Ionic liquids, functionalized particulates, and fluoropolymer composites
The present invention relates to (i) novel fluoroionic compounds capable of dispersing particulate filler compositions into a fluoropolymer; (ii) novel particulate compositions in which particulates are surface-functionalized with a fluoroionic compound; (iii) fluoropolymer composite materials containing the surface-functionalized particulates of (ii) incorporated into a fluoropolymer; (iv) crosslinked versions of (iii); v) methods for producing the crosslinked material of (iv); and (vi) articles of manufacture containing the compositions (iii) and (iv).
1. A fluoropolymer composite material comprising a fluoropolymer having incorporated therein a surface-functionalized particulate composition comprising a particulate having adhered to its surface an ionic compound of the general formula
wherein M represents a ring or ring system containing at least one nitrogen atom in the ring or ring system;
R a is a hydrocarbon linking group bound to a nitrogen atom of M and having at least one carbon atom, and optionally including one or more non-fluoro heteroatoms or heteroatom-containing groups;
R b is a fluoro-substituted hydrocarbon group having at least one carbon atom and at least one fluorine atom and optionally including one or more non-fluoro heteroatoms or heteroatom-containing groups;
the subscript v is 0 or 1, where a value of 0 for a subscript represents the absence of a group to which the subscript is appended, and a value of 1 represents the presence of a group to which the subscript is appended;
the subscript w is a positive integer representing the number of —(R a ) v —R b units bound to an equal number of ring nitrogen atoms;
+c represents a positive charge of magnitude c having a value of at least 1 and equal to the number of ring nitrogen atoms bound to —(R a ) v —R b ;
X −r represents an anion with negative charge −r, where r is a value of 1, 2, or 3;
the subscripts b and d are integers such that c×d=b×r,
wherein the general formula 2 is according to the formula
wherein:
R 1 and R 3 are, independently, hydrocarbon linking groups having at least one carbon atom, and optionally including one or more non-fluoro heteroatoms or heteroatom-containing groups;
R 2 is either a hydrogen atom, or a fluoro-substituted hydrocarbon group having at least one carbon atom and at least one fluorine atom and optionally including one or more non-fluoro heteroatoms or heteroatom-containing groups, or a heteroatom-containing group only when m is 1, wherein —R 1 —R 2 represents a vinyl group;
R 4 is a fluoro-substituted hydrocarbon group having at least one carbon atom and at least one fluorine atom and optionally including one or more non-fluoro heteroatoms or heteroatom-containing groups;
the subscripts m and p are independently 0 or 1, where a value of 0 for a subscript represents the absence of a group to which the subscript is appended, and a value of 1 represents the presence of a group to which the subscript is appended;
X −r represents an anion with negative charge −r, where r is a value of 1, 2, or 3; and
the subscripts a and b are positive integers such that a=b×r’wherein m is 1.
2. The fluoropolymer composite material of claim 1 , wherein the particulate has a composition comprising a metal.
3. The fluoropolymer composite material of claim 1 , wherein the particulate has a composition comprising a non-carbon main group element.
4. The fluoropolymer composite material of claim 3 , wherein the particulate has a composition comprising an oxide, sulfide, nitride, or phosphide material.
5. The fluoropolymer composite material of claim 4 , wherein the particulate has a composition comprising glass.
6. The fluoropolymer composite material of claim 1 , wherein the particulate has a composition comprising a carbon-based composition.
7. The fluoropolymer composite material of claim 6 , wherein the carbon-based composition is a hydrocarbon composition.
8. The fluoropolymer composite material of claim 6 , wherein the carbon-based composition is a graphene-containing composition.
9. The fluoropolymer composite material of claim 8 , wherein the particulate is selected from graphene sheets, graphite nanoparticles, carbon nanotubes, fullerenes, carbon nanohorns, carbon nanobuds, and combinations thereof.
10. The fluoropolymer composite material of claim 1 , wherein R 2 is a hydrogen atom.
11. The fluoropolymer composite material of claim 10 , wherein R 1 is a hydrocarbon linking group having 1 to 6 carbon atoms and no heteroatoms.
12. The fluoropolymer composite material of claim 11 , wherein p is 1.
13. The fluoropolymer composite material of claim 12 , wherein R 3 is a hydrocarbon linking group having 1 to 6 carbon atoms.
14. The fluoropolymer composite material of claim 13 , wherein R 4 is a fluoro-substituted hydrocarbon group having 1 to 30 carbon atoms and at least one fluorine atom.
