Method of functionalizing fluoropolymers with acidic side chains exhibiting improved properties, the fluoropolymers thereof, and methods of using
The invention relates to a method of making fluoropolymers without excessive degradation of the polymer backbone. The invention also relates to the fluoropolymers made by this method, and method of using the fluoropolymers.
1. A method of making a functionalized fluoropolymer, comprising:
mixing an aromatic molecule with an aprotic solvent to form a mixture;
adding a reactive base to the mixture to form a second mixture;
converting the aromatic molecule of the second mixture to an aromatic alkoxide and hydrogen gas;
reacting at least a portion of the hydrogen gas with a fluoroelastomer; and
mixing the aromatic alkoxide and the fluoroelastomer to form the functionalized fluoropolymer.
2. The method of claim 1 , wherein the aprotic solvent is at least one of a methylethylketone (MEK), a dimethylacetamide (DMAc), a dimethyl sulfoxide (DMSO), or a dimethylformamide (DMF).
3. The method of claim 1 , wherein a molar equivalents of the reactive base to the mixture is about 1.5.
4. The method of claim 1 , wherein the aromatic molecule comprises a sub stituent.
5. The method of claim 1 , wherein the aromatic molecule is a phenol.
6. The method of claim 4 , wherein the substituent is selected from FIG. 2 .
7. The method of claim 1 , wherein the reactive base is a metal hydride.
8. The method of claim 7 , wherein the metal hydride is at least one of a NaH, a LiH, a KH, a MgH 2 , or a CaH 2 .
9. The method of claim 4 , further comprising post functionalizing the substituent to a second substituent of FIG. 2 .
10. The method of claim 1 , wherein the aromatic molecule is mixed with the aprotic solvent at a temperature between about −10° C. to about 25° C.
11. The method of claim 1 , wherein the mixing of the aromatic alkoxide and the fluoroelastomer is at a temperature between about 40° C. and about 60° C.
12. The method of claim 1 , wherein the second mixture does not include Li 2 CO 3 , NaOH, Na 2 CO 3 , or KHCO 3 .
13. The method of claim 1 , wherein the aromatic molecule is a phenol or diethyl-4-hydroxyphenyl phosphonate.
14. The method of claim 1 , wherein the fluoroelastomer is selected from the group consisting of a vinylidene difluoride polymer, a fluoroelastomer polymer with adjacent CH and CF, a polyvinylidene difluoride with a hexafluoropropylene or a tetrafluoroethylene, and combinations thereof.
15. The method of claim 1 , further comprising chemically modifying the functionalized fluoropolymer with an HPA.
16. The method of claim 1 , wherein a molar ratio of the reactive base to the mixture is between about 1:10 and about 1:10,000.
17. The method of claim 1 , wherein a percent yield of the functionalized fluoropolymer is between about 70% and about 95%.
18. The method of claim 1 , wherein a ratio of the aromatic molecule to the aprotic solvent is between about 5 g:100 ml and about 25 g:100 ml.