Fluorinated monomers, anion exchange polymers and methods of making the same

Abstract

Trifluorovinyl monomers, compositions containing the trifluorovinyl monomers and processes for synthesizing the trifluorovinyl monomers are disclosed. Further, the trifluorovinyl monomers may be copolymerized with fluorinated comonomers by disclosed processes. Fluorinated monomers with functionalized hydrocarbon side chains may be used to make stable fluorinated cationic ionomers suitable for uses including ion exchange and electrochemical applications.

Description

TITLE FLUORINATED MONOMERS, ANION EXCHANGE POLYMERS AND METHODS OF MAKING THE SAME CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional ApplicationNo.63 / 612,780 filed December 20, 2023, the disclosures of which are incorporated herein by reference in its entirety. BACKGROUND

[0002] Perfluorinated polymers functionalized with anionic substituents such ascarboxylate or sulfonate, also known as perfluoroionomers, find extensive application as membranes in electrochemical applications such as in fuel cells, water electrolysis cells, flow batteries, and chloralkali cells. Much less is known about highly fluorinated ionomers bearing cationic substituents such as quaternary ammonium groups, guanidinium groups, or alkylated heterocyclic group such as imidazolium or pyridinium. Such cationic-substituted fluoropolymers would find use in ion exchange applications as well as in electrochemical membranes for processes operating under basic conditions. In the area of electrolyzers for green hydrogen generation, the use of anion exchange membranes allows the elimination of expensive stack components including iridium, platinum, and titanium, thus leading to lower stack capital costs. In the area of fuel cells, similar advantages are found. Anion exchange membranes have also found application in electrodialysis and electrochemical CO2removal from the air, sea, or point sources, and electrochemical reduction of CO2 to valuable chemicals and fuels. Anion exchange polymers and cation ion exchange polymers can also be combined into bipolar membranes for water electrolysis and CO2removal and reduction.

[0003] Key benefits of fluoropolymer anion exchange membranes and ionomers arethat they likely behave like Nafion™ membrane and have excellent ionic conductivity and chemical, thermal, and mechanical stability. Their excellent balance of conductivity and mechanical property originates from their bi-continuous microstructure that allows efficient hydration of the tethered cations, eliminating the need for excess water uptake.These polymers will also have a reasonable glass transition temperature modestly higher than the device operating temperature so that hot pressing can be implemented to improve the interface between the membrane and the catalyst layer and the integration of the catalysts layer, leading to lower internal device resistance and better device performance and durability.

[0004] For use in electrochemical cells, anion exchange membranes in thehydroxylic media must be stable at pH values greater than 7. In particular, the cationic group (e.g., quaternary ammonium group), must be separated from the fluorocarbon portion of the polymer in order to avoid the possibility of HF elimination from structures bearing vicinal hydrogen and fluorine substituents. In addition, oxidative stability is frequently important not only to minimize hydrogen transfer reactions during the polymerization process used to manufacture the ionomer, but also to provide long term stability in ultimate application. This requirement eliminates a number of aromatic and polyether type structures frequently used as spacer groups in polymer chemistry. One approach to preparing such ionomers is to co-polymerize a fluorinated co-monomer with a suitably substituted co-monomer bearing a cation substituent or bearing a group capable of being easily converted to a cationic substituent.

[0005] Anion exchange ionomers having a perfluorinated backbone have beenprepared from poly(TFE-co-PSEPVE) or poly(TFE-co-PFSVE) by reaction of the pendent sulfonyl fluoride group with amines or deprotonated amines to give sulfonamides which are ultimately converted to cationic end groups by alkylation. Such ionomers have been disclosed by Liu, et al. in Journal of Physical Chemistry C, Vol. 121, pages 17546-17551 (2017), by Liu, et al. in Polymer Chemistry, Vol.7, pages 2904-2912 (2016), by Kim, et al. in Macromolecules, Vol.46, pages 7826-7833 (2013), Park, et al. in ECS Transactions, Vol.80, pages 957-966 (2017), and Divekar, et al. in Journal of Polymer Science B, Polymer Physics, Vol.57, pages 700-712 (2019). This approach does provide cationic ionomers with a perfluorinated backbone; however, these polymers are susceptible to hydrolysis due to hydroxide attack at the SO2-N bond of the sulfonamide end group.

[0006] Reaction of perfluoroionomer precursors bearing SO2F end groups withtertiary amines such as trimethylamine, 1,4-dimethyl piperazine, and N-methyl pyridine,or trimethyl phosphine have been reported to yield ionomers with cationic end groups by Holly, et al. in Journal of Applied Polymer Science, Vol.127, pages 298-307 (2013) and Journal of Polymer Science B, Polymer Physics, Vol.50, pages 552-562 (2012), and by Lee, et al. in Membranes, Vol.10, page 306 (2020). However, quaternization of tertiary amines using F-sulfonyl fluorides often fails to give true cationic polymers with hydrolysis of the SO2-F bond occurring as the primary reaction as reported by Bosnjakovic, et al. in Journal of Membrane Science, Vol.467, pages 136-141 (2014) and by Hillman, et al. in Journal of Material Chemistry, Vol.1, pages 1018-1021 (2013).

[0007] An alternative approach is to react the carboxyl form of Nafion™ with 4-fluoroaniline followed by reaction with tetramethylguanidine as reported by Kim, et al. in Macromolecules, Vol.46, pages 7826-7833 (2013). However, this polymer contains the base-sensitive Rf-C(O)-NHR group in the side chain.

[0008] Willdorf-Cohen et al. have employed poly(TFE-co-C2H4) polymers as thebackbone which were then grafted with vinylbenzylammonium groups (see ACS Applied Energy Materials, Vol.6, pages 1085-1092 (2023)). These materials have vicinal H and F substituents in the backbone which is undesirable due to the potential for HF elimination under the basic conditions in an anion exchange membrane fuel cell. Other grafts have been prepared using FEP backbones by Slade, et al. in Solid State Ionics, Vol.176, pages 585-597 (2005); however, membranes prepared from these ionomers had relatively low conductivity and were unstable at 60°C.

[0009] There is a need for stable highly fluorinated cationic ionomers. In addition,there is a need for fluorinated monomers bearing stable, hydrocarbon side chains functionalized with cationic substituents suitable for co-polymerization with fluorinated monomers to form cationic ionomers. There is also a need for fluorinated monomers having hydrocarbon side chains functionalized in such a way that they can be co- polymerized with fluorinated monomers and then further functionalized to form highly fluorinated cationic ionomers. SUMMARY

[0010] Processes for synthesizing trifluorovinyl monomers and the compositionsthereof are disclosed herein. Further, processes for making copolymers comprising the trifluorovinyl monomers, and the resulting copolymers, are also disclosed.The present disclosure provides trifluorovinyl tertiary amines of Formula (1), CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22 (1) wherein x = 0 or 1; y = 1-7; z = 0-4; R1is CH3 or CF3, R2are independently selected from CH3, C2-C8straight chain or branched alkyl, C5-C8cycloalkyl, or together with nitrogen comprise a 5- to 8-membered ring, Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1-5, or a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1-5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound.

[0011] The present disclosure also provides trifluorovinyl bis(tertiary amine)compounds of Formula (2), CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22]2(2) wherein x, z, R2, and Rfare as defined above, and each y is independently 1 to 7.

[0012] The present disclosure also provides trifluorovinyl quaternary ammoniumsalts of Formula (3), [CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22R3]+1[Q-n]1 / n (3) wherein R3is CH3, C2-C8 straight chain or branched alkyl or C5-C8 cycloalkyl, Q = a monovalent anion such as Cl, Br, I, OH, HCO3, HSO4, H2PO4, BF4, PF6, O3SR4wherein R4= C1-C3alkoxy, C1-C6straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl, or a divalent anion such as CO3, SO4 or HPO4, or a trivalent anion such as PO4, wherein n is the charge on Q, and wherein x, y, z, R1, R2, and Rfare as defined above.

[0013] The present disclosure also provides cationic trifluorovinyl bis(quaternaryammonium) salts of the Formula (4), {CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22R3]2}+2[Q-n]2 / n(4) wherein x, y, z, R2, R3, Rf, Q and n are as defined above. The present disclosure also provides trifluorovinyl alkyl chlorides of Formula (5), CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R5)(CH2)rCl (5)wherein R5is CH3, (CH2)rCl, or CF3; r is an integer = 1 to 7, and x, z, and Rfare as defined above.

[0014] The present disclosure also describes trifluorovinyl cyclic ethers representedby Structure (6) wherein p = 1 to 4

[0015] The present disclosure also provides trifluorovinyl tertiary amines of Formula(7), CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2 (7) wherein a = 0 to 4; b = 0 or 1; R1is selected from CH3 and CF3; R7are both H or both CH3; and x, z, and Rfare as defined above.

[0016] The present disclosure also provides cationic trifluorovinyl quaternaryammonium salts of Formula (8), [CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2R3]+1[Q-n]1 / n(8) wherein a, b, x, z, Q, n, Rf, R1, R3, and R7are as defined above.

[0017] The present disclosure also provides trifluorovinyl alkyl nitriles of Formula (9),CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(R6)(CH2)mCN (9)wherein m = 0 to 5; R1is CH3or CF3; R6is selected from the group consisting of CH3and OCH3 provided that when R6= CH3 then m = 0; and x, z, and Rfare as defined above.

[0018] The present disclosure also provides processes for the syntheses oftrifluorovinyl compounds of Formulas (1), (2), (3), (4), (5), (6), (7), (8), and (9).

[0019] The present disclosure also provides trifluorovinyl monomers useful forsynthesis of copolymers bearing quaternary ammonium substituents.

[0020] The present disclosure also provides a process for preparing a copolymerderived from co-polymerization of one or more co-monomers with a trifluorovinyl monomer of Formulas (3), (4), (5), (6), (8) or (9), wherein comprising at least one of the co-monomer(s) is (are) a fluorinated co-monomer that may be selected from the group consisting of, consisting essentially of or comprising, CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3, CF2=CFOC2F5, CF2=CFOC3F7, cyclo-[OC(CF3)2OCF=CF]- (4,5-difluoro-2,2- bis(trifluoromethyl-1,3-dioxole), cyclo-[OC(=CF2)OCF2CF(CF3)]- (2-difluoromethylene- 4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane), cyclo-[OC(=CF2)OCF(CF3)CF(CF3)]- (2- difluoromethylene-4,5-difluoro-4,5-bis(trifluoromethyl)-1,3-dioxolane), CF2=CFOCF2CF2CF=CF2, and cyclo-[OCF=C(OCF3)OCF2]- (2,2,4-trifluoro-5- (trifluoromethoxy)-1,3-dioxole). In one embodiment, at least one comonomer comprises CF2=CF2, CF2=CFCF3, CF2=CFOCF3, CF2=CFOC2F5, CF2=CFOC3F7, cyclo- OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3)- , CF2=CFOCF2CF2CF=CF2, or cyclo-[OCF=C(OCF3)OCF2]-. In a further embodiment, at least one comonomer comprises CF2=CF2, CF2=CFCF3, CF2=CFOCF3, CF2=CFOC2F5or CF2=CFOC3F7.

[0021] The present disclosure also provides an embodiment of a copolymer of TFEand trifluorovinyl quaternary ammonium monomer of Formula (3) or (4).

[0022] In a further embodiment, a process is disclosed for preparing a copolymer ofTFE and a trifluorovinyl quaternary ammonium monomer of Formula (3) useful as an anion exchange ionomer.

[0023] In one embodiment, a copolymer of TFE and a trifluorovinyl alkyl chloridemonomer of Formula (5) is disclosed wherein the product copolymer is further reacted with an amine to form an ionomer bearing quaternary ammonium substituents.

[0024] The ratio of trifluorovinyl monomer to comonomer may be selected toachieve a concentration of cationic end groups in the resulting copolymer suitable for use in anion exchange membranes in fuel cell and / or water electrolysis applications. In some embodiments, perfluorinated copolymers comprising TFE and trifluorovinyl monomer as described herein may have an equivalent weight (EW) of from about 600EW to about 5000 EW, or from about 600 EW to about 1500 EW, or from about 700 EW to 1000 EW. The equivalent weight of an ionomer may be determined by titration.

[0025] The present disclosure further provides a membrane fabricated from apolyfluorinated cation exchange ionomer. In an embodiment, an anion exchange membrane is prepared from the ionomers disclosed herein that is suitable for use in fuel cell and / or water electrolysis applications. BRIEF DESCRIPTION OF THE FIGURES

[0026] Figure 1 is an image of solid state 19F NMR of an embodiment of an AEMcopolymer described herein.

[0027] Figure 2 is an image of a solid state 13C NMR of an embodiment of acopolymer described herein.

[0028] Figure 3 image of solid state 19F NMR of an embodiment of an AEMcopolymer described herein.

[0029] Figure 4 is a DSC image of an embodiment of a copolymer described herein.DETAILED DESCRIPTION

[0030] Where a range of numerical values is recited herein, including lists of upperand lower values, unless otherwise provided, the range is intended to include endpoints thereof, and all integers and fractions within the range. Ranges set forth herein are intended to include the particular ranges specifically described, and any combination of values therein, including the minimum and maximum values recited. Compounds of Formula (1)

[0031] Trifluorovinyl tertiary amines are disclosed having a composition representedby Formula (1), CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22(1) wherein x = 0 or 1; y = 1 to 7; z = 0 to 4; R1is selected from CH3and CF3; R2are independently selected from the group consisting of CH3, C2-C8 straight chain or branched alkyl, C5-C8cycloalkyl, or together with nitrogen comprise a 5- to 8-membered ring; and Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound.

[0032] In some embodiments, tertiary amines of Formula (1) include those whereinx = 1; z = 0 to 2; Rf= (CF2)i where i = 1 to 3; R1= CH3; y = 1 to 3; and R2= CH3.

[0033] In other embodiments, tertiary amines of Formula (1) include those wherein x= 1, z = 0 to 2, Rf= (CF2)iwhere i = 1 to 3, R1= CF3, y = 1 to 3, and R2= CH3.

[0034] In some embodiments, trifluorovinyl tertiary amines of Formula (1) includethose wherein x = 0, z = 0, Rf= (CF2)i where i = 1 to 3, R1= CH3, y = 1 to 3, and R2= CH3.

[0035] In other embodiments, trifluorovinyl tertiary amines of Formula (1) includethose wherein x = 0, z = 0, Rf= (CF2)i where i = 1 to 3, R1= CF3, y = 1 to 3, and R2= CH3.

[0036] In some embodiments, trifluorovinyl tertiary amines of Formula (1) includethose wherein x = 1, z = 0 to 2, Rf= (CF2)i where i = 1 to 3, R1= CH3, y = 1 to 3, and NR22 comprises N-piperidyl (cyclo-N(CH2)5-), 2-, 3-, or 4-methyl-substituted piperidyl (cyclo-N[CH(CH3)]1(CH2)4-), pyrrolidyl (cyclo-N(CH2)4-), or 2- or 3-methyl-substituted pyrrolidyl ((cyclo-N[CH(CH3)]1(CH2)3-).

[0037] In other embodiments, trifluorovinyl tertiary amines of Formula (1) includethose wherein x = 1, z = 0 to 2, Rf= (CF2)iwhere i = 1 to 3, R1= CF3, y = 1 to 3, and NR22comprises N-piperidyl (cyclo-N(CH2)5-), 2-, 3-, or 4-methyl-substituted piperidyl (cyclo-N[CH(CH3)]1(CH2)4-), pyrrolidyl (cyclo-N(CH2)4-), or 2- or 3-methyl-substituted pyrrolidyl ((cyclo-N[CH(CH3)]1(CH2)3-).

[0038] In some embodiments, trifluorovinyl tertiary amines of Formula (1) includethose wherein x = 0, z = 0, Rf= (CF2)I where i = 1 to 3, R1= CH3, y = 1 to 3, and NR22 comprises N-piperidyl (cyclo-N(CH2)5-), 2-, 3-, or 4-methyl-substituted piperidyl (cyclo- N[CH(CH3)]1(CH2)4-), pyrrolidyl (cyclo-N(CH2)4-), or 2- or 3-methyl-substituted pyrrolidyl ((cyclo-N[CH(CH3)]1(CH2)3-).

[0039] In other embodiments, the trifluorovinyl tertiary amines of Formula (1) includethose wherein x = 0, z = 0, Rf= (CF2)iwhere i = 1 to 3, R1= CF3, y = 1 to 3, and NR22comprises N-piperidyl (cyclo-N(CH2)5-), 2-, 3-, or 4-methyl-substituted piperidyl (cyclo- N[CH(CH3)]1(CH2)4-), pyrrolidyl (cyclo-N(CH2)4-), or 2- or 3-methyl-substituted pyrrolidyl ((cyclo-N[CH(CH3)]1(CH2)3-).

