Aromatic sulfonic acid derivative, sulfonic acid group-containing polymer, block copolymer, polymer electrolyte material, polymer electrolyte form article, and polymer electrolyte fuel cell

Patent metadata

Field	Value
Publication number	US-9553326-B2
Application number	US-201514843695-A
Country	US
Kind code	B2
Filing date	Sep 2, 2015
Priority date	Jun 28, 2011
Publication date	Jan 24, 2017
Grant date	Jan 24, 2017

Abstract

Provided are an aromatic sulfonic acid derivative and a sulfonic acid group-containing polymer, each of which has excellent proton conductivity even under low humidification conditions, while having excellent mechanical strength and chemical stability, and enables a solid polymer fuel cell to achieve high output and excellent physical durability when used therein. This aromatic sulfonic acid derivative has a specific structure and is characterized in that a sulfonic acid group is introduced into more than 50% of all the phenyl groups. This sulfonic acid group-containing polymer is characterized by being obtained by polymerization using the aromatic sulfonic acid derivative, and is also characterized by having a specific structure.

First claim

The invention claimed is:

1. A compound comprising an aromatic sulfonic acid derivative as represented by formula (M1), wherein a sulfonic acid group is contained in more than 50% of all phenyl groups:

wherein, in the formula (M1), n 1 is an integer of 1 or greater; a 1 to a 4 are each an integer of 0 or greater; M's are independently a hydrogen, a metal cation, an ammonium cation, or a hydrocarbon group with a carbon number of 1 to 20; X 1 's are independently a halogen atom; Y 1 is an electron-withdrawing group; and Z 1 is an electron-withdrawing group, —O—, —S—, or direct bonding.

2. The compound as claimed in claim 1 , wherein the formula (M1) is as represented by formula (M2):

wherein, in the formula (M2), n 2 is an integer of 1 or greater; M's are independently a hydrogen, a metal cation, an ammonium cation, or a hydrocarbon group with a carbon number of 1 to 20; X 2 's are independently F or Cl; and Y 2 is —CO—or —SO 2 —.

3. The compound as claimed in claim 2 , wherein the formula (M2) is as represented by formula (M3):

wherein, in the formula (M3), n 3 is an integer of 1 to 3, and M's are independently a hydrogen, a metal cation, an ammonium cation, or a hydrocarbon group with a carbon number of 1 to 20.

4. A block copolymer comprising one or more segments (A1) containing an ionic group and one or more segments (A2) containing no ionic group, wherein the segments (A1) comprises a constituent unit as represented by formula (S1):

wherein, in the formula (S1), X 4 is a sulfonic acid group; c 1 is an integer of 1 or greater; Y 4 is an electron-withdrawing group; and Z 4 is an electron-withdrawing group, —O—, —S—, or direct bonding; X 4 , c 1 , Y 4 , and Z 4 each represent one group or number or a plurality of different groups or numbers; and * indicates bonding sites to constituent units as represented by the formula (S1) or to other constituent units.

5. The block copolymer as claimed in claim 4 , wherein the electron-withdrawing group Y 4 is —CO—.

6. The block copolymer as claimed in claim 4 , wherein Z 4 is —O—.

7. The block copolymer as claimed in claim 4 , wherein the segment (A1) containing an ionic group comprises at least a constituent unit as represented by formula (Q1) and/or formula (Q2) and a constituent unit as represented by formula (Q4), the molar fractions of the constituent units represented by the formulae (Q1), (Q2), (Q3), and (Q4) meeting formula (T1):
0≦Y<X<Z<1  (T1)

wherein relative to a total molar quantity of the constituent units represented by any of the formulae (Q1) to (Q4), X is a sum of the molar fractions of the constituent units represented by the formula (Q1) and the formula (Q2) while Y and Z are respectively molar fractions of the constituent units represented by the formulae (Q3) and (Q4), and wherein formula X+Y+Z=1 is met:

wherein, in the formulae (Q1) to (Q4), X 2 's and X 3 's are independently a sulfonic acid group; Y 2 is an electron-withdrawing group or direct bonding; Y 3 is an electron-withdrawing group; Z 2 and Z 3 are each an electron-withdrawing group, —O—, or —S—; b 1 and b 2 are integers that meet the relation b 1 +b 2 =1; b 3 and b 4 are integers that meet the relation 2≦b 3 +b 4 ≦8; each phenylene group in the formulae (Q1) to (Q4) is either unsubstituted or substituted with an arbitrarily selected group other than an ionic group; and * indicates bonding sites to constituent units as represented by any of the formulae (Q1) to (Q4) or to other constituent units.

8. The block copolymer as claimed in claim 4 , wherein the segment (A2) containing no ionic group comprises a constituent unit as represented by formula (NP1):

wherein any site shown in the formula (NP1) is either unsubstituted or substituted arbitrarily but contains no ionic group; Y 7 is an electron-withdrawing group; Z 7 is an electron-withdrawing group, —O—, —S—, or direct bonding; and * indicates bonding sites to constituent units as represented by the formula (NP1) or to other constituent units.

9. The block copolymer as claimed in claim 8 , wherein the constituent units represented by the formula (NP1) are constituent units as represented by formula (NP3):

wherein * indicates bonding sites to constituent units as represented by the formula (NP3) or to other constituent units.

10. The block copolymer as claimed in claim 4 further comprising one or more linker portions to connect the segments together.

11. The block copolymer as claimed in claim 4 having an ion exchange capacity of 1.5 meq/g to 3.5 meq/g.

12. The block copolymer as claimed in claim 4 , wherein the molar content ratio of A1/A2 between the segment (A1) containing an ionic group and the segment (A2) containing no ionic group is 0.2 or more and 5 or less.

13. The block copolymer as claimed in claim 4 , wherein the segment (A1) containing an ionic group and the segment (A2) containing no ionic group have a number average molecular weight of 5,000 or more and 50,000 or less and the block copolymers have a weight average molecular weight of 100,000 or more and 1,000,000 or less.

14. A polymer electrolyte material comprising the block polymer of claim 4 .

15. A polymer electrolyte form article comprising the polymer electrolyte material as claimed in claim 14 .

16. A polymer electrolyte fuel cell comprising the polymer electrolyte material as claimed in claim 14 .

Assignees

• Toray Industries

Inventors

• Izuhara Daisuke
• Umeda Hiroaki
• Amano Emi
• Kunita Tomoyuki

Classifications

• H01M8/1039

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

• C07C309/44

  containing doubly-bound oxygen atoms bound to the carbon skeleton · CPC title

• H01M2008/1095

  Fuel cells with polymeric electrolytes · CPC title

• C08G65/4012

  Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones · CPC title

• H01M8/1032 Primary

  having sulfur, e.g. sulfonated-polyethersulfones [S-PES] · CPC title