Process for producing fluorinated copolymer
View Patent ↗Provided is a process for producing a fluorinated copolymer which is capable of providing an ion exchange membrane which can suppress a decrease in current efficiency by impurities in an aqueous alkali chloride solution as a raw material on electrolysis of the alkali chloride aqueous solution. Also provided is a process for producing a fluorinated copolymer that comprises washing a fluorinated copolymer comprising a fluorinated monomer having a carboxylic acid type functional group and a fluorinated olefin, with a washing solvent containing a fluorinated solvent at a temperature of at least 40° C. and at most a boiling point of the washing solvent.
1. A process for producing a fluorinated copolymer, the process comprising:
polymerizing a fluorinated monomer with a fluorinated olefin to obtain the fluorinated copolymer,
washing a fluorinated copolymer having a molecular weight M determined by GPC against a polymethacrylate standard and comprising repeating units of a fluorinated monomer having a carboxylic acid functional group or a functional group capable of being converted to a carboxylic acid functional group by hydrolysis or neutralization and repeating units of a fluorinated olefin, with a washing solvent comprising a fluorinated solvent, at a temperature of at least 40° C. and at most the boiling point of the washing solvent, to obtain a purified fluoropolymer; wherein the fluorinated solvent is at least one member selected from the group consisting of a hydrochlorofluorocarbon, a hydrofluorocarbon and a hydrofluoroether,
wherein the amount of the washing solvent is from 1 to 100 times, by mass, of the fluorinated copolymer,
wherein the content of the fluorinated solvent in the washing solvent is from 10 to 100 parts by mass based on 100 parts by mass of the washing solvent, and
wherein the washing removes a low molecular weight component having a logM value of from 2.0 to 3.5 from the fluorinated copolymer such that the low molecular weight component is a proportion of at most 10 mass % of the purified fluoropolymer based on 100 mass % of the purified fluoropolymer having a logM of at least 2.0.
2. The process for producing a fluorinated copolymer according to claim 1 ,
wherein the fluorinated monomer is represented by the 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), and
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, 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.
3. The process for producing a fluorinated copolymer according to claim 1 , wherein the fluorinated olefin is tetrafluoroethylene.
4. The process for producing a fluorinated copolymer according to claim 1 , wherein the fluorinated solvent is a hydrofluorocarbon or a hydrofluoroether.
5. The process for producing a fluorinated copolymer according to claim 1 , wherein the fluorinated solvent is CF 2 HCF 2 OCH 2 CF 3 .
6. The process for producing a fluorinated copolymer according to claim 1 , the process further comprising:
wherein the polymerizing is solution polymerization.
7. The process for producing a fluorinated copolymer according to claim 1 , wherein the fluorinated copolymer has an ion exchange capacity of from 0.8 to 1.3 meq/g dry resin.
8. The process according to claim 6 , wherein a polymerization medium in the solution polymerization comprises a hydrochlorofluorocarbon, a hydrofluorocarbon, a hydrofluoroether, a hydrocarbon, a chlorocarbon, or an alcohol.
9. The process for producing a fluorinated copolymer according to claim 1 , wherein the washing solvent is a fluorinated solvent.
10. The process according to claim 1 , wherein the fluorinated monomer is at least one selected from the group consisting of
CF 2 ═CF—O—CF 2 CF 2 —COOCH 3 ,
CF 2 ═CF—O—CF 2 CF 2 —CF 2 —COOCH 3 ,
CF 2 ═CF—O—CF 2 CF 2 —CF 2 CF 2 —COOCH 3 ,
CF 2 ═CF—O—CF 2 CF 2 —O—CF 2 CF 2 —COOCH 3 ,
CF 2 ═CF—O—CF 2 CF 2 —O—CF 2 CF 2 —CF 2 —COOCH 3 ,
CF 2 ═CF—O—CF 2 CF 2 —O—CF 2 CF 2 —CF 2 CF 2 —COOCH 3 ,
CF 2 ═CF—O—CF 2 —CF 2 CF 2 —O—CF 2 CF 2 —COOCH 3 ,
CF 2 ═CF—O—CF 2 CF(CF 3 )—O—CF 2 CF 2 —COOCH 3 ,
CF 2 ═CF—O—CF 2 CF(CF 3 )—O—CF 2 —CF 2 CF 2 —COOCH 3 .
11. The process according to claim 1 , wherein the fluorinated olefin is a fluoroolefin having 2 to 3 carbon atoms and at least one fluorine atom in its molecule.
12. The process according to claim 1 , wherein the fluorinated copolymer further comprises units of at least one additional monomer selected from the group consisting of CF 2 ═CF 2 —R f or CF 2 ═CF—OR f , wherein R f is a C 1-10 perfluoroalkyl group, and CF 2 ═CFO(CF 2 ) v CF═CF 2 , wherein v is an integer of from 1 to 3.
13. The process according to claim 12 , wherein a proportion of the additional monomer is at most 30 mass %, based on the total content of monomers.
14. The process according to claim 1 , further comprising, at the time of the washing with the fluorinated solvent, re-esterification by using trimethyl orthoformate or trimethyl orthoacetate.