[0040] Trifluorovinyl tertiary amine compounds having a composition represented byFormula (1) may be produced from polyfluoroalkyl halide compounds of Formula (1-1), CXF2CXF(CF2)z(O)x(Rf)CF2Y (1-1)wherein each X = Cl, Y is selected from Br or I; and x, z, and Rfare as defined above for Formula (1). Compounds of Formula (1-1) may be obtained commercially or by procedures disclosed in the literature and known in the art. Compounds of Formula (1- 1) suitable for use in making trifluorovinyl tertiary amine compounds include but are not limited to CClF2CClFCF2Br, CClF2CClFCF2I, CClF2CClFCF2CF2Br, CClF2CClFCF2CF2I, CClF2CClFOCF2CF2CF2I, CClF2CClFOCF2CF2Br, CClF2CClFOCF2CF2I, CClF2CClFOCF2CF2CF2CF2I, and CClF2CClFOCF2CF(CF3)OCF2CF2I.

[0041] In one embodiment, a process for making a trifluorovinyl tertiary amines ofFormula (1), comprises reacting a polyfluoroalkyl halide compound of Formula (1-1) with an alkyl or aryl magnesium halide. Alkyl or aryl magnesium halides suitable for use herein include Grignard reagents of formula RMgZ, wherein R = C1-C6 alkyl, or aryl, and Z = Cl, Br, or I. Examples of suitable alkyl or aryl magnesium halides for processes herein include but are not limited to methyl magnesium bromide, ethyl magnesium bromide, ethyl magnesium chloride, isopropyl magnesium chloride, phenyl magnesium chloride, or p-tolyl magnesium bromide. In some embodiments, Grignard reagents for use in the processes herein include C1-C3alkyl magnesium chlorides or C1-C3alkyl magnesium bromides.

[0042] Alkyl or aryl magnesium halides may be provided as a solution in a solventsuch as diethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, or tert-butyl methyl ether. Reaction of the polyfluoroalkyl halide compounds of Formula (1-1) with an alkyl or aryl magnesium halide may be conducted in an ethereal solvent such as diethyl ether, dibutyl ether, tetrahydrofuran, methyl tetrahydrofuran, dioxane, ethylene glycol dimethyl ether (glyme), or diethylene glycol dimethyl ether (diglyme). The amount of alkyl or aryl magnesium halide suitable for use herein may be from one mole of alkyl or aryl magnesium halide per mole of compound of Formula (1-1) to about 1.3 moles of alkyl or aryl magnesium halide to one mole of compound of Formula (1-1), or from about 1.05 toabout 1.15 moles of alkyl or aryl magnesium halide to one mole of compound of Formula (1-1).

[0043] Reactions of the compound of Formula (1-1) with an alkyl magnesium halidemay be conducted at temperatures of from about -78°C to about 0°C, or from about - 50°C to about -20°C, with continuous stirring, or at sufficiently low temperatures to minimize decomposition of organometallic intermediates. Suitable reaction times are from about 0.5 hour (h) to about 10 h, or from about 2 h to about 6 h. Following reacting a polyfluoroalkyl halide compound of Formula (1-1) with alkyl magnesium halide, a bis(cyclopentadienyl)zirconium dichloride compound may be then added while maintaining a temperature of the mixture between about -50°C to about -20°C, with additional stirring time of about 2 h to about 6 h to provide organometallic reactive intermediate solution. Bis(cyclopentadienyl)zirconium dichloride may be used in an amount of about one mole per mole of compound of Formula (1-1) to about 1.3 moles of the bis(cyclopentadienyl)zirconium dichloride compound to one mole of compound of Formula (1-1). The use of bis(cyclopentadienyl)-zirconium dichloride compounds, also known as zirconocene promoters, for Grignard reactions was reported by Fujiu, et al. in Dalton Transactions, Vol.44, pages 19464-19468 (2015), the teachings of which are incorporated by reference, herein. A bis(cyclopentadienyl)zirconium dichloride compound suitable for this process include bis(cyclopentadienyl)zirconium dichloride ((^5-C5H5)2ZrCl2), bis(methylcyclopentadienyl)zirconium dichloride ([^5- C5H4(CH3)]2ZrCl2), bis(pentamethylcyclopentadienyl)zirconium dichloride ([^5- C5(CH3)5]2ZrCl2), (cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride ([^5-C5(CH3)5](^5-C5H5)ZrCl2), and bis(indenyl)zirconium dichloride ([^5-(C9H7)]2ZrCl2).an organometallic reactive intermediate solutionmay be contacted with an alkenyl ketone that is added undiluted or as a solution in a solvent such as an alkane (pentane, hexane, heptane, etc.) or arene (toluene, xylene, etc.) or an ether such as that used in the Grignard reactions. An alkenyl ketone may comprise a compound having composition represented by Formula (1-2), R1C(O)(CH2)qCH=CH2 (1-2) wherein R1is CH3 or CF3; and q = 0 to 4. Ketones of Formula (1-2) may be obtained commercially or by procedures disclosed in the literature and known in the art.Examples of alkenyl ketones suitable for use herein include, but are not limited to, CH3C(O)CH=CH2, CF3C(O)CH=CH2, CH3C(O)CH2CH=CH2, CH3C(O)CH2CH2CH=CH2, CF3C(O)CH2CH=CH2 and CF3C(O)CH2CH2CH=CH2.

[0045] The alkenyl ketone may be contacted with an organometallic reactiveintermediate solution in an amount of about 1.0 to 1.2 moles of alkenyl ketone to one mole of organometallic reactive intermediate. The addition of alkenyl ketone to organometallic reactive intermediate solution may be conducted at a temperature of from about -50°C to about -30°C with continuous stirring. After the addition, the reaction may be gradually warmed to a temperature of from about 0°C to about 40°C, or from about 15°C to about 30°C, and optionally stirred, for a time sufficient to react alkenyl ketone with organometallic reactive intermediate solution. The progress of the reaction may be monitored by NMR spectroscopy or by gas chromatography with a mass selective detector. After the reaction is sufficiently completed, the mixture may be hydrolyzed with water or dilute aqueous mineral acids and filtered. After washing the solid with solvent, the organic phase in the filtrate may be separated, washed with water, and dried over a desiccating agent such as magnesium sulfate, sodium sulfate or calcium chloride. The dried organic phase may be concentrated and distilled to recover the product, a fluoroalkyl hydroxyalkene compound having a structure represented by Formula (1-3), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)qCH=CH2 (1-3) wherein q, x, z, and Rfare as defined above, and R1is CH3or CF3.

[0046] In a further embodiment, the hydroxy group in the compound of Formula (1-3) then may be methylated with a methylating reagent to provide a fluoroalkyl methoxyalkene compound having a composition represented by Formula (1-4), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH=CH2(1-4) wherein q, x, z, Rfand R1are as defined above. Suitable methylating reagents for the process include, but are not limited to, dimethyl sulfate, methyl methanesulfonate, methyl trifluoromethanesulfonate, and methyl p-toluenesulfonate, halomethanes, CH3Z where Z = Cl, Br, or I, and dimethylcarbonate, in the presence of a non-aqueous base. Methylating agents may be used in a stoichiometric amount, that is, one molemethylating agent per mole of OH group to be methylated. An excess of methylating agent may be used in an amount that is approximately no more than 1 mole % to 20 mole %, where any excess may be quenched with water or aqueous ammonia prior to isolation of the product. Methylation reactions may be conducted in a solvent such as an alkane (e.g., hexane, heptane, and the like), aromatic hydrocarbon (e.g., toluene), a chloroocarbon (e.g., methylene chloride or chloroform), or an ether (e.g., diethyl ether or glyme), or alkane nitrile (e.g., acetonitrile). Solvents may comprise from about 20 wt% to about 98 wt% of the reaction mixture, or from about 50 wt% to about 90 wt% of the reaction mixture. A suitable reaction temperature for the methylation step is, for example, from about -20°C to about 40°C, or about 0°C to about 30°C.

[0047] In an embodiment where alkylation is conducted by reaction of iodomethane,the compound of Formula (1-3) may be first deprotonated with a non-aqueous base such as sodium methoxide, sodium hydride, sodium amide, lithium diisopropylamide, butyl lithium, or potassium tert-butoxide. Bases may be added as solids, oil dispersions, or solutions in solvents such as diethyl ether, tetrahydrofuran, cyclohexane, or hexane. A stoichiometric amount of non-aqueous base may be added with an excess of less than or equal to 10 mole %. The deprotonation reaction may be conducted in solvent such as an alkane (e.g., hexane, heptane, and the like), aromatic hydrocarbon (e.g., toluene), or an ether (e.g., diethyl ether or glyme) or alkane nitrile (e.g., acetonitrile) at a temperature of from about -78°C to about 40°C, or from about -50°C to about -20°C. After conversion of the alcohol to the conjugate base, iodomethane may be added at a temperature of from about -50°C to about -20°C to gradually warm the reaction mixture to a temperature of about 0°C to about 40°C, or about 10°C to about 30°C.

[0048] A fluoroalkyl methoxyalkene compound of Formula (1-4) may be recoveredfrom the reaction by treatment with water followed by extraction of the product with an extraction solvent. Suitable extraction solvents include diethyl ether, dichloromethane, ethyl acetate, and the like. The organic phase from the extraction may be separated, washed with water, and dried over a desiccating agent such as, magnesium sulfate, sodium sulfate or calcium chloride. The dried organic phase may then be concentrated under vacuum and distilled to give the compound of Formula (1-4), examples of which include, but are not limited to, CClF2CClFCF2C(CH3)(OCH3)CH=CH2,CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2CH=CH2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH=CH2, CClF2CClFCF2CF2C(CH3)(OCH3)CH=CH2, CClF2CClFCF2CF2C(CF3)(OCH3)CH=CH2, CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH2CH=CH2, CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH=CH2, CClF2CClFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH=CH2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH=CH2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH=CH2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH=CH2, CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH2CH=CH2, CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH=CH2, CClF2CClFOCF2CF2C(CF3)(OCH3)CH=CH2, CClF2CClFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH=CH2, and CClF2CClFOCF2CF(CF3)OCF2CF2C(CH3)(OCH3)CH2CH2CH=CH2.

[0049] In a further embodiment, a compound of Formula (1-4) may be thenconverted to an amine, for example, by reacting the olefinic group with a borane followed by hydroxylamine-O-sulfonic acid to give fluoroalkyl primary amine compound of the Formula (1-5), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2NH2 (1-5) wherein z, x, Rf, and R1are as defined above for Formula (1) and q = 0-4, by a process described in “Organic Synthesis via Boranes” (H. C. Brown, published by John Wiley & Sons, 1975, page 90), and the teachings of which are hereby incorporated by reference herein.

[0050] A fluoroalkyl primary amine of Formula (1-5) may then be methylated with amethylating agent such as bromomethane, iodomethane, dimethyl sulfate, methyl methanesulfonate, methyl trifluoromethanesulfonate, or methyl p-toluenesulfonate, resulting in a fluoroalkyl tertiary amine compound having the Formula (1-6), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2N(CH3)2(1-6) wherein z, x, Rfand R1are as defined above for Formula (1) and q = 0-4, by amino alkylation. Known processes for amino alkylation that are suitable for use herein mayinclude those that are described, for example, by J. March, “Advanced Organic Chemistry”, published by John Wiley & Sons, 1985, pages 364-366, the teachings of which are incorporated by reference, herein.

[0051] Alternatively, primary amine compounds of Formula (1-5) may be alkylatedwith a halo compound having the formula R3Z wherein Z is Cl, Br, or I, and R3is C2-C8straight chain or branched alkyl halides or C5-C8 cycloalkyl halides to provide a fluoroalkyl tertiary amine compound having a composition represented by Formula (1- 7), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2NR32 (1-7) wherein z, x, Rf, and R1are as defined above for Formula (1) and q = 0-4, and R3is C2- C8straight chain or branched alkyl, or C5-C8cycloalkyl. Examples of C2-C8alkyl halides include ethyl bromide, butyl bromide, or n-hexyl iodide. Examples of C5-C8 cycloalkyl halides include iodocyclopentane, iodocyclohexane, and bromocyclohexane.

[0052] Alternatively, the fluoroalkyl methoxyalkene compound of Formula (1-4) maybe aminomethylated to provide a compound having a composition represented by Formula (1-8), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2CH2N(CH3)2(1-8)wherein z, x, Rf and R1 are as defined above for Formula (1) and q = 0-4, by reactionwith CO, H2O, and dimethylamine in the presence of a rhodium catalyst, (see F.Jachimowicz and J. W. Raksis in Journal of Organic Chemistry, Vol. 47, pages 445-447(1982) the teachings of which are incorporated by reference, herein.)

[0053] Alternatively, the fluoroalkyl methoxyalkene compound of Formula (1-4) maybe converted to fluoroalkyl aldehyde compound of Formula (1-9), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2C(O)H (1-9)wherein z, x, Rfand R1are as defined above for Formula (1) and q = 0-4, by hydroboration with borane or 9-borabicyclo[3.3.1]nonane (9-BBN) followed by carbonylation (H. C. Brown, “Organic Synthesis via Boranes”, John Wiley & Sons, 1975, pages 56-57 and 130-131), the teachings of which are incorporated by reference.

[0054] Alternatively, fluoroalkyl methoxyalkene compound of Formula (1-4) may beoxidized to fluoroalkyl aldehyde of Formula (1-10) CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2C(O)H (1-10)wherein z, x, Rfand R1are as defined above for Formula (1) and q = 0-4, by Wacker oxidation using a copper-promoted palladium process in the presence of air and water as described in “Advanced Organic Chemistry” (J. March, John Wiley & Sons, 1985, pages 1084-1086), the teachings of which are incorporated by reference, herein.

[0055] Alternatively, conversion of fluoroalkyl methoxyalkene compound of Formula(1-4) to fluoroalkyl aldehyde compound of Formula (1-11), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qC(O)H (1-11)wherein z, x, Rfand R1are as defined above for Formula (1) and q = 0-4, may be effected by osmium tetroxide-catalyzed sodium periodate oxidation.

[0056] Oxidation of fluoroalkyl methoxyalkene of Formula (1-4) may be conducted ina polar solvent such as acetonitrile, butyronitrile, dimethylsulfone, tetramethylene sulfone, acetone, 3-pentanone, ethyl acetate, or dimethyl carbonate; water may be present in an amount of from 5 volume % of the total solvent volume to 50 volume %, or from about 10 volume % to about 30 volume %. An amount of solvent volume suitable for the process is from about 5 mL of solvent per gram of compound of Formula (1-4) to about 50 mL per gram, or from about 10 mL of solvent per gram to about 30 mL per gram. Suitable temperatures for the oxidation are from about 0°C to about 100°C, or from about 15°C to about 40°C. Sodium periodate may be used in at least a stoichiometric quantity up to 2.5 equivalents, or in some embodiments no more than two equivalents of sodium periodate to inhibit unwanted side reactions. Osmium tetroxide catalyst may be added as an aqueous solution at a concentration of 2 wt% to 5 wt% with the amount of OsO4relative to the amount of compound of Formula(4), ranging from about 1 mole of OsO4 per 100 moles of compound of Formula (1-4) to about 1 mole of OsO4per 1000 moles of compound of Formula (1-4), or from about 1 mole of OsO4per 200 moles of compound of Formula (1-4) to about 1 mole of OsO4per 500 moles of compound of Formula (1-4). The product fluoroalkyl aldehyde compound of Formula (1-11) may be isolated by extraction into an organic layer using an extractionsolvent such as diethyl ether, ethyl acetate, or dichloromethane followed by phase separation, drying over a desiccant, concentration and distillation using methods known in the art.

[0057] Fluoroalkyl aldehyde compounds of Formulas (1-9), (1-10), and (1-11) maythen be converted to fluoroalkyl tertiary amine compounds of Formulas (1-12), (1-13), and (1-14), respectively, CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2CH2N(CH3)2(1-12) CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2N(CH3)2(1-13) CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2N(CH3)2 (1-14) wherein z, x, Rfand R1are as defined above for Formula (1) and q = 0-4, by reaction with dimethylamine and a reducing agent. The reaction may be conducted in a solvent such as acetonitrile, propionitrile, butyronitrile, dimethylsulfoxide, N,N- dimethylformamide, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate.

