Cross-linkable polymers comprising sulfonic acid functional groups

Patent metadata

Field	Value
Publication number	US-9574037-B2
Application number	US-201414786196-A
Country	US
Kind code	B2
Filing date	Apr 16, 2014
Priority date	Apr 22, 2013
Publication date	Feb 21, 2017
Grant date	Feb 21, 2017

Abstract

The present invention pertains a fluoropolymer [polymer (F)] comprising: —recurring units derived from at least one ethylenically unsaturated fluorinated monomer [monomer (FM)]; —from 5% to 60% by moles [with respect to the total moles of recurring units of polymer (F)] of recurring units derived at least one ethylenically unsaturated fluorinated monomer containing at least one —SO 2 F functional group [monomer (IO)]; and —from 0.01% to 10% by moles [with respect to the total moles of recurring units of polymer (F)] of recurring units derived from at least one monomer comprising an azide group [monomer (Az)], to a process for its manufacture, to a cross-linkable composition comprising the same, to a process for cross-linking the same and to articles comprising the cross-linked polymer.

First claim

The invention claimed is:

1. A fluoropolymer [polymer (F)] comprising:
recurring units derived from at least one ethylenically unsaturated fluorinated monomer [monomer (FM)];
from 5% to 60% by moles, with respect to the total moles of recurring units of polymer (F), of recurring units derived at least one ethylenically unsaturated fluorinated monomer containing at least one —SO 2 F functional group [monomer (IO)]; and
from 0.01% to 10% by moles, with respect to the total moles of recurring units of polymer (F), of recurring units derived from at least one monomer comprising an azide group [monomer (Az)], wherein monomer (Az) does not comprise a (per)fluorovinyl ether end group of formula CF 2 ═CF—O—.

2. The polymer (F) of claim 1 , wherein monomer (Az) complies with formula (I):
CX 1 X 2 ═CX—(CX 3 X 4 ) t —(O) p —R f —(CH 2 ) n —[S(O) q ] s N 3   (I)

wherein: X, X 1 , X 2 , X 3 and X 4 equal to or different from each other, are independently H or F, t is 0 or 1, p is 0 or 1, n is an integer from 0 to 4, s is 0 or 1, q is 1 or 2, and R f is a divalent fluorocarbon group, optionally interrupted by one or more ethereal oxygen atoms, with the proviso that, when p is 1, t is also 1.

3. The polymer (F) of claim 2 , wherein monomer (Az) complies with formula (IV):
CX″ 1 X″ 2 ═CX″—R″ f —(CH 2 ) n —[S(O) q″ ] s″ N 3   (IV)

wherein: X″, X″ 1 and X″ 2 , equal to or different from each other, are independently H or F, n″ is an integer from 0 to 4, s″ is 0 or 1, q″ is 1 or 2, R″ f is a divalent fluorocarbon group, optionally interrupted by one or more ethereal oxygen atoms, wherein the sp 2 hybridized carbon atom of the terminal double bond ═CX″— is bound to a sp 3 carbon atom of the R″ f group.

4. The polymer (F) of claim 3 , wherein q″ is 2 and s″ is 1.

5. The polymer (F) of claim 3 , wherein monomer (Az) complies with formula (VI):
CX″X″ 2 ═CX″—R* f —SO 2 N 3   (VI)

wherein: X″, X″ 1 and X″ 2 , equal to or different from each other, are independently H or F, R* f is a divalent perfluoroalkyl group, optionally interrupted by one or more ethereal oxygen atoms.

6. The polymer (F) of claim 3 , wherein monomer (Az) complies with formula (VIII):
CX″ 1 X″ 2 ═CX″—R* f —(CH 2 ) n *—SO 2 N 3   (VIII)

wherein: X″, X″ 1 and X″ 2 , equal to or different from each other, are independently H or F, n* is an integer from 1 to 4; R* f is a divalent perfluoroalkyl group, optionally interrupted by one or more ethereal oxygen atoms.

7. The polymer (F) of claim 3 , wherein monomer (Az) complies with formula (XII):
CX″ 1 X″ 2 ═CX″—R″ f —(CH 2 ) n″ —N 3   (XII)

wherein: X″, X″ 1 and X″ 2 , equal to or different from each other, are independently H or F, n″ is an integer from 0 to 4, R″ f is a divalent fluorocarbon group, optionally interrupted by one or more ethereal oxygen atoms, wherein the sp 2 hybridized carbon atom of the terminal double bond ═CX″— is bound to a sp 3 carbon atom of the R″ f group.

8. The polymer (F) of claim 2 , wherein monomer (Az) complies with formula (X):
CX a 1 X a 2 ═CX a —CF 2 —O—R a f —(CH 2 ) na —SO 2 N 3   (X),

wherein: X a , X a 1 and X a 2 , equal to or different from each other, are independently H or F, na is an integer from 0 to 4 and —R a f — is a divalent perfluoroalkyl group having 1 to 6 carbon atoms.

9. The polymer (F) of claim 2 , wherein the monomer (Az) complies with formula (XVII):
CX 1 X 2 ═CX—CX 3 X 4 —O—R** f —SO 2 N 3   (XVII)

wherein: X, X 1 , X 2 , X 3 and X 4 , equal to or different from each other, are independently H or F, R** f is a divalent fluorinated group, optionally comprising one or more than one ethereal oxygen atom.

10. A process for the manufacture of the polymer (F) of claim 1 , said process comprising polymerizing a monomer mixture comprising at least one monomer (FM), at least one monomer (IO) and at least one monomer (Az).

11. A cross-linkable composition [composition (CC)] comprising the polymer (F) according to claim 1 and at least one curing agent in an amount of between 0.5% and 10% by weight relative to the polymer (F).

12. A method of cross-linking the polymer (F) of claim 1 , the method comprising submitting polymer (F) to UV radiation and/or thermal treatment.

13. A cross-linked polymer (F) obtained by the method of claim 12 .

14. An article comprising the cross-linked polymer (F) of claim 13 .

15. The polymer (F) of claim 5 , wherein R* f is a divalent perfluoroalkyl group of formula —(CF 2 ) m″ —, wherein m″ is an integer from 1 to 12.

16. The polymer (F) of claim 6 , wherein R* f is a divalent perfluoroalkyl group of formula —(CF 2 ) m″ —, wherein m″ is an integer from 1 to 12.

17. The polymer (F) of claim 8 , wherein X a , X a 1 and X a 2 are each independently F, na is 0 and —R a f — is —CF 2 CF 2 —.

18. The polymer (F) of claim 9 , wherein X, X 1 , X 2 , X 3 and X 4 are each independently F.

19. A method of cross-linking composition (CC) according to claim 11 , the method comprising submitting composition (CC) to UV radiation and/or thermal treatment.

20. A cross-linked composition (CC) obtained by the method of claim 19 .

Assignees

• Solvay Specialty Polymers It

Inventors

• Tortelli Vito
• Monzani Cristiano
• Oldani Claudio
• Merlo Luca

Classifications

• C08F216/1475

  Monomers containing sulfur and oxygen · CPC title

• C08L27/18

  Homopolymers or copolymers or tetrafluoroethene · CPC title

• C08F214/262 Primary

  with fluorinated vinyl ethers · CPC title

• C08F2216/1491

  Chemistry & Metallurgy · mapped topic

• C08F2216/1475

  Chemistry & Metallurgy · mapped topic