Low equivalent weight ionomer
View Patent ↗An ionomer and a process for forming the ionomer such that the ionomer has (1) low equivalent weight; below 950, preferably between 625 and 850, and most preferably between about 700 and about 800; and (2) high conductivity, (greater than 0.15 S/cm). In an alternative embodiment, the ionomer has (1) low equivalent weight; below 950, preferably between 625 and 850, and most preferably between about 700 and about 800; and (2) acceptably low hydration, (less than about 75 weight percent). These ionomers are adapted to be processed into thin films that have acceptable physical stability. They are thus extremely well-suited for low humidity or high temperature fuel cell applications.
1. A membrane comprising a fluorinated ionomer comprising at least
(a) a substantially fluorinated backbone;
(b) pendant groups derived from an ionomeric monomer of the formula
where X is F, Cl or Br or mixtures thereof; n is an integer equal to zero, one or two; R f and R f′ are independently selected from the group of F, Cl, perfluoroalkyl radical, and chloroperfluoroalkyl radical; Y is an acid group or a functional group convertible to an acid group; a is zero or an integer greater than zero; and b is an integer greater than zero; and
(c) pendant groups derived from a vinyl ether monomer that has at least two vinyl ether groups of the form, CA 2 ═CB—O—, where the vinyl groups are separated by greater than four atoms; A is independently selected from the group containing F, Cl, and H; and B is independently selected from F, Cl, H and OR i , where R i is a branched or straight chain alkane that may be partially, substantially or completely fluorinated or chlorinated;
wherein the concentration of the pendant groups derived from the ionomeric monomer and the vinyl ether monomer is between about 10 mole percent and about 45 mole percent of the final product, and wherein the concentration of the pendant groups derived from the vinyl ether monomer is present in the final product between about 0.05 and about 2 mole percent.
2. A membrane as defined in claim 1 wherein the vinyl ether monomer for forming the pendant groups derived from the vinyl ether monomer has a formula of the form CA 2 ═CB—O—R—O—CB═CA 2 , where A is independently selected from the group containing F, Cl, and H; B is independently selected from F, Cl, H and OR i , where R i is a branched or straight chain alkane that may be partially, substantially or completely fluorinated or chlorinated; and R is straight chain alkane with 3 to 15 carbon atoms that may be partially, substantially or completely fluorinated or chlorinated.
3. A membrane as defined in claim 1 wherein the pendant groups derived from the vinyl ether monomer are present in the product in an amount between about 0.05 and about 1 mole percent.
4. A membrane as defined in claim 1 wherein the concentration of the pendant groups derived from the ionomeric monomer and the vinyl ether monomer is between about 30 mole percent and about 40 mole percent of the final product.
5. A membrane as defined in claim 1 wherein the vinyl ether monomer has the formula CF 2 ═CF—O—CF 2 CF 2 CF 2 —O—CF═CF 2 .
6. A membrane as defined in claim 1 wherein the pendant groups derived from the vinyl monomer are present in the product in an amount between about 0.05 and about 1 mole percent.
7. A membrane as defined in claim 1 wherein the ionic conductivity of the acid form of a membrane hydrated at room temperature formed from said ionomer is greater than about 0.15 S/cm at room temperature.
8. A membrane comprising a fluorinated ionomer produced by the process of
(i) forming a mini-emulsion of a mixture of deionized water, a perfluorinated surfactant, optionally dissolved in an aqueous solution; a liquid perfluorinated hydrocarbon having a molecular weight below 2000 and an ionomeric monomer;
(ii) pressurizing said mini-emulsion in an agitated reactor with at least one substantially fluorinated alkene gas;
(iii) initiating polymerization with a free radical initiator in said reactor;
(iv) maintaining a known pressure of the substantially fluorinated alkene gas for a period of time; and
(v) adding, during one or more of the process steps (i) through (iv), a vinyl ether monomer having at least two vinyl ether groups of the form, CA 2 ═CB—O—, where the vinyl groups are separated by greater than four atoms; A is independently selected from the group containing F, Cl, and H; and B is independently selected from F, Cl, H and OR i ,
where
R i is a branched or straight chain alkane that may be partially, substantially or completely fluorinated or chlorinated.
9. A membrane as defined in claim 1 wherein said product has an equivalent weight between about 600 and about 950, and the ionic conductivity of the acid form of a membrane hydrated at room temperature prepared from said product is greater than about 0.15 S/cm at room temperature.
10. A membrane as defined in claim 1 further comprising a porous support and said fluorinated ionomer impregnated within said porous support.
11. A membrane as defined in claim 2 comprising a porous support and said fluorinated ionomer impregnated within said porous support.
12. A membrane as defined in claim 3 comprising a porous support and said fluorinated ionomer impregnated within said porous support.
13. A membrane as defined in claim 4 comprising a porous support and said fluorinated ionomer impregnated within said porous support.
14. A membrane as defined in claim 5 comprising a porous support and said fluorinated ionomer impregnated within said porous support.
15. A membrane as defined in claim 6 comprising a porous support and said fluorinated ionomer impregnated within said porous support.
16. A membrane as defined in claim 7 comprising a porous support and said fluorinated ionomer impregnated within said porous support.
17. A membrane as defined in claim 10 wherein said porous support is expanded polytetrafluoroethylene.
18. A membrane as defined in claim 11 wherein said porous support is expanded polytetrafluoroethylene.
19. A membrane as defined in claim 12 wherein said porous support is expanded polytetrafluoroethylene.
20. A membrane as defined in claim 13 wherein said porous support is expanded polytetrafluoroethylene.
21. A membrane as defined in claim 14 wherein said porous support is expanded polytetrafluoroethylene.
22. A membrane as defined in claim 15 wherein said porous support is expanded polytetrafluoroethylene.
23. A membrane as defined in claim 16 wherein said porous support is expanded polytetrafluoroethylene.
24. A membrane as defined in claim 10 wherein said fluorinated ionomer substantially completely impregnates said porous support.
25. A membrane as defined in claim 11 wherein said fluorinated ionomer substantially completely impregnates said porous support.
26. A membrane as defined in claim 12 wherein said fluorinated ionomer substantially completely impregnates said porous support.
27. A membrane as defined in claim 13 wherein said fluorinated ionomer substantially completely impregnates said porous support.
28. A membrane as defined in claim 14 wherein said fluorinated ionomer substantially completely impregnates said porous support.
29. A membrane as defined in claim 15 wherein said fluorinated ionomer substantially completely impregnates said porous support.
30. A membrane as defined in claim 16 wherein said fluorinated ionomer substantially completely impregnates said porous support.