[0058] In some embodiments, the amount of solvent in the reaction may be fromabout 5 mL of solvent per gram of fluoroalkyl aldehyde compound of Formula (1-9), (1- 10), or (1-11) to about 50 mL per gram, or from about 10 mL of solvent per gram to about 30 mL per gram. The compound of Formula (1-9), (1-10), or (1-11) may be dissolved or suspended in the solvent mixture at a temperature of from about -30°C to about 30°C, or from about -15°C to about 0°C. The dimethylamine may be added to the reaction as a gas or as a solution in a non-hydroxylic solvent such as diethyl ether, tetrahydrofuran, or the like. Sufficient dimethylamine is added to completely react with the aldehyde functionality of a compound of Formula (1-9), (1-10), or (1-11). At least a stoichiometric amount of dimethylamine is added; however, in some embodiments an amount up to about 3 moles of dimethylamine per mole of a compound of Formula (1- 9), (1-10), or (1-11) may be used. Alternatively, about 1.3 moles of dimethylamine to about 2.5 moles may be added per mole of the aldehyde compound of Formula (1-9), (1-10), or (1-11).

[0059] After the addition of dimethylamine is complete, a reducing agent may beadded such as hydrogen gas in the presence of a catalyst such as Raney nickel orpalladium on carbon, zinc with hydrochloric acid, zinc with sodium hydroxide, or a hydride such as sodium hydride, sodium borohydride, sodium cyanoborohyride, sodium trimethoxyborohydride, sodium triacetoxyborohydride, or sodium triethylborohydride. The reducing agent may be added in an amount of at least two moles per mole of aldehyde functional group up to ten equivalents, or the amount of reducing agent added may be from about two to about six moles per mole of aldehyde functionality. After the reducing agent has been added, the temperature of the reaction may be increased to about 25°C and the mixture stirred for a time sufficient to allow complete conversion of the aldehyde, and an imine intermediate, to the fluoroalkyl tertiary amine compound of Formula (1-12), (1-13) or (1-14). Conversion may be monitored by NMR or gas chromatography. When conversion is sufficiently completed, the reaction may be treated with aqueous sodium bicarbonate to consume remaining reducing agent, and the reaction may be extracted with an extracting solvent such as diethyl ether, ethyl acetate, or dichloromethane followed by phase separation, drying over a desiccant, concentration and distillation using methods known in the art.

[0060] Examples of fluoroalkyl tertiary amine compounds of Formulas (1-12), (1-13),and (1-14) that may be prepared by the processes of this invention include, but are not limited to, CClF2CClFCF2C(CH3)(OCH3)CH2CH2N(CH3)2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2N(CH3)2, CClF2CClFCF2CF2C(CF3)(OCH3)CH2N(CH3)2, CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH2N(CH3)2, CClF2CClFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2N(CH3)2, CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2,CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH2N(CH3)2,CClF2CClFOCF2CF2C(CF3)(OCH3) CH2N(CH3)2, CClF2CClFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2, and CClF2CClFOCF2CF(CF3)OCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2.

[0061] Fluoroalkyl tertiary amine compounds of Formula (1-12), (1-13), and (1-14),generally represented as Formula (1-15), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)q(CH2)tN(CH3)2 (1-15) wherein x, z, Rf, and R1are as defined above for Formula (1), q = 0 to 4; t = 1 to 3, and y = q+t, are converted to trifluorovinyl tertiary amine compounds of Formula (1), by reaction with a dechlorinating reagent.

[0062] A dechlorinating reagent may include a reducing metal such as zinc,magnesium, or cadmium. Optionally, said dechlorinating reagent may be promoted with metal chloride such as ZnCl2, MgCl2 or CdCl2. The reducing metal may be activated before use by washing with aqueous hydrochloric acid having a concentration of about 1M to about 5M followed by washing with water and acetone and vacuum drying. A reducing metal may be generated by reaction of a metal chloride with an alkali metal such as sodium or potassium as generally described in Topics in Current Chemistry, (R. D. Rieke, Vol.59, pages 1-31 (1975)) the teachings of which are incorporated by reference herein, or by using lithium napthalenide.

[0063] Dechlorination may be conducted in an aprotic solvent such asdimethylsulfoxide, N,N-dimethylformamide, N-methylpyrrolidinone, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate. An amount of solvent employed in the dechlorination may vary from about 0.5 mL of solvent per gram of compound of Formula (1-15) to about 30 mL per gram, or from about 1 mL of solvent per gram to about 10 mL per gram. The dechlorinating reagent may be suspended in the solvent under an atmosphere of nitrogen with rapid stirring. The amount of dechlorinating reagent employed may be at least one mole of dechlorinating agent per mole of vinyl ether functionality to be generated to about eight moles of dechlorinating agent, or from about 2 moles to about six moles of dechlorinating reagent for each mole of vinyl ether to be dechlorinated. The compound of Formula (1-15) may then be added to a dechlorination reagent suspension and the reaction mixture may be heated with rapid stirring to a temperature of fromabout 20°C to about 120°C, or from about 40°C to about 100°C. When the compounds of Formula (1-15) have been sufficiently dechlorinated as determined by a suitable analysis such as NMR or gas chromatography, in some embodiments the reaction mixture may be filtered and then treated with water, aqueous sodium chloride, or aqueous ammonium chloride and the product compound of Formula (1) extracted with an extracting solvent such as diethyl ether, ethyl acetate, or dichloromethane followed by phase separation, drying the solvent phase over a desiccant followed by concentration, and distillation using methods known in the art.

[0064] Exemplary trifluorovinyl tertiary amine compounds of Formula (1) that may beprepared by the processes of this invention include, but are not limited to, CF2=CFCF2C(CH3)(OCH3)CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2N(CH3)2, CF2=CFCF2CF2C(CF3)(OCH3)CH2N(CH3)2, CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2N(CH3)2, CF2=CFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2N(CH3)2, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CF3)(OCH3)CH2N(CH3)2, and CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2. Compounds of Formula (2)

[0065] In another embodiment, a trifluorovinyl bis(tertiary amine) of Formula (2), isprovided,CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22]2(2) wherein x, z, R2, and Rfare as defined above for Formula (1), and wherein each y is independently 1 to 7.

[0066] In some embodiments, trifluorovinyl bis(tertiary amine) compounds ofFormula (2) include those wherein x = 1, z = 0 to 2, Rf= (CF2)iwhere i = 1 to 3, y = 1 to 3, and R2= CH3.

[0067] In some embodiments, trifluorovinyl bis(tertiary amine) compounds ofFormula (2) include those wherein x = 0, z = 0, Rf= (CF2)iwhere i = 1 to 3, y = 1 to 3, and R2= CH3.

[0068] Trifluorovinyl bis(tertiary amine) compounds of Formula (2) may be preparedstarting from dialkenyl ketones Formula (2-1), C(O)[(CH2)uCH=CH2]2 (2-1) wherein each u is independently 0 to 4. Ketones of Formula (2-1) are known in the art. Examples of ketones suitable for preparation of compounds of Formula (2) include, but are not limited to, CH2=CHCH2C(O)CH2CH=CH2, CH2=CHCH2CH2C(O)CH2CH2CH=CH2, CH2=CHC(O)CH2CH=CH2, CH2=CHC(O)CH=CH2, and CH2=CH(CH2)4C(O)CH2)4CH=CH2.

[0069] Dialkenyl ketones reacted with organometallic reactive intermediate solutionas disclosed above may form compounds containing dienyl groups (herein, referred to as fluoroalkyl hydroxy diene compounds) of Formula (2-2) CClF2CClF(CF2)z(O)xCF2(Rf)C(OH)[(CH2)uCH=CH2]2(2-2) wherein x, z, and Rfare as defined above for Formula (1) and u = 0-4.

[0070] Fluoroalkyl hydroxy diene of Formula (2-2) may be methylated with amethylating reagent to provide fluoroalkyl methoxy diene compound of Formula (2-3), CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)uCH=CH2]2(2-3) wherein x, z, and Rfare defined as above for Formula (1) and u = 0-4. Examples of compounds of Formula (2-2) that may be prepared by the process disclosed herein include, but are not limited to, CClF2CClFCF2C(OCH3)[CH=CH2]2, CClF2CClFCF2CF2C(OCH3)[CH2CH2CH=CH2]2,CClF2CClFCF2CF2(OCH3)[CH2CH=CH2]2, CClF2CClFCF2CF2C(OCH3)[CH=CH2]2, CClF2CClFOCF2CF2CF2C(OCH3)[CH2CH2CH=CH2]2, CClF2CClFOCF2CF2C(OCH3)[CH2CH2CH=CH2]2, CClF2CClFOCF2CF2C(OCH3)[CH2CH=CH2]2, CClF2CClFOCF2CF2C(OCH3)[CH=CH2]2, CClF2CClFOCF2CF2CF2CF2C(OCH3)[CH2CH=CH2]2, and CClF2CClFOCF2CF(CF3)OCF2CF2C(OCH3)[CH2CH2CH=CH2]2.

[0071] In some embodiments, a fluoroalkyl methoxy diene compound of Formula (2-3) is then converted to an amine by the processes disclosed above to provide a fluoroalkyl bis(tertiary amine) compound of Formula (2-4), CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)u(CH2)tN(CH3)2]2 (2-4) wherein x, z, and Rfare defined as above for Formula (1), u = 0-4, and t = 1 to 3. Examples of fluoroalkyl bis(tertiary amine) compounds of Formula (2-4) that may be prepared by processes disclosed herein include, but are not limited to, CClF2CClFCF2C(OCH3)[CH2CH2N(CH3)2]2, CClF2CClFCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2, CClF2CClFCF2CF2C(OCH3)[CH2CH2CH2N(CH3)2]2, CClF2CClFCF2CF2C(OCH3)[CH2N(CH3)2]2, CClF2CClFCF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CClF2CClFOCF2CF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CClF2CClFOCF2CF2C(OCH3)[CH2CH2CH2N(CH3)2]2, CClF2CClFOCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2, CClF2CClFOCF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CClF2CClFOCF2CF2C(OCH3)[CH2N(CH3)2]2 and CClF2CClFOCF2CF2CF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2.

[0072] Fluoroalkyl bis(tertiary amine) compounds of Formula (2-4) may beconverted to trifluorovinyl bis(tertiary amine) compounds of Formula (2) (where y = u+t) by reaction with a dechlorinating reagent as disclosed above. Non-limiting examples of trifluorovinyl bis(tertiary amine) compounds of Formula (2) that may be prepared by the processes of this invention include, but are not limited to, CF2=CFCF2C(OCH3)[CH2CH2N(CH3)2]2,CF2=CFCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2, CF2=CFCF2CF2C(OCH3)[CH2CH2CH2N(CH3)2]2, CF2=CFCF2CF2C(OCH3)[CH2N(CH3)2]2, CF2=CFCF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CF2=CFOCF2CF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2N(CH3)2]2, CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2, CF2=CFOCF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CF2=CFOCF2CF2C(OCH3)[CH2N(CH3)2]2, and CF2=CFOCF2CF2CF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2. Compounds of Formula (3)

[0073] A trifluorovinyl quaternary ammonium salt having a composition representedby Formula (3) may be prepared by processes disclosed herein, [CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22R3]+1[Q-n]1 / n (3) wherein R3is CH3, C2-C8 straight chain or branched alkyl, or C5-C8 cycloalkyl, Q = a monovalent anion such as Cl, Br, I, OH, HCO3, HSO4, H2PO4, BF4, PF6, O3SR4(where R4= C1-C3 alkoxy, C1-C6 straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl), or a divalent anion such as CO3, SO4, or HPO4, or a trivalent anion such as PO4, wherein n is the charge on Q, and wherein x, y, z, R1, R2, and Rfare as defined above for Formula (1).

[0074] In some embodiments, trifluorovinyl quaternary ammonium salts of Formula(3) include those wherein x = 1; z = 0 to 2; Rf= (CF2)i where i = 1 to 3; R1= CH3; y = 1 to 3; R2= CH3; R3= CH3or n-C4H9, and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n =(3) include those wherein x = 0, z = 0, Rf= (CF2)iwhere i = 1 to 3, R1= CH3; y = 1 to 3; R2= CH3; R3= CH3or n-C4H9, and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n = 1, R4

[0076] In some embodiments, trifluorovinyl quaternary ammonium salts of Formula(3) include those wherein x = 1, z = 0 to 2, Rf= (CF2)iwhere i = 1 to 3, R1= CF3; y = 1 to 3; R2= CH3; R3= CH3 or n-C4H9, and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n =

[0077] In some embodiments, trifluorovinyl quaternary ammonium salts of Formula(3) include those wherein x = 0, z = 0, Rf= (CF2)i where i = 1 to 3, R1= CF3; y = 1 to 3; R2= CH3; R3= CH3 or n-C4H9, and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n = 1, R4= CH3, CF3, OCH3, C6H4-4-CH3), or CO3(n = 2).

[0078] Trifluorovinyl quaternary ammonium salts of Formula (3) may be prepared byalkylation of trifluorovinyl tertiary amines of Formula (1), for example, by reaction with an alkylating agent such as alkyl halide, alkyl tosylate, alkyl methanesulfonate, or an alkyl triflate. Reactions suitable for use herein include reactions generically termed Menschutkin reactions, that have been previously described (J. March, “Advanced Organic Chemistry”, published by John Wiley & Sons, 1985, pages 364-366). Suitable alkylating agents for the process of forming trifluorovinyl quaternary ammonium salts of Formula (3) include the compounds R3L or R3Q, where R3is defined above and L and Q are leaving groups such as Cl, Br, I, OSO2OCH3, or O3SR4where R4is C1-C3 alkoxy, C1-C6straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl. Examples of R3L include, but are not limited to, bromomethane, iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, dimethyl sulfate, diethyl sulfate, methyl p- toluenesulfonate (methyl tosylate), methyl methanesulfonate, methyl trifluoromethane sulfonate (methyl triflate), methyl 1,1,2,2-tetrafluoroethanesulfonate, bromocyclohexane, iodocyclopentane, and 1-iodohexane.

[0079] Alkylation reactions suitable for use herein may be conducted in thepresence of a solvent. Suitable solvents for the process include, water, alcohols (e.g., methanol or ethanol), acetone, mixtures of alcohol and water or acetone and water, ethers (e.g., diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dimethyl carbonate), chlorocarbons (e.g., dichloromethane or chloroform), and esters (e.g., ethyl acetate), and mixtures thereof.

[0080] Solvent employed in the alkylation reaction may be from about 1 mL ofsolvent per gram of compound of Formula (1) to about 30 mL per gram, or from about 2 mL of solvent, per gram to about 15 mL per gram. The temperatures for the alkylation step may be from about 20°C to about 60°C and may be suitably facile so that stirring at room temperature is sufficient to form the trifluorovinyl quaternary ammonium salt compound of Formula (3). The compound of Formula (3) may be purified byrecrystallization. Alternatively, in some embodiments, a compound of Formula (3) may be isolated by introducing a non-miscible solvent, precipitating the quaternary ammonium salt and isolating it by filtration, optionally, followed by washing the product with a non-miscible solvent and drying under vacuum. The initial counterions, L, may be substituted for other counterions, Q, by anion exchange reactions using a salt of counterion Q or by use of an anion exchange resin. For example, in one embodiment, a compound of Formula (1) is reacted with iodomethane to form a compound of Formula (3) where L = I, and the iodide counterion may be substituted for chloride by passing a solution of the iodide through an anion exchange column in the chloride form to provide a solution of the compound of Formula (3) wherein Q = Cl. Alternatively, a solution of the compound of Formula (3) where Q = I, may be reacted with silver trifluoromethanesulfonate to precipitate silver iodide, forming a solution of the compound of Formula (3) wherein Q = O3SCF3.

[0081] Examples of trifluorovinyl quaternary ammonium salts of Formula (3) thatmay be prepared by the processes disclosed herein, include but are not limited to, [CF2=CFCF2C(CH3)(OCH3)CH2CH2N(CH3)2(C2H5)]Br, [CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)3](O3SOCH3), [CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3), [CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2(C2H5)]Cl, [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)3](O3SCH3), [CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2N(CH3)3]I, [CF2=CFOCF2CF2C(CH3)(OCH3)CH2N(CH3)3]Cl, [CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SC6H4-4-CH3), and [CF2=CFOCF2CF(CF3)OCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2(C4H9)](Br).

[0082] In some embodiments, trifluorovinyl quaternary ammonium salts Formula (3)may be obtained by first reacting fluoroalkyl tertiary amines of Formula (1-7) or (1-15) with an alkylating agent, R3Q, to provide fluoroalkyl quaternary ammonium salts having the Formula (3-1) and (3-2), respectively. [CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2NR33]Q (3-1)[CClF2CClF(CF2) z(O) x(Rf)CF2C(R1)(OCH3)(CH2)q(CH2)tN(CH3)2R3]Q (3-2)wherein x, z, R3, and Q are as defined above for Formula (3), t = 1-3, and R1is CH3or CF3. The conditions for the alkylation step are as described for preparation of compounds of Formula (3) as described above. The quaternary ammonium salts of Formulas (3-1) and (3-2) may then be dechlorinated using a dechlorinating agent such as a reducing metal under conditions described above for dechlorinating fluoroalkyl tertiary amine compounds of Formula (1-15), to provide trifluorovinyl quaternary ammonium salts of Formula (3). Compounds of Formula (4)

[0083] The present invention also provides trifluorovinyl bis(quaternary ammonium)salts having the Formula (4). {CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22R3]2}+2[Q-n]2 / n(4) wherein x, z, R2, R3, Rf, Q and n are as defined above in Formula (3), and each y is independently 1 to 7.