15. The fluoropolymer composite material of claim 14 , wherein all hydrogen atoms of R 4 are substituted by fluorine atoms.
16. The fluoropolymer composite material of claim 15 , wherein R 4 contains 4 to 12 carbon atoms.
17. The fluoropolymer composite material of claim 15 , wherein R 4 contains 6 to 10 carbon atoms.
18. The fluoropolymer composite material of claim 1 , wherein the fluoropolymer is a homopolymer, copolymer, terpolymer, or higher multipolymer comprising a recurring unit according to the formula
wherein X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , and X 7 can be, independently within a unit and between units, a hydrogen atom, a fluorine atom, chorine atom, a group R representing a hydrocarbon group containing 1 to 6 carbon atoms or a fluoro-substituted hydrocarbon group containing 1 to 6 carbon atoms and at least one fluorine atom, or a group —OR;
the subscript f is a positive integer;
the subscript g is 0 or 1, where a value of 0 for a subscript represents the absence of a group to which the subscript is appended, and a value of 1 represents the presence of a group to which the subscript is appended; and
the subscript h is 0 or a positive integer.
19. The fluoropolymer composite of claim 18 , wherein the fluoropolymer is fluorinated ethylene propylene, polytetrafluoroethylene, a poly(perfluoroalkylvinylether), polyhexafluoropropylene, polyhexafluoropropylene oxide, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinylfluoride, poly(ethylene-tetrafluoroethylene), poly(ethylene-chlorotrifluoroethylene), or a copolymer, mixture, or combination thereof.
20. The fluoropolymer composite material of claim 1 , further comprising crosslinked bonds.
21. The fluoropolymer composite material of claim 20 , wherein the crosslinked bonds are between the fluoropolymer and particulate, or between fluoropolymer regions, or between particulates, or a combination thereof.
22. The fluoropolymer composite material of claim 20 , wherein the crosslinked bonds comprise linked vinyl groups, ester linkages, amido linkages, ether linkages, urea linkages, carbamate linkages, imido linkages, diazene linkages, or a combination thereof.
23. The fluoropolymer composite material of claim 20 , wherein the crosslinked bonds comprise linked vinyl groups.
24. A fluoropolymer composite material comprising a fluoropolymer having incorporated therein a carbon-based particulate having adhered to its surface an ionic compound of the general formula
wherein:
R 1 and R 3 are, independently, hydrocarbon linking groups having at least one carbon atom, and optionally including one or more non-fluoro heteroatoms or heteroatom-containing groups;
R 2 is either a hydrogen atom, or a fluoro-substituted hydrocarbon group having at least one carbon atom and at least one fluorine atom and optionally including one or more non-fluoro heteroatoms or heteroatom-containing groups, or a heteroatom-containing group only when m is 1, wherein —R 1 —R 2 represents a vinyl group;
R 4 is a fluoro-substituted hydrocarbon group having at least one carbon atom and at least one fluorine atom and optionally including one or more non-fluoro heteroatoms or heteroatom-containing groups;
the subscripts m and p are independently 0 or 1, where a value of 0 for a subscript represents the absence of a group to which the subscript is appended, and a value of 1 represents the presence of a group to which the subscript is appended;
X −r represents an anion with negative charge −r, where r is a value of 1, 2, or 3; and
the subscripts a and b are positive integers such that a=b×r.
25. A fluoropolymer composite material comprising a fluoropolymer having incorporated therein a carbon-based particulate having adhered to its surface an ionic compound of the general formula
wherein:
R 3 is a hydrocarbon linking group having 1 to 6 carbon atoms;
R 4 is a fluoro-substituted hydrocarbon group having 1 to 30 carbon atoms and at least one fluorine atom;
R 5 is a hydrocarbon group having 1 to 6 carbon atoms;
the subscript p is 0 or 1, where a value of 0 for a subscript represents the absence of a group to which the subscript is appended, and a value of 1 represents the presence of a group to which the subscript is appended, wherein R 5 represents a vinyl group;
X −r represents an anion with negative charge −r, where r is a value of 1, 2, or 3; and
the subscripts a and b are positive integers such that a=b×r.
26. The fluoropolymer composite material of claim 25 , wherein R 4 contains 4 to 12 carbon atoms and at least one fluorine atom.
27. The fluoropolymer composite material of claim 25 , wherein R 4 contains 6 to 10 carbon atoms and at least one fluorine atom.
28. The fluoropolymer composite material of claim 25 , wherein R 5 contains 1 to 3 carbon atoms.