic polymer membrane according to claim 1 , wherein the group represented by the formula (2) is —SO 2 NH 2 .
3. The method for producing an ionic polymer membrane according to claim 1 , wherein in the step (B), the amount of the compound (a) to be used, is from 0.5 to 20 by molar ratio to the group represented by the formula (2) in the polymer (ii).
4. The method for producing an ionic polymer membrane according to claim 1 , wherein in the step (E), the polymer membrane is thermally treated at a temperature of at most 160° C.
5. The method for producing an ionic polymer membrane according to claim 1 , wherein the polymer (i) is a perfluoropolymer.
6. A method for producing a catalyst layer for a polymer electrolyte fuel cell, wherein the catalyst layer is produced as an ionic polymer membrane by the method for producing an ionic polymer membrane as defined in claim 1 .
7. A method for producing an electrolyte membrane for a polymer electrolyte fuel cell, wherein the electrolyte membrane is produced as an ionic polymer membrane by the method for producing an ionic polymer membrane as defined in claim 1 .
8. The method for producing an electrolyte membrane for a polymer electrolyte fuel cell according to claim 7 , wherein the electrolyte membrane further contains at least one type of atoms selected from the group consisting of cerium and manganese.
9. A method for producing a membrane/electrode assembly for a polymer electrolyte fuel cell, which comprises an anode having a catalyst layer, a cathode having a catalyst layer, and an electrolyte membrane disposed between the anode and the cathode, wherein either one or each of the electrolyte membrane and the catalyst layers, is formed as an ionic polymer membrane by the method for producing an ionic polymer membrane as defined in claim 1 .