[0084] In some embodiments, trifluorovinyl bis(quaternary ammonium) salts ofFormula (4) include those wherein x = 1, z = 0 to 2, Rf= (CF2)i where i = 1 to 3, y = 1 to 3, and R2= CH3, R3= CH3 or n-C4H9, and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(nFormula (4) include those wherein x = 0, z = 0, Rf= (CF2)i where i = 1 to 3, y = 1 to 3, and R2= CH3, R3= CH3 or n-C4H9, and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n =byalkylation of trifluorovinyl bis(tertiary amine) compounds of Formula (2) by reaction with alkylating agents, R3L, such as those described above under the conditions described above. Initial counterions, L, may be substituted for other counterions, Q, by anion exchange reactions as described above. The alkylation reaction may be conducted in the presence of a solvent as described above. Examples of compounds of cationic trifluorovinyl monomers of Formula (4) that may be prepared by the processes of this invention include, but are not limited to, {CF2=CFCF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SOCH3)2,{CF2=CFCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2(C2H5)]2}(I)2, {CF2=CFCF2CF2C(OCH3)[CH2CH2CH2N(CH3)3]2}(O3SCH3)2, {CF2=CFCF2CF2C(OCH3)[CH2N(CH3)2(C2H5)]2}(O3SCF3)2, {CF2=CFCF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SC6H4-4-CH3)2, {CF2=CFOCF2CF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SCF3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2N(CH3)3]2}(O3SCF3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)3]2}(O3SCH3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2(C2H5)]2}(O3SCF3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SCH3)2, {CF2=CFOCF2CF2C(OCH3)[CH2N(CH3)3]2}(Cl)2 and {CF2=CFOCF2CF2CF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2(C4H9)]2}(Br)2.

[0087] In some embodiments, trifluorovinyl bis(quaternary ammonium) salts ofFormula (4) may be obtained by first reacting fluoroalkyl bis(tertiary amine) compounds of Formula (2-4) with an alkylating agent, R3Q, to provide a fluoroalkyl bis(quaternary ammonium) salt having the Formula (4-1), {CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)u(CH2)tN(CH3)2R3]2}+2(Q)2 (4-1) wherein t, x, z, Rf, R3, and Q are as defined above in Formula (3), and u = 0 - 4. The conditions for the alkylation step are as described for conversion of trifluorovinyl tertiary amines compounds of Formula (1) to trifluorovinyl quaternary ammonium salts of Formula (3) as described above. Fluoroalkyl bis(quaternary ammonium) salts of Formulas (4-1) may then be dechlorinated using a dechlorinating agent such as a reducing metal under conditions described above for dechlorinating fluoroalkyl tertiary amine compounds of Formula (1-15), to provide trifluorovinyl bis(quaternary ammonium) salts of Formula (4). Compounds of Formula (5)

[0088] The present invention also provides a trifluorovinyl alkyl chloride compoundhaving a composition represented by Formula (5), CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R5)(CH2)rCl (5)wherein R5is CH3, (CH2)rCl, or CF3; each r is an integer from 1 to 7, and x, z, and Rfare as defined above in Formula (1).

[0089] In some embodiments, trifluorovinyl alkyl chloride compounds of Formula (5)include those wherein x = 1; z = 0 to 2; and Rf= (CF2)i where i = 1 to 3, r = 1 to 4, R5= CH3.

[0090] In some embodiments, trifluorovinyl alkyl chloride compounds of Formula (5)include those wherein x = 1; z = 0 to 2; and Rf = (CF2)iwhere i = 1 to 3, r = 1 to 4, R5= CF3.

[0091] In some(5)include those wherein x = 1; z = 0 to 2; and Rf= (CF2)iwhere i = 1 to 3, r = 1 to 4, R5= (CH2)rCl.

[0092] In some embodiments, trifluorovinyl alkyl chloride compounds of Formula (5)include those with x = 0; z = 0; and Rf= (CF2)iwhere i = 1 to 3, r = 1 to 4, R5= CH3.

[0093] In some embodiments, trifluorovinyl alkyl chloride compounds of Formula (5)include those with x = 0; z = 0; and Rf= (CF2)i where i = 1 to 3, r = 1 to 4, R5= CF3.

[0094] In some embodiments, trifluorovinyl alkyl chloride compounds of Formula (5)include those with x = 0; z = 0; and Rf= (CF2)i where i = 1 to 3, r = 1 to 4, R5= (CH2)rCl.

[0095] The starting materials for trifluorovinyl alkyl chloride compounds of Formula(5) may include a fluoroalkyl methoxyalkene compound having the of Formula (5-1), CClF2CClF(CF2)z(O)x(Rf)CF2C(R8)(OCH3)(CH2)vCH=CH2(5-1) wherein x, z, and Rfare as defined above in Formula (1); R8is CH3, CF3, or (CH2)vCH=CH2, and each v is independently an integer from 0 to 5. Fluoroalkyl methoxyalkene compounds of Formula (5-1) may be prepared according to the processes discussed above for fluoroalkyl methoxyalkene compounds of Formula (1-4).

[0096] Conversion of fluoroalkyl methoxyalkene compounds of Formula (5-1) to atrifluorovinyl alkyl chloride of Formula (5) may be effected by known processes. For example, a fluoroalkyl methoxyalkene compound of Formula (5-1) may be converted to an fluoroalkyl alcohol having the of Formula (5-2), CClF2CClF(CF2)z(O)x(Rf)C(R9)(OCH3)(CH2)vCH2CH2OH (5-2)wherein v, x, z, and Rfare as defined above in Formula (5-1), R9is CH3, CF3, or (CH2)vCH2CH2OH, by a hydroboration reaction to give the borane derivative, asdescribed in “Boranes in Organic Chemistry” (H.C. Brown, published by W. A. Benjamin, 1962).

[0097] The product resulting from hydroboration of fluoroalkyl methoxyalkenecompound of Formula (5-1) may then be oxidized, for example, as described in “Organic Synthesis via Boranes” (H. C. Brown, published by John Wiley & Sons, 1975, pages 21-26 and 87-89), the teachings of which are incorporated by reference here. Oxidation may be carried out in an ethereal solvent such as diethyl ether, tetrahydrofuran, or 1,2-dimethoxyethane, or in an alcohol. In some embodiments, hydrogen peroxide is utilized as the oxidizing agent with the reaction temperature from about 0°C to about 50°C. The reaction is exothermic; the hydrogen peroxide addition is conducted slowly with temperature control, and under a continuous purge of nitrogen in the presence of about one mole sodium hydroxide to one mole of borane. The amount of hydrogen peroxide employed in the oxidation process depends on the borane derivative and may be about one mole of hydrogen peroxide per mole of carbon-boron bond in the borane. After the addition of hydrogen peroxide is complete and heated for a time sufficient to oxidize the borane, the reaction may be hydrolyzed with water and the product may be extracted with an extracting solvent such as diethyl ether, ethyl acetate, or dichloromethane followed by phase separation, drying over a desiccant, concentration and distillation using methods well-known to those skilled in the art, to provide fluoroalkyl alcohol of Formula (5-2).

[0098] Fluoroalkyl alcohol of Formula (5-2) may then be converted to fluoroalkylhalide of Formula (5-3), CClF2CClF(CF2)z(O)x(Rf)CF2C(R10)(OCH3)(CH2)vCH2CH2X (5-3)wherein x, z, v, and Rfare defined as above in Formula (5-1); and R10= CH3, CF3, or (CH2)v+2X, wherein X = Cl, Br or I by reaction with a halogenating reagent such as PBr3, PCl3, POCl3, PCl5, SOCl2 or aqueous HCl promoted with ZnCl2, HBr, or HI. Halogenating reagents suitable for use herein include those described in “Advanced Organic Chemistry” (J. March, John Wiley & Sons, 1985, pages 382-384), the teachings of which are incorporated by reference.

[0099] The fluoroalkyl halide of Formula (5-3) where X = Cl, may be thendechlorinated to provide a trifluorovinyl alkyl chloride of Formula (5) where X = Cl. Dechlorination may be carried out using a procedure like that described above for conversion of fluoroalkyl tertiary amine of Formula (1-15) to trifluorovinyl tertiary amine of Formula (1). Dechlorination of fluoroalkyl halide compounds of Formula (5-3) where X = Cl may be carried out using zinc powder optionally pre-washed with aqueous hydrochloric acid.

[0100] Non-limiting examples of trifluorovinyl alkyl halide compounds of Formula (5)that may be prepared by the processes of this invention include CF2=CFCF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2Cl, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF2C(OCH3)(CH2CH2Cl)2, CF2=CFOCF2CF2C(OCH3)(CH2Cl)2, CF2=CFCF2CF2C(OCH3)(CH2CH2Cl)2, CF2=CFCF2CF2C(OCH3)(CH2Cl)2, CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2CH2Cl, and CF2=CFOCF2CF(CF3)OCF2CF2C(CF3)(OCH3)CH2CH2CH2Cl.

[0101] In some embodiments, a fluoroalkyl bromide is provided having the Formula(5-4), CClF2CClF(CF2)z(O)x(Rf)CF2C(R11)(OCH3)(CH2)vCH2CH2Br (5-4)wherein v, x, z, and Rfare as defined above in Formula (5-1); and R11is CH3, CF3, or (CH2)v+2Br. In one embodiment compounds may be prepared by anti-Markovnikov (Kharasch) addition of HBr to a compound of Formula (5-1) under free radical conditions (J. March, “Advanced Organic Chemistry”, John Wiley & Sons, 1985, pages 679-681). The product, predominantly a compound of Formula (5-4), may be accompanied by isomeric fluoroalkyl bromide compound having the Formula (5-5), CClF2CClF(CF2)z(O)x(Rf)CF2C(R11)(OCH3)(CH2)vCHBrCH3 (5-5)wherein v, x, z, Rfand R11are as defined above in Formula (5-1), in amounts of up to 25 weight percent.

[0102] In other embodiments of this invention, a fluoroalkyl iodide compound isprovided having the Formula (5-6), CClF2CClF(CF2)z(O)x(Rf)CF2C(R12)(OCH3)(CH2)vCH2CH2I (5-6)wherein v, x, z, and Rfare as defined above in Formula (5-1), and R12is CH3, CF3, or (CH2)v+2I. In one embodiment, compounds of Formula (5-6) may be prepared by a halogen exchange reaction such as a reaction of sodium iodide with compounds of fluoroalkyl halides of Formulas (5-3), wherein X = Cl or Br, in a polar solvent (for example, see J. March, “Advanced Organic Chemistry”, John Wiley & Sons, 1985, pages 381-382, incorporated herein by reference). Non-limiting examples of compounds of Formulas (5-4) and (5-6) that may be prepared by processes disclosed herein include but are not limited to CClF2CClFCF2C(CH3)(OCH3)CH2CH2Br, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2I, CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2Br, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2I, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2Br, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH2I, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2I, CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH2Br, CClF2CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2Br, CClF2CClFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2CH2I, and CClF2CClFOCF2CF(CF3)OCF2CF2C(CF3)(OCH3)CH2CH2CH2Br.

[0103] Processes are also provided for converting fluoroalkyl halides of Formula (5-3) to fluoroalkyl tertiary amines of Formula (1-15) wherein R1= R10= CH3or CF3, t = 2, and v=q as defined above, or to fluoroalkyl bis(tertiary amine) compounds of Formula (2-4) wherein R10= (CH2)v+2X, t = 2, and v=u as defined above. In some embodiments, conversion is carried out by reaction of fluoroalkyl halide compounds of Formula (5-3) with dimethylamine. The reaction may be conducted in a polar solvent such as acetonitrile, propionitrile, butyronitrile, dimethylsulfoxide, N,N-dimethylformamide,diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, or dimethyl carbonate or a mixture thereof. The amount of solvent in the reaction may vary from about 5 mL of solvent per gram of compound of Formula (5-3) to about 50 mL per gram of compound of Formula (5-3), or from about 10 mL of solvent per gram to about 30 mL per gram, and the compound of Formula (5-3) may be dissolved or suspended in the solvent mixture at a temperature of from about -10°C to about 80°C, or from about 0°C to about 50°C. The dimethylamine may be added to the reaction as a gas or as a solution in a non-hydroxylic solvent such as diethyl ether, tetrahydrofuran, or the like. Sufficient dimethylamine that may be added to completely react the compound of Formula (5-3) may be at least a stoichiometric amount of dimethylamine, or up to about 3 moles of dimethylamine per mole of compound of Formula (5-3). In some embodiments, about 1.3 moles to about 2.5 moles of dimethylamine are added per mole of the compound of Formula (5-3). If R10is (CH2)v+2X, then twice the amount of dimethylamine is used.

[0104] In other embodiments the fluoroalkyl halide compounds of Formula (5-3) maybe reacted with secondary amines of formula NHR132 wherein R13are independently selected from the group consisting of CH3, C2-C8straight chain or branched alkyl, C5-C8cycloalkyl, or together with nitrogen comprise a 5- to 8-membered ring. Examples of secondary amines suitable for the process described herein include dimethylamine, diethylamine, dibutylamine, diisopropylamine, di-n-hexylamine, morpholine, pyrrolidine, 2-methyl pyrrolidine, 2,5-dimethyl pyrrolidine, piperidine, 2-, 3- or 4-methylpiperidine, 2,6-dimethylpiperidine, or 3,5-dimethylpiperidine.

[0105] A fluoroalkyl tertiary amine compound suitable for use herein may include acompound having a structure represented by Formula (5-7), CClF2CClF(CF2)z(O)x(Rf)CF2C(R14)(OCH3)(CH2)vCH2CH2NR22(5-7) wherein v, x, z, Rf, and R2are as defined above, and R14is CH3, CF3, or (CH2)vCH2CH2NR22, and may be dechlorinated to form trifluorovinyl tertiary amine compounds of Formula (1) wherein R14= CH3or CF3, or trifluorovinyl bis(tertiary amine) compounds of Formula (2) wherein R14= (CH2)vCH2CH2NR22 through the procedures used for dechlorinating compounds of the fluoroalkyl tertiary amines of Formula (1-15) or fluoroalkyl bis(tertiary amine) compounds of Formula (2-4) as described above.

[0106] In some embodiments, trifluorovinyl alkyl chloride compounds of Formula (5),are provided herein, that may be prepared by reacting ketones of the typeR5C(O)(CH2)rCl wherein x, z, r, Rf , R5 are as defined above, with organometallicreactive intermediate solutions derived from polyfluoroalkylhalide compounds of Formula (1-1). Examples of these ketones, known in the art, include CF3C(O)CH2Cl, CH3C(O)CH2Cl, CH2ClC(O)CH2Cl, CH2ClCH2C(O)CH2Cl, CH2ClCH2C(O)CH2CH2Cl, CH2ClCH2CH2C(O)CH2CH2CH2Cl, and CH2ClCH2CH2CH2C(O)CH2CH2CH2CH2Cl.

[0107] In some embodiments, useful trifluorovinyl alkyl chloride compounds ofFormula (5), are provided herein, wherein x, z, and Rfare as defined above, and r = 1 to 7 and R5is CH3 or CF3, may be prepared by reacting ketones of the type R5C(O)(CH2)rCl with organometallic reactive intermediate solutions derived from polyfluoroalkylhalide compounds of Formula (1-1). Ketones which may be used include CH3C(O)CH2CH2CH2Cl, CH3C(O)CH2CH2CH2CH2Cl, CF3C(O)(CH2)5Cl, CH3C(O)(CH2)5Cl, CF3C(O)(CH2)6Cl, CH3C(O)(CH2)6Cl, and CH3C(O)(CH2)7Cl.

[0108] Products of the reaction of these ketones with organometallic reactiveintermediate solutions are fluoroalkyl hydroxyalkyl chloride compounds having a composition represented by Formula (5-8), CClF2CClF(CF2)z(O)x(Rf)CF2C(R5)(OH)(CH2)wCl (5-8)wherein x, z and Rfare defined as above in Formula (5-1); and w = 1 to 7 and R5is CH3, CF3, or (CH2)wCl.

[0109] Compounds of Formula (5-8) may be converted to fluoroalkyl methoxyalkylchloride compounds having a composition represented by Formula (5-9), CClF2CClF(CF2)z(O)x(Rf)CF2C(R5)(OCH3)(CH2)wCl (5-9)wherein z, x, w, Rfand R5are defined as above, by a methylation process as described above for conversion of compounds of Formula (1-3) to compounds of Formula (1-4).

