Fluorinated copolymer and ion exchange membrane

Patent metadata

Field	Value
Publication number	US-9604180-B2
Application number	US-201314082702-A
Country	US
Kind code	B2
Filing date	Nov 18, 2013
Priority date	May 18, 2011
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

To provide a fluorinated copolymer which is capable of providing an ion exchange membrane having little adverse effect due to impurities in an alkali chloride aqueous solution on electrolysis of the alkali chloride aqueous solution. To use a fluorinated copolymer of a fluorinated monomer having a carboxylic acid type functional group with a fluorinated olefin, wherein the proportion of components having a common logarithm (log M) of a molecular weight M being from 2.0 to 3.5 is at most 10 mass % per 100 mass % of components having a common logarithm (log M) of a molecular weight M being at least 2.0, contained in a CClF 2 CF 2 CClFH soluble content.

First claim

What is claimed is:

1. A fluorinated copolymer comprising units of i) a fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization and ii) a fluorinated olefin,
wherein the proportion of components having a common logarithm (logM) of a molecular weight M of from 2.0 to 3.5 is at most 10 mass % per 100 mass % of components having a common logarithm (logM) of a molecular weight M of at least 2.0, and
wherein the proportion of components is determined by measuring a soluble content of the fluorinated copolymer by the following extraction method:
a powdery fluorinated copolymer comprising units of a fluorinated olefin and a fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization is mixed with CClF 2 CF 2 CClFH with a mass ten times the fluorinated copolymer; a resulting mixture is stirred at 65° C. for 5 or more hours; the mixture is cooled to room temperature, and then methanol with a mass twice the fluorinated copolymer is added to the mixture; the mixture is filtrated, and CClF 2 CF 2 CClFH and methanol are distilled off from a filtrate to obtain a soluble content.

2. The fluorinated copolymer according to claim 1 , which has an ion exchange capacity of from 0.8 to 1.3 meq/g dry resin.

3. The fluorinated copolymer according to claim 1 , wherein the fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization is represented by formula (1):
CF 2 ═CF—(O) p —(CF 2 ) q —(CF 2 CFX) r —(O) s —(CF 2 ) t —(CF 2 CFX′) u -A  (1)

wherein
X is a fluorine atom or a trifluoromethyl group,
X′ is a fluorine atom or a trifluoromethyl group,
A is a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization,
p is 0 or 1,
q is an integer of from 0 to 12,
r is an integer of from 0 to 3,
s is 0 or 1,
t is an integer of from 0 to 12, and
u is an integer of from 0 to 3,
1≦p+s, and
1≦r+u.

4. The fluorinated copolymer according to claim 3 , wherein the functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization is at least one member selected from the group consisting of —CN, —COF, —COOR 1 , —COOM, and —CONR 2 R 3 ,
wherein R 1 is a C 1-10 alkyl group,
wherein M is an alkali metal or a quaternary ammonium salt group, and
wherein each of R 2 and R 3 is a hydrogen atom or a C 1-10 alkyl group, and R 2 and R 3 may be the same or different.

5. The fluorinated copolymer according to claim 1 , wherein the fluorinated olefin is tetrafluoroethylene.

6. The fluorinated copolymer according to claim 1 , wherein the proportion of the components having a common logarithm (logM) of a molecular weight M being from 2.0 to 3.5 is at most 5 mass %.

7. The fluorinated copolymer according to claim 1 , wherein the functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization is at least one member selected from the group consisting of —CN, —COF, —COOR 1 , —COOM, and —CONR 2 R 3 ,
wherein R 1 is a C 1-10 alkyl group,
wherein M is an alkali metal or a quaternary ammonium salt group, and
wherein each of R 2 and R 3 is a hydrogen atom or a C 1-10 alkyl group, and R 2 and R 3 may be the same or different.

8. The fluorinated copolymer according to claim 1 , wherein the fluorinated copolymer is obtained by washing with a fluorinated solvent as a washing solvent.

9. The fluorinated copolymer according to claim 8 , wherein the washing solvent is from 1 to 100 times the mass of the fluorinated copolymer.

10. The fluorinated copolymer according to claim 8 , wherein the temperature of said washing is from room temperature to 150° C.

11. An ion exchange membrane comprising the fluorinated copolymer as in claim 1 .

12. An ion exchange membrane according to claim 11 , further comprising
a layer containing a fluorinated copolymer having a sulfonic acid functional group or a functional group capable of being converted to a sulfonic acid group by hydrolysis or neutralization.

13. The ion exchange membrane according to claim 11 , which is used for electrolysis of a sodium chloride aqueous solution.

14. A fluorinated copolymer comprising units of i) a fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization and ii) a fluorinated olefin,
wherein the proportion of components having a common logarithm (logM) of a molecular weight M of from 2.0 to 3.5 is at most 10 mass % per 100 mass % of components having a common logarithm (logM) of a molecular weight M of at least 2.0,
wherein the fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization is represented by formula (1):
CF 2 ═CF—(O) p —(CF 2 ) q —(CF 2 CFX) r —(O) s —(CF 2 ) t —(CF 2 CFX′) u -A  (1)

wherein
X is a fluorine atom or a trifluoromethyl group,
X′ is a fluorine atom or a trifluoromethyl group,
A is a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization,
p is 1,
q is 0,
r is 1,
s is 0 or 1,
t is an integer of from 1 to 3, and
u is 0 or 1,
1≦p+s, and
1≦r+u, and
wherein the proportion of components is determined by measuring a soluble content of the fluorinated copolymer by the following extraction method:
a powdery fluorinated copolymer comprising units of a fluorinated olefin and a fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization is mixed with CClF 2 CF 2 CClFH with a mass ten times the fluorinated copolymer; a resulting mixture is stirred at 65° C. for 5 or more hours; the mixture is cooled to room temperature, and then methanol with a mass twice the fluorinated copolymer is added to the mixture; the mixture is filtrated, and CClF 2 CF 2 CClFH and methanol are distilled off from a filtrate to obtain a soluble content.

15. The fluorinated copolymer according to claim 14 , wherein the functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization is at least one member selected from the group consisting of —CN, —COF, —COOR 1 , —COOM, and —CONR 2 R 3 ,
wherein R 1 is a C 1-10 alkyl group,
wherein M is an alkali metal or a quaternary ammonium salt group, and
wherein each of R 2 and R 3 is a hydrogen atom or a C 1-10 alkyl group, and R 2 and R 3 may be the same or different.

16. The fluorinated copolymer according to claim 14 , wherein the units of the fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization are units of:
CF 2 ═CF—O—CF 2 CF 2 —CF 2 —COOCH 3 .

17. A process for producing a fluorinated copolymer according to claim 1 , the process comprising:
(I) obtaining a fluorinated copolymer by polymerizing a mixture comprising i) a fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid group by hydrolysis or neutralization and ii) a fluorinated olefi

Assignees

• Asahi Glass Co Ltd

Inventors

• Hattori Yukiko
• Fukunaga Shintaro
• Umemura Kazuo
• Aida Shigeru
• Tsuji Atsushi
• Tomita Toshinori

Classifications

• C08F6/06 Primary

  Treatment of polymer solutions {(C08F6/001, C08F6/006, C08F6/008, C08F6/02, C08F6/04 take precedence)} · CPC title

• C08J5/2243

  obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 · CPC title

• B01D71/44 Primary

  Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42 · CPC title

• B32B27/08

  of synthetic resin · CPC title

• C25B1/46

  in diaphragm cells · CPC title