Compositions of matter useful as ionic liquids of the formula Z + A − , wherein Z + is a cation selected from the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, and phosphonium, ammonium cations with specified substituents, and A − is selected from the group consisting of the following three anions wherein R 11 , R 12 and R 13 are as specified. R 11 —CHF—CF 2 —SO 3 − Formula I R 12 —CF 2 —CF 2 —SO 3 − Formula II (R 13 —CHF—CF 2 —SO 2 ) 2 N − Formula III.
1. A composition of matter of the Formula Z + A − , wherein Z + is a cation of the formula below:
Imidazolium
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of:
(i) H
(ii) halogen
(iii) —CH 3 , —C 2 H 5 , or C 3 to C 25 straight-chain, branched or cyclic alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2 and SH;
(iv) —CH 3 , —C 2 H 5 , or C 3 to C 25 straight-chain, branched or cyclic alkane or alkene comprising one to three heteroatoms selected from the group consisting of O, N and S, and optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2 and SH;
(v) C 6 to C 25 unsubstituted aryl or C 6 to C 25 unsubstituted heteroaryl having one to three heteroatoms independently selected from the group consisting of O, N and S; and
(vi) C 6 to C 25 substituted aryl or C 6 to C 25 substituted heteroaryl having one to three heteroatoms independently selected from the group consisting of O, N and S; and wherein said substituted aryl or substituted heteroaryl has one to three substituents independently selected from the group consisting of:
(1) —CH 3 , —C 2 H 5 , or C 3 to C 25 straight-chain, branched or cyclic alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, F, I, OH, NH 2 and SH,
(2) OH,
(3) NH 2 , and
(4) SH;
optionally at least two of R 1 , R 2 , R 3 , R 4 , and R 5 can together form a cyclic or bicyclic alkyl or alkenyl group;
and A − is an anion selected from the group consisting of Formulae I, II and III:
wherein:
R 11 is selected from the group consisting of:
(1) halogen;
(2) —CH 3 , —C 2 H 5 or C 3 to C 15 straight-chain or branched alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(3) —OCH 3 , —OC 2 H 5 or C 3 to C 15 straight-chain or branched alkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(4) C 1 to C 15 straight-chain or branched fluoroalkyl, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(5) C 1 to C 15 straight-chain or branched fluoroalkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(6) C 1 to C 15 straight-chain or branched perfluoroalkyl; and
(7) C 1 to C 15 straight-chain or branched perfluoroalkoxy;
wherein:
R 12 is selected from the group consisting of:
(1) —CH 3 , —C 2 H 5 or C 3 to C 15 straight-chain or branched alkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(2) C 1 to C 15 straight-chain or branched fluoroalkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH; and
(3) C 1 to C 15 straight-chain or branched perfluoroalkoxy; and
wherein:
R 13 is selected from the group consisting of:
(1) halogen;
(2) —CH 3 , —C 2 H 5 or C 3 to C 15 straight-chain or branched alkane or alkene, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(3) —OCH 3 , —OC 2 H 5 or C 3 to C 15 straight-chain or branched alkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(4) C 1 to C 15 straight-chain or branched fluoroalkyl, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(5) C 1 to C 15 straight-chain or branched fluoroalkoxy, optionally substituted with at least one member selected from the group consisting of Cl, Br, I, OH, NH 2 and SH;
(6) C 1 to C 15 straight-chain or branched perfluoroalkyl; and
(7) C 1 to C 15 straight-chain or branched perfluoroalkoxy.
2. The composition of claim 1 wherein the anion is 1,1,2,2-tetrafluoroethanesulfonate; 2-chloro-1,1,2-trifluoroethanesulfonate; 1,1,2,3,3,3-hexafluoropropanesulfonate; 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate; 1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate; 2-(1,2,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate; 2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate; 2-(1,1,2,2-tetrafluoro-2-iodoethoxy)-1,1,2,2-tetrafluoroethanesulfonate; 1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)ethanesulfonate; N,N-bis(1,1,2,2-tetrafluoroethanesulfonyl)imide; or N,N-bis(1,1,2,3,3,3-hexafluoropropanesulfonyl)imide.
3. The composition of claim 1 wherein Z + is imidazolium; and A− is 1,1,2,2-tetrafluoroethanesulfonate, 2-chloro-1,1,2-trifluoroethanesulfonate, 1,1,2,3,3,3-hexafluoropropanesulfonate, 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate, 1,1,2-trifluoro-2-(pentafluoroethoxy)ethanesulfonate, 2-(1,2,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate, 2-(1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate, 2-(1,1,2,2-tetrafluoro-2-iodoethoxy)-1,1,2,2-tetrafluoroethanesulfonate, 1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)ethanesulfonate, N,N-bis(1,1,2,2-tetrafluoroethanesulfonyl)imide, or N,N-bis(1,1,2,3,3,3-hexafluoropropanesulfonyl)imide.
4. The composition of claim 1 wherein said composition comprises 1-butyl-2,3-dimethylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-butyl-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-ethyl-3-methylimidazolium 1,1,2,3,3,3-hexafluoropropanesulfonate, 1-hexyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-dodecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-hexadecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, 1-octadecyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate, N-(1,1,2,2-tetrafluoroethyl)propylimidazole 1,1,2,2-tetrafluoroethanesulfonate, N-(1,1,2,2-tetrafluoroethyl)ethylperfluorohexylimidazole 1,1,2,2-tetrafluoroethanesulfonate, 1-butyl-3-methylimidazolium 1,1,2,3,3,3-hexafluoropropanesulfonate, 1-butyl-3-methylimidazolium 1,1,2-trifluoro-2-(trifluoromethoxy)ethanesulfonate, 1-butyl-3-methylimidazolium 1,1,2-trifluoro-2-(perfluoroethoxy)ethanesulfonate, 1ethyl-3-methylimidazolium 1,1,2,2-tetrafluoro-2-(pentafluoroethoxy)sulfonate, or 1-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoroocty)imidazolium 1,1,2,2-tetrafluoroethanesulfonate.