[0110] Fluoroalkyl methoxyalkyl chloride compounds of Formula (5-9) may then beconverted to trifluorovinyl alkyl chloride compounds of Formula (5) by a dechlorination process as disclosed above, and which may be carried out using zinc powder optionally pre-washed with aqueous hydrochloric acid.

[0111] Examples of trifluorovinyl alkyl chloride compounds of Formula (5) that maybe prepared by processes provided herein, include, but are not limited to, CF2=CFCF2C(CH3)(OCH3)CH2Cl, CF2=CFCF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFCF2CF2C(CH3)(OCH3)CH2Cl, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFCF2CF2C(CF3)(OCH3)CH2Cl, CF2=CFCF2CF2C(CH2Cl)(OCH3)CH2Cl, CF2=CFOCF2CF2C(CH2CH2Cl)(OCH3)CH2CH2Cl, CF2=CFOCF2CF2C(CH2Cl)(OCH3)CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2Cl, CF2=CFOCF2CF2C(CF3)(OCH3)CH2Cl, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2Cl, CF2=CFOCF2CF2C(CH2Cl)(OCH3)CH2Cl, CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2Cl, CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF(CF3)OCF2CF2C(CH3)(OCH3)CH2Cl, CF2=CFOCF2CF(CF3)OCF2CF2C(CF3)(OCH3)CH2CH2CH2Cl CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF2C(CF3)(OCH3)(CH2)5Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)(CH2)4Cl, CF2=CFCF2CF2C(CF3)(OCH3)(CH2)6Cl, CF2=CFOCF2CF2C(CH3)(OCH3)(CH2)6Cl, CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF2C(OCH3)(CH2CH2Cl)2, CF2=CFOCF2CF2C(OCH3)(CH2Cl)2, CF2=CFCF2CF2C(OCH3)(CH2CH2Cl)2, CF2=CFCF2CF2C(OCH3)(CH2Cl)2, and CF2=CFCF2CF2C(CH3)(OCH3)(CH2)4Cl.

[0112] In some embodiments, trifluorovinyl monomers of Formula (5) are co-polymerized with tetrafluoroethylene (TFE) to form copolymers that may be reacted with tertiary amines to form quaternary ammonium ionomers. A copolymer of monomer of Formula (5) may be reacted with an imidazole or guanidine derivative to form imidazolium and guanidinium groups. Examples of imidazole may include imidazole, 1- methylimidazole, 1-methylbenzimidazole, and 1-butylimidazole. Examples of guanidine include 1,1,3,3-tetramethylguanidine.Compounds of Formula (6)

[0113] In a further embodiment, trifluorovinyl cyclic ether having the structurerepresented by (6), is disclosed.R1is CH3or CF3.

[0114] In some embodiments, trifluorovinyl cyclic ethers of Formula (6) includethose wherein x = 1; z = 0 to 2; and Rf= (CF2)iwhere i = 1 to 3, R1= CH3, and p = 1 to 3.

[0115] In some embodiments, trifluorovinyl cyclic ethers of Formula (6) includethose wherein x = 1; z = 0 to 2; and Rf= (CF2)iwhere i = 1 to 3, R1= CF3, and p = 1 to 3.

[0116] In some embodiments, trifluorovinyl cyclic ethers of Formula (6) includethose wherein x = 0; z = 0; and Rf= (CF2)i where i = 1 to 3, R1= CH3, and p = 1 to 3.

[0117] Inthose wherein x = 0; z = 0; and Rf= (CF2)iwhere i = 1 to 3, R1= CF3, and p = 1 to 3.

[0118] In some embodiments, trifluorovinyl cyclic ethers of Formula (6) includethose wherein x = 0; z = 0; and Rf= (CF2)iwhere i = 1 to 3, R1= CH3or CF3, and p = 1.

[0119] In some embodiments, trifluorovinyl cyclic ethers of Formula (6) includethose wherein x = 1; z = 0 to 2; and Rf= (CF2)i where i = 1 to 3, R1= CH3 or CF3, and p = 1.

[0120] Starting materials for trifluorovinyl cyclic ethers of Formula (6) includechloroketones having a composition represented by Formula (6-1), R1C(O)(CH2)pCl (6-1)wherein p =1 - 4, and R1is CH3or CF3. Examples of chloroketones suitable for preparing compounds of Formula (6) include CF3C(O)CH2Cl, CH3C(O)CH2Cl,CH3C(O)CH2CH2Cl, CH3C(O)CH2CH2CH2Cl, CH3C(O)CH2CH2CH2CH2Cl, CF3C(O)CH2CH2Cl, and CF3C(O)CH2CH2CH2Cl.

[0121] Chloroketones of Formula (6-1) may be reacted with organometallic reactiveintermediate solution derived from compounds of Formula (1-1) as described above to form fluoroalkyl hydroxyalkyl chlorides represented by Formula (6-2), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)pCl (6-2)wherein x, z, p, Rfand R1are as defined above, using methods and processes described herein for compounds of Formula (1-3). The amount of chloroketone of Formula (6-1) contacted with organometallic reactive intermediate solution may be from about 1.0 to about 1.2 moles of chloroketone to one mole of organometallic reactive intermediate.

[0122] In some embodiments, fluoroalkyl hydroxyalkyl chloride compounds ofFormula (6-2) are reacted with a strong, non-nucleophilic base in a solvent to deprotonate the hydroxyl group. Bases suitable for the process disclosed herein include alkaline or alkaline-earth metal hydrides where the alkaline metal is a Group 1A metal of the Periodic Table excluding hydrogen and the alkaline-earth metal is a Group 2A metal of the Periodic Table excluding beryllium. Examples of an alkaline or alkaline-earth metal hydrides suitable for the process of the invention include lithium hydride, sodium hydride, or calcium hydride. Solvents suitable for the process include those used for preparation of organometallic reactive intermediate solutions including ethereal solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, methyl tetrahydrofuran, dioxane, ethylene glycol dimethyl ether (glyme), or diethylene glycol dimethyl ether (diglyme). Temperatures suitable for reaction of compounds of Formula (6-2) with said strong base include ranges from about -30°C to about 50°C, and from about -20°C to about 30°C.

[0123] After the addition of the strong base, the reaction is gradually warmed to atemperature of from about 0°C to about 80°C, or from about 15°C to about 40°C and for a time sufficient to close the ring. The progress of the reaction may be monitored by NMR spectroscopy. After the reaction is sufficiently completed, the mixture may be hydrolyzed with water or dilute aqueous mineral acids and then filtered. After washing the solid with solvent, the organic phase in the filtrate is separated, washed with water,and the organic phase dried over a desiccating agent such as magnesium sulfate, sodium sulfate or calcium chloride. The dried organic phase may be concentrated and distilled to recover the product, a fluoroalkyl cyclic ether having the structure represented by (6-3). (6-3)wherein z, x, p, Rf, and R1are as defined above.

[0124] Fluoroalkyl cyclic ether compounds of Formula (6-3) may then bedechlorinated to trifluorovinyl cyclic ether compounds of Formula (6) by following the methods and process used for the preparation of trifluorovinyl tertiary amines of Formula (1) from fluoroalkyl tertiary amines of Formula (1-15) as described above. Examples of trifluorovinyl cyclic ethers of Formula (6) that may be prepared by the processes of this disclosure include, but are not limited to, CF2=CFCF2-cyclo- [C(CH3)OCH2-], CF2=CFCF2CF2-cyclo-[C(CH3)OCH2-], CF2=CFOCF2CF2-cyclo- [C(CH3)OCH2-], CF2=CFOCF2CF2-cyclo-[C(CF3)OCH2-], CF2=CFCF2CF2-cyclo- [C(CH3)OCH2CH2-], CF2=CFCF2CF2-cyclo-[C(CH3)OCH2CH2CH2-], CF2=CFOCF2CF2- cyclo-[C(CH3)OCH2CH2CH2CH2-], CF2=CFOCF2CF2-cyclo-[C(CH3)OCH2CH2CH2-], CF2=CFOCF2CF2-cyclo-[C(CF3)OCH2CH2CH2CH2-], CF2=CFOCF2CF2CF2CF2-cyclo- [C(CH3)OCH2CH2CH2-], CF2=CFOCF2CF(CF3)OCF2CF2-cyclo-[C(CH3)OCH2CH2-], CF2=CFCF2-cyclo-[C(CH3)OCH2CH2CH2-] and CF2=CFCF2-cyclo-[C(CH3)OCH2CH2-]. Compounds of Formula (7)

[0125] Trifluorovinyl tertiary amines represented by Formula (7) are also disclosed,CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2 (7) wherein a = 0-4, b = 0 or 1, R7are both H or both CH3, and x, z, R1, and Rfare as defined above in Formula (1).

[0126] In some embodiments, trifluorovinyl tertiary amines of Formula (7) includethose wherein x = 1; z = 0 to 2; and Rf= (CF2)i where i = 1 to 3; R1= CH3; R7= CH3; a = 0 to 2; and b = 1.

[0127] In some embodiments, trifluorovinyl tertiary amines of Formula (7) includethose wherein x = 0; z = 0; and Rf= (CF2)iwhere i = 1 to 3; R1= CH3; R7= CH3; a = 0 to 2; and b = 1.

[0128] Trifluorovinyl tertiary amine compounds of Formula (7) may be prepared bythe reaction of organometallic reactive intermediate solution as disclosed above with an aminoketone. Aminoketones suitable for use herein include compounds of Formula (7- 1) R1C(O)(CH2)a[C(R7)2]bCH2N(CH3)2 (7-1) wherein a, b, and R7are as defined above in Formula (7); and R1is CH3 or CF3, that may be obtained commercially or prepared by procedures disclosed in the literature and known in the art. Examples of aminoketones suitable for the processes described herein include CH3C(O)C(CH3)2CH2N(CH3)2, CH3C(O)CH2C(CH3)2CH2N(CH3)2, and CH3C(O)CH2CH2C(CH3)2CH2N(CH3)2, CH3C(O)CH2N(CH3)2, CH3C(O)CH2CH2N(CH3)2, CH3C(O)CH2CH2CH2N(CH3)2, CF3C(O)CH2CH2CH2N(CH3)2, CH3C(O)CH2CH2CH2CH2N(CH3)2, and CH3C(O)(CH2)5N(CH3)2.

[0129] Aminoketones as described herein may be added to organometallic reactiveintermediate solutions, derived from polyfluoroalkyl halide compounds of Formula (1-1), undiluted or as a solution in a solvent such as an alkane (pentane, hexane, heptane, and the like), arene (toluene, xylene and the like), or an ether such as that used in the Grignard reactions.

[0130] An amount of aminoketone of Formula (7-1) contacted with saidorganometallic reactive intermediate solution may be from about 1.0 to 1.2 moles of aminoketone per mole of organometallic reactive intermediate. Addition of aminoketone to organometallic reactive intermediate solution may be conducted at a temperature of from about -50°C to about -20°C with continuous stirring. After addition, the reaction may be gradually warmed to a temperature of from about 0°C to about 40°C, or from about 10°C to about 30°C, optionally stirring the reaction for a time sufficient to reactaminoketone with organometallic reactive intermediate solution. Progress of the reaction may be monitored by NMR spectroscopy, and after the reaction is sufficiently completed, the mixture may be hydrolyzed with water. The organic phase is separated, washed with water, and dried over a desiccating agent such as magnesium sulfate, sodium sulfate or calcium chloride. The dried organic phase may be concentrated and distilled to recover the product fluoroalkyl hydroxy tertiary amine compound having a composition represented by Formula (7-2), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)a[C(R7)2]bCH2N(CH3)2(7-2) wherein a, b, x, z, Rf, R1, and R7are as defined above in Formula (7).

[0131] The hydroxy group in fluoroalkyl hydroxy tertiary amine compound ofFormula (7-2) may be selectively methylated with a methylating reagent to provide fluoroalkyl methoxy tertiary amine compound of Formula (7-3), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2 (7-3) wherein a, b, x, z, Rf, R1, and R7are as defined above in Formula (7). Suitable methylating reagents include dimethyl sulfate, methyl methanesulfonate, methyl p- toluenesulfonate, or iodomethane.

[0132] In some embodiments, fluoroalkyl hydroxy tertiary amines of Formula (7-2)are at least partially deprotonated with a base such as solid potassium hydroxide, sodium methoxide, sodium hydride, potassium hydride, sodium amide, lithium diisopropylamide, butyl lithium, or potassium tert-butoxide, prior to addition of the methylating agent. Bases may be added in the form of solids, oil dispersions, or solutions in solvents such as diethyl ether, tetrahydrofuran, cyclohexane, or hexane. Bases may be added in a stoichiometric amount of one mole of base to one mole of compound of Formula (7-2), with at most an excess of 10%. Deprotonation reactions conducted in solvent such as those disclosed herein may be at a temperature of from about -78°C to about 40°C, or from about -50°C to about +20°C. After the alcohol has been at least partially converted to the conjugate base, the methylating agent is added at a temperature of from about -50°C to about -20°C and the reaction mixture gradually warmed to about 0°C to about 40°C, or about 10°C to about 30°C. Methylating agentsmay be employed in a stoichiometric amount, that is, one mole methylating agent per mole of OH group to be methylated.

[0133] In another embodiment, excess methylating agent may be employed to alsomethylate the amino group of fluoroalkyl methoxy tertiary amines compound of Formula (7-3), thereby forming fluoroalkyl quaternary ammonium salt having structure represented by Formula (7-4) in one step, [CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)3]Q (7-4)wherein a, b, x, z, Rf, R1, and R7are as defined above in Formula (7), and Q is the anion derived from the methylating agent.

[0134] Methylation reactions described herein may be conducted in a solvent suchas an alkane (e.g., hexane, heptane, etc.), aromatic hydrocarbon (e.g., toluene), a chlorinated hydrocarbon (e.g., methylene chloride or chloroform), an ether (e.g., diethyl ether or glyme), or alkane nitrile (e.g., acetonitrile). Solvent(s) may comprise from about 20 wt% to about 98 wt% of the reaction mixture, or from about 50 wt% to about 90 wt% of the reaction mixture.

[0135] Fluoroalkyl methoxy tertiary amines of Formula (7-3) may be recovered fromthe reaction by treatment with water followed by extraction of the product with an extraction solvent. Suitable extraction solvents include diethyl ether, dichloromethane, ethyl acetate, and the like. The organic phase from the extraction may be separated, washed with water, and dried over a desiccating agent such as magnesium sulfate, sodium sulfate or calcium chloride. The dried organic phase may be concentrated under vacuum and distilled to give fluoroalkyl methoxy tertiary amine of Formula (7-3). Examples of compounds of Formula (7-3) that may be prepared by processes disclosed herein, include, but are not limited to CClF2CClFCF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2, CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2N(CH3)2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2, CClF2CClFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)2, CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2,CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2, and CClF2CClFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2.

[0136] Examples of fluoroalkyl quaternary ammonium salts of Formula (7-4) thatmay be prepared by processes disclosed herein include, but are not limited to [CClF2CClFCF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)3]I, [CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)3](O3SOCH3), [CClF2CClFCF2CF2C(CH3)(OCH3)CH2N(CH3)3](O3SC6H4-4-CH3), [CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)3]Br, [CClF2CClFCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)3](O3SOCH3), [CClF2CClFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)3](O3SOCH3), [CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)3]I, [CClF2CClFOCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)3](O3SOCH3), [CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)3]I, [CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)3](O3SOCH3), and [CClF2CClFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SC6H4-4-CH3). In further embodiments, the anionic portion of fluoroalkyl quaternary ammonium salts may be changed to other counterions by ion-exchange methods as described herein.

[0137] Fluoroalkyl methoxy tertiary amines of Formula (7-3) may be dechlorinated totrifluorovinyl tertiary amines of Formula (7) by methods and procedures detailed herein for converting fluoroalkyl tertiary amines of Formula (1-15) to trifluorovinyl tertiary amines of Formula (1).

[0138] Examples of trifluorovinyl tertiary amines of Formula (7) that may beprepared by processes disclosed herein include, but are not limited to CF2=CFCF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2, CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2, CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2,CF2=CFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2, and CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2.

[0139] In some embodiments, processes are described for making trifluorovinyltertiary amines of Formula (7) wherein organometallic reactive intermediate solution is generated from reaction of a Grignard reagent, RMgZ as described above, with a polyfluoroalkenyl halide compound having a structure represented by Formula (7-5), CF2=CF(CF2)z(O)x(Rf)CF2Y (7-5)wherein x, z, and Rf, are as defined above in Formula (7) and Y is Br or I, and bis(cyclopentadienyl)zirconium dichloride as described above for preparation of fluoroalkyl hydroxyalkene compounds of Formula (1-3). Non-limiting examples of compounds of Formula (7-5) include, CF2=CFCF2Br, CF2=CFCF2I, CF2=CFCF2CF2Br, CF2=CFCF2CF2I, CF2=CFOCF2CF2Br, CF2=CFOCF2CF2I, CF2=CFOCF2CF2CF2Br, CF2=CFOCF2CF2CF2I, CF2=CFCF2OCF2CF2Br, CF2=CFCF2OCF2CF2I, CF2=CFCF2OCF2CF2CF2Br, CF2=CFOCF2CF2CF2CF2Br, CF2=CFOCF2CF2CF2CF2I, CF2=CFOCF2CF2CF2OCF2CF2I, and CF2=CFOCF2CF(CF3)OCF2CF2I. An organometallic reactive intermediate solution may be contacted with aminoketone of Formula (7-1) to form trifluorovinyl hydroxy tertiary amine having a composition represented by Formula (7-6) in accordance with methods and procedures described above, for example, for preparing fluoroalkyl tertiary amines of Formula (7-2), CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)a[C(R7)2]bCH2N(CH3)2(7-6) wherein a, b, x, z, Rf, R1, and R7are as defined above.

[0140] In some embodiments, trifluorovinyl hydroxy tertiary amines of Formula (7-6)may be selectively methylated at the hydroxyl group using a methylating agent such as dimethyl sulfate, methyl methanesulfonate, methyl p-toluenesulfonate, iodomethane, or methyl trifluoromethanesulfonate, to provide trifluorovinyl tertiary amines of Formula (7)as described above for synthesis of fluoroalkyl methoxy tertiary amines of Formula (7- 3).

[0141] In other embodiments, reaction of organometallic reactive intermediatesolution derived from polyfluoroalkenyl halides of Formula (7-5) with bis(dimethylamino)ketones having a structure represented by Formula (7-7), (CH3)2N(CH2)cC(O)(CH2)cN(CH3)2 (7-7) wherein c is 1 or 2, provides trifluorovinyl hydroxy bis(tertiary amine) compounds having a structure represented by Formula (7-8), CF2=CF(CF2)z(O)x(Rf)CF2C(OH)[(CH2)cN(CH3)2]2 (7-8) where c, x, z, and Rfare as defined above. The bis(dimethylamino)ketones of Formula (7-7) may be obtained commercially or prepared by procedures disclosed in the literature and known in the art. Examples of ketones of Formula (7-7) includes (CH3)2NCH2C(O)CH2N(CH3)2 and (CH3)2NCH2CH2C(O)CH2CH2N(CH3)2. Reaction of bis(dimethylamino)ketones of Formula (7-7) with organometallic reactive intermediate solution is conducted according to the methods disclosed herein for preparation of trifluorovinyl hydroxy tertiary amines of Formula (7-6) and fluoroalkyl hydroxyalkenes of Formula (1-3).

[0142] In some embodiments, trifluorovinyl hydroxy bis(tertiary amine) compoundsof Formula (7-8) may be selectively methylated at the hydroxyl group using a methylating agent such as dimethyl sulfate, methyl methanesulfonate, methyl p- toluenesulfonate, iodomethane, or methyl trifluoromethanesulfonate, to provide trifluorovinyl methoxy bis(tertiary amine) compounds of Formula (7-9) (Formula (2) wherein y = c and R2= CH3) as described above for synthesis of fluoroalkyl methoxy tertiary amines of Formula (7-3), CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)cN(CH3)2]2(7-9)amine) compounds of Formula (7-8) may be methylated at both the hydroxyl group and the amino groups using an excess of methylating agent to provide trifluorovinyl bis(quaternary ammonium) salts of Formula (4) wherein y = c, R2and R3are all CH3, and Q is derived from the methylating agent. For example, when the methylating agentis methyl methanesulfonate, Q is O3SCH3. The amount of methylating agent should be at least three moles of methylating agent per mole of compound of Formula (7-8) to 3.2 moles of methylating agent per mole of trifluorovinyl hydroxy bis(tertiary amine) of Formula (7-8). This exhaustive methylation may be conducted sequentially by first methylating the hydroxyl group followed by the amino groups or in one step.

[0144] In some embodiments, reaction of the organometallic reactive intermediatesolution derived from polyfluoroalkyl halide compounds of Formula (1-1) with bis(dimethylamino)ketones of Formula (7-7) provides fluoroalkyl hydroxy bis(tertiary amine) compounds of Formula (7-10), CClF2CClF(CF2)z(O)x(Rf)CF2C(OH)[(CH2)cN(CH3)2]2 (7-10) wherein c, x, z, and Rfare as defined above. The reaction may be conducted according to the methods disclosed herein for fluoroalkyl hydroxyalkenes of Formula (1-3).

[0145] In some embodiments, fluoroalkyl hydroxy bis(tertiary amine) compounds ofFormula (7-10) may be selectively methylated at the hydroxyl group to provide fluoroalkyl bis(tertiary amine) compounds, as described above for synthesis of fluoroalkyl methoxy tertiary amine compounds of Formula (7-3).

[0146] In other embodiments, fluoroalkyl hydroxy bis(tertiary amine) compounds ofFormula (7-10) may be methylated at both the hydroxyl group and the amino groups using an excess of methylating agent to provide a fluoroalkyl bis(quaternary ammonium) salt having a composition represented by Formula (7-11) {CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)cN(CH3)2]2}Q (7-11)wherein Q is derived from the methylating agent as described above.

[0147] In some embodiments, fluoroalkyl bis(quaternary ammonium) salts ofFormula (7-11) may be dechlorinated using a dechlorinating agent such as reducing metal under conditions described above for dechlorinating fluoroalkyl tertiary amines of Formula (1-15), to provide trifluorovinyl bis(quaternary ammonium) salts of Formula (4) wherein c = y and R2and R3are all CH3.

[0148] In other embodiments, a reaction of organometallic reactive intermediatesolution derived from polyfluoroalkenyl halide compounds of Formula (7-5) with a cyclic aminoketone represented by a structure of Formulas (7-12a) or (7-12b),O l1provides trifluorovinyl cyclic hydroxyamine compounds having a structure represented by Formulas (7-13a) or (7-13b),wherein l is 3, 4, or 5, l1 and l2 are 1 to 3, provided that l1 + l2 =3 to 5; x = 0 or 1; z = 0 to 4, and Rfis a straight chain or branched perfluoroalkylene group CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkj = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound. The cyclic aminoketones of Structures (7-12a) and (7-12b) may be obtained commercially or prepared by procedures disclosed in the literature and known in the art. Examples of cyclic aminoketones of Formula (7-12) include N-methylcaprolactam (cyclo-CH3NC(O)(CH2)5-, hexahydro-1-methyl-3H-azepin-3-one (cyclo-CH3NCH2C(O)(CH2)4-),hexahydro-1-methyl-4H-azepin-4-one (cyclo-CH3N(CH2)2C(O)(CH2)3-), 1-methyl-2- piperidone (cyclo-CH3NC(O)(CH2)4-), 1-methyl-3-piperidinone (cyclo-CH3NCH2C(O)(CH2)3-), 1-methy-4-piperidone (cyclo-CH3N(CH2)2C(O)(CH2)2-), N-methyl-2-pyrrolidone (cyclo-CH3NC(O)(CH2)3-), and 1-methyl-3-pyrrolidinone (cyclo-CH3NCH2C(O)(CH2)2-). Contact of cyclic aminoketones of Structures (7-12a) or (7-12b) with organometallic reactive intermediate solutions is conducted according to themethods disclosed herein for preparing trifluorovinyl hydroxy tertiary amine compounds of Formula (7-6) and fluoroalkyl hydroxyalkene compounds of Formula (1-3).

[0149] In some embodiments, a trifluorovinyl cyclic hydroxyamine compound havingthe structure (7-13a) or (7-13b) may be selectively methylated at the hydroxyl group using a methylating agent such as dimethyl sulfate, methyl methanesulfonate, methyl p- toluenesulfonate, iodomethane, or methyl trifluoromethanesulfonate, to provide a trifluorovinyl cyclic methoxyamine compound represented by a structure (7-14a) or (7- 14b) as described above for synthesis of fluoroalkyl methoxy tertiary amine compounds of Formula (7-3). (7-14a)wherein l, l1, l2, x, z, and Rfare as defined above. In other embodiments, trifluorovinyl cyclic hydroxyamine compounds of Structures (7-13a) and (7-13b) may be methylated at both the hydroxyl group and the amino group using an excess of methylating agent to provide trifluorovinyl cyclic quaternary ammonium salts having a structure represented by Formulas (7-15a) and (7-15b)(7-15a)or are to + to x = 0 or 1; z = 0 to 4, and Rfis a straight chain or branched perfluoroalkylene group CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, and Q is the counteranion derived from the methylating agent. The methylation may be carried out sequentially or in one step. The total amount of methylating agent added to trifluorovinyl cyclic hydroxyamine of Formula (7-13) should be at least two moles of methylating agent per mole of trifluorovinyl cyclic hydroxyamine of Formula (7-13) to 2.2 moles of methylating agent per mole of compound of Formula (7-13).

[0150] In other embodiments, the trifluorovinyl methoxy cyclic amine compounds ofStructures (7-14a) and (7-14b) may be further alkylated with an alkylating agent, R3Q, wherein R3is C2-C8 straight chain or branched alkyl, and C5-C8 cycloalkyl and Q is Cl, Br, I, or O3SR4and R4= CH3, CF3, OCH3, or C6H4-4-CH3, to provide trifluorovinyl cyclic quaternary ammonium salts having a structure represented by Formulas (7-16a) and (7- 16b),+ H3COwherein l is 3, 4, or 5, l1 andl2 are 1 to 3, provided that l1 + l2 =3 to 5; x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkj = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound. The total amount of alkylating agent added to trifluorovinyl cyclic methoxyamine compounds of Structures (7-14a) or (7-14b) should be at least one moles of alkylating agent per mole of compound of Structure (7-14a) or (7-14b) to 1.2 moles of alkylating agent per mole of a compound having a structure represented by Formulas (7-14a) or (7-14b).

[0151] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-15a) include x = 1, z = 0-2, Rf= (CF2)iwhere i = 1 to 3, l is 3 to 5, and cyclic aminoketones of Structure (7-12a) are N-methylcaprolactam (cyclo-CH3NC(O)(CH2)5-)where l = 5,1 methyl-2-piperidone (cyclo-CH3NC(O)(CH2)4-) where l = 4, and N-methyl-2-pyrrolidone (cyclo-CH3NC(O)(CH2)3-) where l = 3. In some embodiments, trifluorovinyl cyclic quaternary ammonium salts of Structure (7-16a) include x = 1, z = 0, R3is C2-C6 straight chain or branched alkyl, and C5 or C6 cycloalkyl and Q is Cl, Br, I, or O3SR4and R4= CH3, CF3, OCH3, or C6H4-4-CH3,and Rf= (CF2)iwhere i = 1 to 3, l is 3 or 4. In an(7- 16a) include x = 1, z = 0-2, R3is C2-C6 straight chain or branched alkyl, and C5 or C6cycloalkyl and Q is Cl, Br, I, or O3SR4and R4= CH3, CF3, OCH3, or C6H4-4-CH3,and Rf= (CF2)i where i = 1 to 3, l is 3 to 5,

[0152] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-15a) include x = 0, z = 0, Rf= (CF2)iwhere i = 1 to 3, and l is 3 to 5, and cyclic aminoketones ofCH3NC(O)(CH2)5-) = 4- l= 4, and N-methyl-2-pyrrolidone (cyclo-CH3NC(O)(CH2)3-) where l = 3. In an alternativeembodiment, trifluorovinyl cyclic quaternary ammonium salts of Structure (7-16a) include x = 0, z = 0, R3is C2-C6 straight chain or branched alkyl, and C5 or C6 cycloalkyl and Q is Cl, Br, I, or O3SR4and R4= CH3, CF3, OCH3, or C6H4-4-CH3, and Rf= (CF2)i where i = 1 to 3, and l is 3 to 5.

[0153] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-15b) include x = 1, z = 0-2, Rf= (CF2)i where i = 1 to 3, l1 is 1 and l2 is 3, and cyclic aminoketone of Structure (7-12b) is 1-methyl-3-piperidinone (cyclo- CH3NCH2C(O)(CH2)3-).

[0154] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-15b) include x = 0, z = 0, Rf= (CF2)iwhere i = 1 to 3, l1 is 1 and l2 is 3, and cyclic aminoketone of Structure (7-12b) is 1-methyl-3-piperidinone (cyclo- CH3NCH2C(O)(CH2)3-).

[0155] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-15b) include x = 1, z = 0-2, Rf= (CF2)i where i = 1 to 3, l1 and l2 are both 2, and cyclic aminoketone of Structure (7-12b) is 1-methyl-4-piperidone (cyclo- CH3N(CH2)2C(O)(CH2)2-).

[0156] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-15b) include x = 0, z = 0, Rf= (CF2)i where i = 1 to 3, l1 and l2 are both 2, and cyclic aminoketone of Structure (7-12b) is 1-methyl-4-piperidone (cyclo- CH3N(CH2)2C(O)(CH2)2-).

[0157] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-15b) include x = 1, z = 0 to 2, Rf= (CF2)i where i = 1 to 3, l1 is 1 and l2 is 2, and cyclic aminoketone of Structure (7-12b) is 1-methyl-3-pyrrolidinone (cyclo- CH3N(CH2)C(O)(CH2)2-).

[0158] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-15b) include x = 0, z = 0, Rf= (CF2)i where i = 1 to 3, l1 is 1and l2 is 2, and cyclic aminoketone of Formula (7-12b) is 1-methyl-3-pyrrolidinone (cyclo- CH3N(CH2)C(O)(CH2)2-).

[0159] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofFormula (7-16b) include x = 1, z = 0-2, Rf= (CF2)i where i = 1 to 3, l1 is 1 and l2 is 2 or 3, or l1 is 2 and l2 is 2, R3= C4H9or cyclo-C6H11, and cyclic aminoketone of Structure (7-12b) is 1-methyl-3-pyrrolidinone (cyclo-CH3N(CH2)C(O)(CH2)2-) where l1 = 1 and l2 = 2, or 1-methyl-3-piperidinone (cyclo-CH3NCH2C(O)(CH2)3-) where l1 = 1 and l2 = 3, or 1-methyl-4-piperidone (cyclo-CH3N(CH2)2C(O)(CH2)2-) where l1 is 2 and l2 is 2. In other embodiments, trifluorovinyl cyclic quaternary ammonium salts of Formula (7-16b) include x = 1, z = 0, R3= C4H9 or cyclo-C6H11, and Rf= (CF2)i where i = 1 to 3, l1 is 1 and l2 is 2 or 3, or l1 and l2 are both 2.

[0160] In some embodiments, trifluorovinyl cyclic quaternary ammonium salts ofStructure (7-16b) include x = 0, z = 0, Rf= (CF2)i where i = 1 to 3, l1 is 1 and l2 is 2 or 3, or where l1 and l2 are both 2, R3= C4H9 or cyclo-C6H11, and cyclic aminoketone of Structure (7-12b) is 1-methyl-3-pyrrolidinone (cyclo-CH3N(CH2)C(O)(CH2)2-) l1 = 1 and l2 = 2, or 1-methyl-3-piperidinone (cyclo-CH3NCH2C(O)(CH2)3-) where l1 = 1 and l2 = 3, or 1-methyl-4-piperidone (cyclo-CH3N(CH2)2C(O)(CH2)2-) where l1 is 2 and l2 is 2.

[0161] In other embodiments, reaction of organometallic reactive intermediatesolution derived from polyfluoroalkyl halide compounds of Formula (1-1) with cyclic aminoketones having general Formula (7-12), provides fluoroalkyl cyclic hydroxyamine compounds represented by Structures (7-17a) and (7-17b),(7-17b)wherein l, l1, l2, x, z, and Rfare as defined above. Contact of cyclic aminoketones of Structures (7-12a) and (7-12b) with organometallic reactive intermediate solution is conducted according to the methods disclosed herein for preparing trifluorovinyl hydroxy tertiary amine compounds of Formula (7-6) and fluoroalkyl methoxyalkene compounds of Formula (1-4).

[0162] In some embodiments, fluoroalkyl cyclic hydroxyamine compounds ofStructures (7-17a) and (7-17b) may be selectively methylated at the hydroxyl group using a methylating agent such as dimethyl sulfate, methyl methanesulfonate, methyl p- toluenesulfonate, iodomethane, or methyl trifluoromethanesulfonate, to provide fluoroalkyl cyclic methoxyamine compounds represented by Structures (7-18a) and (7- 18b),of Formula (7-3).

[0163] In other embodiments, fluoroalkyl cyclic hydroxyamine compounds ofStructures (7-17a) and (7-17b) may be methylated at both the hydroxyl group and theamino group using an excess of methylating agent to provide fluoroalkyl cyclic quaternary ammonium salts represented by Structures (7-19a) and (7-19b), (7-19a)wherein l, l1, l2, x, z, and Rfare as defined above and Q is the counteranion derived from the methylating agent. The methylation may be carried out sequentially or in one step. The total amount of methylating agent added to fluoroalkyl cyclic hydroxyamine compound of Structure (7-17a) or (7-17b) should be at least two moles of methylating agent per mole of compound of Formula (7-17a) or (7-17b) to 2.2 moles of methylating agent per mole of compound of Formula (7-17a) or (7-17b).

[0164] In other embodiments, the fluorinated methoxy cyclic amine compounds ofStructures (7-18a) and (7-18b) may be further alkylated with an alkylating agent, R3Q, wherein R3is C2-C8straight chain or branched alkyl, and C5-C8cycloalkyl and Q is Cl, Br, I, or O3SR4and R4= CH3, CF3, OCH3, or C6H4-4-CH3, to provide fluoroalkyl cyclic quaternary ammonium salts represented by Structures (7-20a) and (7-20b),(7-20a)wherein l, l1, l2, x, z, and Rfare as defined above, and Q is the counteranion derived from the methylating agent. The total amount of alkylating agent added to fluoroalkyl cyclic methoxyamine compound of Structure (7-18a) or (7-18b) should be at least one moles of alkylating agent per mole of compound of Formula (7-18a) or (7-18b) to 1.2 moles of alkylating agent per mole of compound of Formula (7-18a) or (7-18b).

[0165] In some embodiments, fluoroalkyl cyclic quaternary ammonium salts ofStructures (7-19a), (7-19b), (7-20a), or (7-20b) may be dechlorinated using a dechlorinating agent such as a reducing metal under conditions described above for dechlorinating fluoroalkyl tertiary amines of Formula (1-15) to trifluorovinyl tertiary amines of Formula (1), to provide trifluorovinyl cyclic quaternary ammonium salts of Structures (7-15a), (7-15b), (7-16a), or (7-16b), respectively. Compounds of Formula (8)

[0166] Trifluorovinyl quaternary ammonium salts of Formula (8) are disclosed,{CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2R3}+1[Q-n]1 / n(8) wherein a, b, x, z, Q, R3, R1, and Rfare as defined above, and R7are both H or both CH3.

[0167] In some embodiments, trifluorovinyl quaternary ammonium salts of Formula(8) include those wherein x = 1; z = 0 to 2; Rf= (CF2)i where i = 1 to 3; R1= CH3; R7= CH3; a = 0 to 2; b = 1; R3= n-C4H9, n-C6H13, or cyclo-C6H11; and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n = 1, R4= CH3, CF3, OCH3, C6H4-4-CH3), or CO3(n = 2).

[0168] In some embodiments, trifluorovinyl quaternary ammonium salts of Formula(8) include those wherein x = 0; z = 0; Rf= (CF2)i where i = 1 to 3; R1= CH3; R7= CH3; a = 0 to 2; b = 1; R3= n-C4H9, n-C6H13, or cyclo-C6H11; and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n = 1, R4= CH3, CF3, OCH3, C6H4-4-CH3), or CO3(n = 2).

[0169] In some embodiments, trifluorovinyl quaternary ammonium salts of Formula(8) include those wherein x = 1; z = 0 to 2; Rf= (CF2)i where i = 1 to 3; R1= CH3; R7= CH3; a = 0 to 2; b = 1; R3= CH3; and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n = 1,(8) include those wherein x = 0; z = 0; Rf= (CF2)iwhere i = 1 to 3; R1= CH3; R7= CH3; a = 0 to 2; b = 1; R3= CH3; and Q = Cl, Br, or I (n = 1), OH (n = 1), O3SR4(n = 1, R4=

[0171] Trifluorovinyl quaternary ammonium salts compounds of Formula (8) areprepared by the process of alkylation of trifluorovinyl tertiary amines of Formula (7) with an alkylating agent such as alkyl halide, alkyl tosylate, alkyl methanesulfonate, or an alkyl triflate. Alkylation may be carried using the methods and procedures described herein for converting compounds of trifluorovinyl tertiary amines of Formula (1) to trifluorovinyl quaternary ammonium salts of Formula (3).

[0172] Methylation of trifluorovinyl hydroxy tertiary amine compounds of Formula (7-6) are disclosed to form trifluorovinyl quaternary ammonium salts of Formula (8) wherein R3is CH3. Methylation may be effected by reacting trifluorovinyl hydroxy tertiary amine compound of Formula (7-6) with a methylating agent such as dimethyl sulfate, methyl methanesulfonate, methyl trifluoromethanesulfonate, or methyl p- toluenesulfonate. Solvents suitable for methylation include alkanes (e.g., hexane, heptane, and the like), aromatic hydrocarbons (e.g., toluene), chlorinated hydrocarbons (e.g., methylene chloride or chloroform), ethers (e.g., diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, dioxane, ethylene glycol dimethyl ether (glyme), or diethyleneglycol dimethyl ether (diglyme), or alkane nitriles (e.g., acetonitrile). Temperatures suitable for the methylation of compounds of Formula (7-6) are from about -30°C to about 50°C, or from about -20°C to about 30°C. The amount of methylating agent may be from about 2 moles of methylating agent per mole of compound of Formula (7-6) to about 2.2 moles of methylating agent per mole of compound of Formula (7-6) for methylation of both the dimethylamino group and the hydroxyl group of the compound of Formula (7-6).

[0173] In some embodiments, trifluorovinyl quaternary ammonium salts of Formula(8), wherein R3= CH3, are prepared by dechlorination of fluoroalkyl quaternary ammonium salts of Formula (7-4) by following the methods and process used for the preparation of trifluorovinyl tertiary amine compounds of Formula (1) from fluoroalkyl tertiary amine compounds of Formula (1-15) as described above.

[0174] Examples of trifluorovinyl quaternary ammonium salts of Formula (8) thatmay be prepared by processes disclosed herein, include, but are not limited to, [CF2=CFCF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)3]I, [CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)3](O3SOCH3), [CF2=CFCF2CF2C(CH3)(OCH3)CH2N(CH3)3](O3SC6H4-4-CH3), [CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)3]Br, [CF2=CFCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)3](O3SOCH3), [CF2=CFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)3](O3SOCH3), [CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3), [CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2(C2H5)](O3SCF3), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2(C4H9)](Br), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2(C6H13)](Br), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2(cyclo-C6H11)](Br), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)3](O3SOCH3), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)3]I, [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)3](O3SOCH3), and [CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SC6H4-4-CH3).

[0175] In one embodiment, methylation of trifluorovinyl hydroxy bis(tertiary amine)compounds of Formula (7-8) may be effected using methods and procedures describedherein for methylation of trifluorovinyl hydroxy tertiary amine compounds of Formula (7- 6) to form trifluorovinyl bis(quaternary ammonium) salts of Formula (4), wherein y = 1 or 2, each R2= CH3 and R3= CH3 and where x, z, Q, and Rfare as defined above. Examples of trifluorovinyl bis(quaternary ammonium) salts derived from methylation of compounds of Formula (7-8) include, but are not limited to {CF2=CFCF2C(OCH3)[CH2N(CH3)3]2}(I)2, {CF2=CFCF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SOCH3)2, {CF2=CFCF2CF2C(OCH3)[CH2N(CH3)3]2}(O3SCH3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SCH3)2, {CF2=CFOCF2CF2C(OCH3)[CH2N(CH3)3]2(O3SCF3)2, and {CF2=CFOCF2CF2CF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SC6H4-4-CH3)2. Compounds of Formula (9)

[0176] Trifluorovinyl alkyl nitrile compounds having a structure represented byFormula (9) are also disclosed CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(R6)(CH2)mCN (9)wherein m = 0-5, R1is CH3 or CF3, and R6is selected from the group consisting of CH3 and OCH3provided that when R6= CH3then m = 0, and x, z and Rfare as defined above.

[0177] In some embodiments, trifluorovinyl alkyl nitrile compounds of Formula (9)include those wherein x = 1; z = 0 to 2; Rf= (CF2)i where i = 1 to 3, R1= CH3; R6= OCH3; and m = 1 to 3.

[0178] In some embodiments, trifluorovinyl alkyl nitrile compounds of Formula (9)include those wherein x = 0; z = 0; Rf= (CF2)i where i = 1 to 3; R1= CH3; R6= OCH3; and m = 1 to 3.

[0179] In some embodiments, trifluorovinyl alkyl nitrile compounds of Formula (9)include those wherein x = 1; z = 0 to 2; Rf= (CF2)i where i = 1 to 3; R1= CF3; R6= OCH3; and m = 1.

[0180] In some embodiments, trifluorovinyl alkyl nitrile compounds of Formula (9)include those wherein x = 0; z = 0; Rf= (CF2)i where i = 1 to 3; R1= CF3; R6= OCH3; and m = 1.

[0181] In some embodiments, trifluorovinyl alkyl nitrile compounds of Formula (9)include those wherein x = 1; z = 0 to 2; Rf= (CF2)i where i = 1 to 3; R1= CH3 or CF3; R6= CH3; and m = 0.

[0182] In some embodiments, trifluorovinyl alkyl nitrile compounds of Formula (9)include those wherein x = 0; z = 0; Rf= (CF2)iwhere i = 1 to 3; R1= CH3or CF3; R6= CH3; and m = 0.

[0183] Starting materials for trifluorovinyl alkyl nitrile compounds of Formula (9)wherein m = 1-5 are cyanoketones having a structure represented by Formula (9-1), R1C(O)(CH2)mCN (9-1)wherein R1is as defined above, that may be obtained commercially or prepared by known procedures. Non-limiting examples of cyanoketones of Formula (9-1) suitable for processes disclosed herein, include CF3C(O)CH2CN, CH3C(O)CH2CN, CH3C(O)CH2CH2CN, CH3C(O)CH2CH2CH2CN, and CH3C(O)CH2CH2CH2CH2CN.

[0184] In some embodiments, cyanoketones are reacted with organometallicreactive intermediate solution derived from polyfluoroalkyl halide compound of Formula (1-1) to form a fluoroalkyl hydroxynitrile compound having a structure represented by Formula (9-2), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)mCN (9-2)where x, z, Rf, and R1are as defined above, and m = 1-5, following the methods and procedures described herein for converting alkenyl ketones of Formula (1-2) to fluoroalkyl hydroxyalkenes of Formula (1-3).

[0185] Fluoroalkyl hydroxynitrile compounds of Formula (9-2) may be methylated toform a fluoroalkyl methoxynitrile compound having a structure represented by Formula (9-3), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)mCN (9-3)where x, z, Rf, and R1are as defined above, and m = 1-5, by following the methylation methods and procedures detailed above for preparation of fluoroalkyl methoxyalkene compounds of Formula (1-4).

[0186] Fluoroalkyl methoxynitrile compounds of Formula (9-3) may be dechlorinatedto provide trifluorovinyl alkyl nitrile compounds of Formula (9), wherein R6= OCH3, by dechlorination procedures, such as those detailed herein for preparation of trifluorovinyl tertiary amine compounds of Formula (1).

[0187] In some embodiments, trifluorovinyl alkyl nitrile compounds of Formula (9),wherein m = 0, R1= CH3 or CF3 and R6= CH3, may be prepared by a process starting with a cyanoalcohol having a structure represented by Formula (9-4), R1C(OH)(CH3)CN (9-4)where cyanoalcohols are converted to a reactive cyanosulfate ester having a composition represented by Formula (9-5), R1C(OT)(CH3)CN (9-5)wherein T = SO2R4, and R4is C1-C3 alkoxy, C1-C6 straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl, by reaction with a sulfonyl chloride compound such as ClSO2CH3or ClSO2C6H4-4-CH3or an anhydride such as (CF3SO2)2O or (CH3SO2)2O. Suitable solvents for the conversion of cyano alcohols of Formula (9-4) to cyanosulfate ester of Formula (9-5) include alkanes (hexane, heptane, etc.), arenes (e.g., toluene), or halocarbons (dichloromethane, 1,2-dichloroethane, chloroform, etc.). Suitable temperatures for conversion of cyanoalcohols of Formula (9- 4) to cyanosulfate ester of Formula (9-5) are from about -20°C to about 60°C, or from about -10°C to about +30°C. Cyanosulfate esters of Formula (9-5) may be isolated from the reaction mixture by extraction following a hydrolysis step using a buffered solution of pH 6.5 to pH 8 such as provided by a mixture of sodium or potassium mono- and dihydrogen phosphate. Extraction solvents include, but are not limited to, diethyl ether, ethyl acetate, or dichloromethane. After separation of the extracted organic phase, removal of the solvent under vacuum provides the cyanosulfate ester of Formula (9-5). The cyanosulfate ester of Formula (9-5) are reacted with organometallic reactive intermediate solution derived from polyfluoroalkyl halide compounds of Formula (1-1). The reaction of cyanosulfate ester of Formula (9-5) with organometallic reactive intermediate solution may be conducted at a temperature of from about -40°C to about 60°C, or from about -30°C to about 30°C. Progress of the reaction may be monitored bygas chromatography or NMR. The amount of cyanosulfate ester of Formula (9-5) relative to organometallic reactive intermediate may be stoichiometric (one mole of cyanosulfate ester per mole or organometallic reactive intermediate) to 1.2 moles of cyanosulfate ester of Formula (9-5) to one mole of organometallic reactive intermediate. After the reaction is sufficiently completed, the mixture may be hydrolyzed with water or dilute aqueous mineral acids and filtered. After washing the solid with solvent, the organic phase in the filtrate may be separated, washed with water, and dried over a desiccating agent such as magnesium sulfate, sodium sulfate or calcium chloride. The dried organic phase may be concentrated and distilled to recover the product, fluoroalkyl nitrile having a structure represented by Formula (9-6), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(CH3)CN (9-6)wherein x, z, Rfand R1are as defined above. Fluoroalkyl nitrile of Formula (9-6) may be converted to trifluorovinyl alkyl nitrile having a structure represented by Formula (9-7) by the dechlorination CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(CH3)CN ` (9-7)process described herein for the conversion of fluoroalkyl tertiary amine of Formula (1- 15) to a trifluorovinyl tertiary amine of Formula (1).

[0188] In another embodiment, cyanosulfate esters of Formula (9-5) may becontacted with organometallic reactive intermediate solutions derived from polyfluoroalkenyl halide compounds of Formula (7-5) to give trifluorovinyl nitrile compounds of Formula (9-7), wherein x, z, Rfand R1are as defined above.

[0189] In another embodiment, the reduction of fluoroalkyl methoxynitrilecompounds of Formula (9-3) to fluoroalkyl primary amines having a structure represented by Formula (9-8), CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)mCH2NH2(9-8) wherein m, x, z, Rfand R1are as defined above, is provided. In one embodiment m = 1 to 5. The reduction may be carried using lithium aluminum hydride, boranes, or catalytically with hydrogen was generally described by J. March in “Advanced Organic Chemistry”, John Wiley & Sons, 1985, page 815. Primary amines of Formula (9-8) maybe converted to tertiary amines of Formula (1-15) by the methods described above for transforming fluoroalkyl primary amines of Formula (1-5) to fluoroalkyl tertiary amines of Formula (1-6) or (1-7).

[0190] Non-limiting examples of trifluorvinyl alkyl nitrile compounds of Formula (9)that may be prepared by processes disclosed herein includeCF2=CFCF2C(CH3)(OCH3)CH2CH2CN, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CN,CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CN, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2CN, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CN, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CN, CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CN, CF2=CFOCF2CF(CF3)OCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2CN, CF2=CFOCF2CF2C(CF3)(CH3)CN, CF2=CFOCF2CF2C(CH3)2CN, and CF2=CFCF2CF2C(CH3)2CN.

[0191] Embodiments disclosed herein also include a method for preparing afluoroalkyl nitrile having a structure represented by Formula (10), Rf1CF2C(CH3)(R1)CN (10)where R1= CH3or CF3and Rf1is a straight or branched chain perfluoroalkyl, chlorofluoroalkyl, or fluoroalkyl group, optionally containing ether linkages, CeHfClgF2e+1-f-gOh wherein e = 1 to 6, f = 0 to 4, g = 0 to 2, and h = 0 to 2 provided that no O-O bonds are present, comprising (i) reacting a cyanoalcohol of Formula (9-4) R1C(OH)(CH3)CN with a sulfonyl chloride such as ClSO2CH3or ClSO2C6H4-4-CH3or an anhydride such as (CF3SO2)2O or (CH3SO2)2O, to form cyanosulfate ester of Formula (9-5), (ii) preparing organometallic reactive intermediate solution by reacting a fluoroalkyl halide compound, Rf1CF2Y, where Y = Br or I and Rf1as defined above, with a Grignard reagent of formula RMgZ, wherein R = C1-C6alkyl, or aryl, and Z = Cl, Br, or I, followed by addition of a bis(cyclopentadienyl)zirconium dichloride compound, and (iii) reacting organometallic reactive intermediate formed in (ii) with cyanosulfate ester compound of Formula (9-5) formed in (i).

[0192] In some embodiments, fluoroalkyl nitrile compounds of Formula (10) includethose wherein Rf1= CF3(CF2)i, CClF2CClF(CF2)i, or CClF2CClFO(CF2)i, where i = 1 to 3, and R1 = CH3 or CF3.

[0193] Embodiments disclosed herein also include a method for preparing afluoroalkenyl nitrile having a structure represented by Formula (11), Rf2CF2C(CH3)(R1)CN (11)where R1= CH3or CF3and Rf2is a straight or branched chain perfluoroalkenyl, chlorofluoroalkenyl, or fluoroalkenyl group, optionally containing ether linkages, CeHfClgF2e-1-f-gOh wherein e, f, g, and h are as defined above, provided that no O-O bonds are present, comprising (a) reacting a cyanoalcohol of Formula (9-4) with a sulfonyl chloride such as ClSO2CH3or ClSO2C6H4-4-CH3or an anhydride such as (CF3SO2)2O or (CH3SO2)2O, to form cyanosulfate ester compound of Formula (9-5), (b) preparing organometallic reactive intermediate solution by reacting a fluoroalkenyl halide compound, Rf2CF2Y, where Y = Br or I and Rf2as defined above, with a Grignard reagent of formula RMgZ, wherein R = C1-C6 alkyl, or aryl, and Z = Cl, Br, or I, followed by addition of bis(cyclopentadienyl)zirconium dichloride, and (c) reacting organometallic reactive intermediate formed in (b) with cyanosulfate ester compound of Formula (9-5) formed in (a).

[0194] In some embodiments, fluoroalkenyl nitrile compounds of Formula (11)include those wherein Rf2= CF2=CF(CF2)i or CF2=CFO(CF2)i, where i = 1 to 3, and R1= CH3or CF3. Polymerization

[0195] Trifluorovinyl compounds of Formulas (3), (4), (5), (6), (7-15a), (7-15b), (7-16a), (7-16b), (8) and (9) may serve as monomers for use in co-polymerization reactions with one or more co-monomers to provide a copolymer that is useful as an ionomer or ionomer precursor. Co-monomers suitable for the processes disclosed herein include, but are not limited to, CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3,CF2=CFOC2F5, CF2=CFOC3F7, cyclo-[OC(CF3)2OCF=CF]- (4,5-difluoro-2,2-bis(trifluoromethyl-1,3-dioxole), cyclo-[OC(=CF2)OCF2CF(CF3)]- (2-difluoromethylene-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane), cyclo-[OC(=CF2)OCF(CF3)CF(CF3)]- (2-difluoromethylene-4,5-diifluoro-4,5-bis(trifluoromethyl)-1,3-dioxolane),CF2=CFOCF2CF2CF=CF2, and cyclo-[OCF=C(OCF3)OCF2]- (2,2,4-trifluoro-5-(trifluoromethoxy)-1,3-dioxole). In one embodiment, at least one comonomer isCF2=CF2, CF2=CFCF3, CF2=CFOCF3, CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3)-, CF2=CFOCF2CF2CF=CF2, or cyclo-[OCF=C(OCF3)OCF2]-. In another embodiment, atleast one comonomer is CF2=CF2, CF2=CFCF3, CF2=CFOCF3, CF2=CFOC2F5or CF2=CFOC3F7.

[0196] In some embodiments, a trifluorovinyl monomer of Formula (3), (4), (5), (6),(7-15a), (7-15b), (7-16a), (7-16b), (8) or (9) is copolymerized with CF2=CF2, and at least one other comonomer selected from CF2=CClF, CF2=CFCF3, CF2=CFOCF3, CF2=CFOC2F5 or CF2=CFOC3F7. In a further embodiment, a trifluorovinyl monomer of Formula (3), (4), (5), (6), (7-15a), (7-15b), (7-16a), (7-16b), (8) or (9) may becopolymerized with CF2=CF2 and a further comonomer selected from cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3)-, CF2=CFOCF2CF2CF=CF2, or cyclo-[OCF=C(OCF3)OCF2]-. The resulting copolymermay be a neutral or cationic, linear copolymer with a perfluorinated backbone, and the inclusion of the comonomer into the backbone may be random or non-random.

[0197] The ratio of trifluorovinyl monomer of Formula (3), (4), (5), (6), (7-15a), (7-15b), (7-16a), (7-16b), (8) or (9) to comonomer may be selected to achieve a desired concentration of cationic end groups in the final ionomer suitable for use in making anion exchange membranes for fuel cell and / or water electrolysis applications.

[0198] In some embodiments, copolymers comprising TFE and a quaternaryammonium trifluorovinyl monomer selected from Formulas (3), (4), (7-15a), (7-15b), (7- 16a), (7-16b), and (8) have an equivalent weight (EW) of optionally, from about 600 EW to about 5000 EW, or from about 600 EW to about 1500 EW, or from about 700 EW to about 1000 EW. In a further embodiment, a copolymer comprising TFE and a quaternary ammonium trifluorovinyl monomer selected from Formulas (3), (4), (7-15a), (7-15b), (7-16a), (7-16b), or (8) has an equivalent weight (EW) of from about 600 EW to about 1500 EW, or from about 700 to about 1100.

[0199] Co-polymerization of a trifluorovinyl monomer of Formula (3), (4), (5), (6), (7-15a), (7-15b), (7-16a), (7-16b), (8) or (9) with a co-monomer described above may be conducted under aqueous or non-aqueous conditions. For example, in a non-aqueous polymerization, a trifluorovinyl compound of Formula (3), (4), (5), (6), (7-15a), (7-15b), (7-16a), (7-16b), (8) or (9) is transferred to a suitable reaction vessel and dissolved or suspended in one or more solvents in the absence of oxygen. Solvents suitable for the polymerization include dichloromethane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane,1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoroheptane, tetradecafluorohexane,octadecafluorooctane, 1-[1-[difluoro(1,2,2,2-tetrafluoroethoxy)methyl]-1,2,2,2-tetrafluoroethoxy]-1,1,2,2,3,3,3-heptafluoropropane, 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2,2-tetrafluoroethoxy)propane, perfluorobutylamine, and perfluoro-2-butyltetrahydrofuran. A co-solvent may be added to aid in solubility of the trifluorovinylmonomer. Suitable co-solvents for polymerization of one or more trifluorovinyl monomers and other co-monomers disclosed herein include dichloromethane, 1,2- dichloroethane, 1,1,1-trifluoro-2,2-difluoroethane, 3,3-dichloro-1,1,1,2,2- pentafluoropropane, and 1,3-dichloro-1,1,2,2,3-pentafluoropropane. Co-polymerizations may be initiated by the use of a free radical initiator such as a peroxide or dissociable azo compound. In order to form free radicals at a useful rate, a suitable initiator for the present polymerization process has a half-life on the order of 0.5 h to 3 h. Peroxide initiators soluble in the fluorocarbon solvents may be used in the co-polymerization media. Peroxide initiators useful for processes described herein include peroxides formed from highly fluorinated carboxylic acids such as perfluoropropanoyl peroxide, perfluorobenzoyl peroxide, and bis[2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)-1- oxopropyl] peroxide. Initiators may be fed to the reactor as a solution in reaction solvent or solvent mixture. An initiator may be added in one portion or fed continuously as the fluoro-co-monomer is being added.

[0200] The co-polymerization of a trifluorovinyl monomer of Formula (3), (4), (5), (6),(7-15a), (7-15b), (7-16a), (7-16b), (8) or (9) with a co-monomer described herein is conducted at temperatures of from about 0°C to about 80°C, or from about 10°C to about 40°C. Co-monomers may be added continuously to the reactor maintaining a high relative concentration of a trifluorovinyl monomer of Formula (3), (4), (5), (6), (7-15a),(7-15b), (7-16a), (7-16b), (8) or (9). The addition of co-monomer may be continued until a pre-determined amount of co-monomer has been added. The co-polymerization may be held at a temperature, for example, in the range of 30°C to 60°C for a hold time, typically 1 hour to 6 hours. The co-polymerization reaction mass is then discharged from the reactor and filtered. The copolymer solid is washed with a solvent suitable for removing any unreacted trifluorovinyl monomers of Formulas (3), (4), (5), (6), (7-15a), (7-15b), (7-16a), (7-16b), (8) or (9) and then dried.

[0201] In some embodiments, co-polymerization of trifluorovinyl a monomer ofFormula (3), (4), (5), (6), (7-15a), (7-15b), (7-16a), (7-16b), (8) or (9) with one or more co-monomers described herein may also be polymerized in an aqueous medium using a peroxide or redox initiator. Such a method of co-polymerization corresponds to those established in the art for the polymerization of tetrafluoroethylene in aqueous media.

[0202] In some embodiments, trifluorovinyl quaternary ammonium monomers ofFormulas (3), (4), (7-15a), (7-15b), (7-16a), (7-16b), or (8) are co-polymerized with tetrafluoroethylene (TFE) to form cationic ionomers. For example, the trifluorovinyl quaternary ammonium monomer, [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3), may be co-polymerized with TFE to form a cationic ionomer. These ionomers may have an equivalent weight (grams of ionomer per mole of quaternary ammonium group) of from about 600 to about 1500. The equivalent weight for a cationic ionomer may be determined by titration of the ionomer in the hydroxide form or by NMR analysis. The inverse of equivalent weight is known as ion exchange capacity (milliequivalents of ions / gram of ionomer). For example, a 1000EW ionomer has an ion exchange capacity of about 1.0.

[0203] In some embodiments, trifluorovinyl monomers of Formula (5) co-polymerized with tetrafluoroethylene (TFE) form a copolymer that may be reacted with a tertiary amine to form a quaternary ammonium ionomer. A resulting quaternary ammonium ionomer may have an equivalent weight (grams of ionomer per mole of quaternary ammonium group) of from about 600 to about 1500. The quaternized copolymers with cationic end groups are useful and may be formed as anion exchange membranes for use in fuel cells and water electrolysis cells.

[0204] Copolymers of trifluorovinyl quaternary ammonium monomers of Formulas(3), (4), (7-15a), (7-15b), (7-16a), (7-16b), and (8) and co-monomers, such as those disclosed herein, having cationic end groups, are useful for ion exchange applications, for example, such as anion exchange membranes for use in fuel cells and / or water electrolysis cells.

[0205] A copolymer prepared by co-polymerizing a trifluorovinyl monomer ofFormula (3), (4), (7-15a), (7-15b), (7-16a), (7-16b), or (8) as described herein, and co- monomer comprising at least one of CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3,CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3)-,CF2=CFOCF2CF2CF=CF2, or cyclo-[OCF=C(OCF3)OCF2]-, may be contacted with asolvent such as methanol, ethanol, n-propanol, water, acetonitrile, N,N- dimethylacetamide, N,N-dimethyl formamide, or dimethylsulfoxide, or mixtures thereof, for example, under vigorous agitation to form a polymer dispersion. In some embodiments, dispersions may be formed having a solids content of from about 2 weight percent to about 30 weight percent, or from about 5 weight percent to 20 weight percent.

[0206] Quaternized copolymers formed by reacting a tertiary amine and co-polymer,wherein the copolymer is formed from the reaction of trifluorovinyl monomers of Formula (5) with co-monomer described herein, may be contacted with a solvent such as methanol, ethanol, n-propanol, water, acetonitrile, N,N-dimethylacetamide, N,N- dimethyl formamide, or dimethylsulfoxide, or mixtures thereof, under vigorous agitation. In some embodiments, resulting dispersions may be formed having solids content of from about 2 weight percent to about 30 weight percent, or from about 5 weight percent to 20 weight percent.

[0207] Copolymers prepared by co-polymerization of a trifluorovinyl quaternaryammonium monomer comprising Formulas (3), (4), (7-15a), (7-15b), (7-16a), (7-16b), or (8), and a fluorinated co-monomer, or quaternized copolymers copolymers formed by reaction of tertiary amines of formula NR33, guanidines, or imidazoles, with copolymers formed from trifluorovinyl monomers of Formula (5) with co-monomers, as describedherein, may be contacted with a solvent. Suitable solvents such as methanol, ethanol, n-propanol, water, acetonitrile, N,N-dimethylacetamide, N,N-dimethyl formamide, or dimethylsulfoxide, or mixtures. In some embodiments, when contacted under vigorous agitation, a dispersion is formed having a solids content of from about 2 weight percent to about 30 weight percent, or from about 5 weight percent to 20 weight percent. Dispersions may be cast onto a substrate such as glass or polymer (e.g., poly(ethylene) or poly(ethylene terephthalate)) and subjected to temperatures of from about 50°C to about 100°C to remove the solvent followed by a coalescence time of 0.5 h to about 10 h at a temperature of from about 80°C to about 120°C to provide an ionomer suitable for applications requiring an anion exchange membrane.

[0208] In other embodiments, copolymers of trifluorovinyl alkyl nitrile compounds ofFormula (9) with co-monomers disclosed herein may be reacted under reducing conditions to convert the cyano group to an amino group (CH2NH2). The amino group may then be quaternized converting the amino-substituted copolymer to a copolymer bearing a cationic group as described herein. In other embodiments, copolymers of trifluorovinyl cyclic ethers of Formula (6), wherein p =1, with the co-monomers disclosed herein may be reacted with ammonia, primary amines, or secondary amines, NH3-xR2xwhere x = 0, 1, or 2, to open the epoxide ring to form a copolymer having - C(R1)(OH)(CH2NH2-xR2x) end groups where R1and R2are as defined above. Conversion of epoxide to β-hydroxyamines is described in “Advanced Organic Chemistry” by J. March, published by John Wiley & Sons, 1985, pages 368-369, and byRamachandran, et al. in Journal of Organic Chemistry, volume 60, pages 41-46, 1995,the teaching of which are incorporated by reference herein. The β-hydroxyamino end groups may be alkylated or methylated as described above for conversion of compounds of Formula (7-17a) to compounds of Formula (7-19a). EXAMPLES Example 1Preparation of CF2=CFOCF2CF2C(CH3)(OCH3)(CH2)3N(CH3)2Step 1

[0209] Under nitrogen protection, CF2=CFOCF2CBrF2 (approximately 100 g, 0.361mole; commercially available) and a stirring bar were added to a 500 mL three-neck flask. The flask was cooled to -20oC and connected to a Dewar-type condenser maintained at -78oC using a dry ice / isopropyl alcohol mixture. Cl2gas was then bubbling slowly through the liquid. Excess Cl2was absorbed by aqueous NaOH solution. The reaction process was monitored by GC-MS; the chlorine gas supply stopped once the reaction finished. The condenser temperature was then warmed to -18oC, and the reaction mixture was purged with nitrogen for approximately 30 mins. The remaining crude product was distilled under vacuum to give 124 g of CClF2CClFOCF2CBrF2, as acolorless liquid (98.7% yield). 19F NMR (376 MHz, CDCl3) δ -69.53 (t, J = 4.2 Hz, 2F), -69.90 – -70.46 (m, 1F), -70.84 (dd, J = 169.5, 8.0 Hz, 1F), -76.84 (ddd, J = 21.5, 10.5,7.0 Hz, 1F), -85.90 (ddt, J = 137.6, 22.3, 4.1 Hz, 1F), -87.65 (ddt, J = 137.5, 8.7, 4.3 Hz,1F).Step 2

[0210] Under nitrogen protection, CClF2CClFOCF2CBrF2 (approximately 40 g, 0.115mole) and 500 mL dry diethyl ether were placed in a three-neck flask equipped with a mechanical stirrer. The mixture was cooled to about -40°C using a dry ice / acetonitrile bath and then a 3M solution of EtMgBr in ether (1.02 equivalents) was slowly added followed by stirring at about -40°C for approximately four hours. Following this, a solution of about 1.05 equivalents of Cp2ZrCl2dissolved in 10 mL of dry 1,4-dioxane was added to the mixture. Stirring was continued for an additional four hours while carefully maintaining the cooling bath's temperature below -20°C. A solution of 1.0 equivalent of 5-hexene-2-one dissolved in dry Et2O was then added gradually, and the mixture was stirred overnight while allowing it to slowly warm to room temperature. Theprogress of the reaction was monitored using 19F NMR spectroscopy. Upon completion,the reaction was quenched with about 100 mL of water and filtered to remove solids. The residual solid was washed three times with Et2O. The washings and reaction filtrate were combined and washed with five 100 mL portions of water. The organic phase was then dried over MgSO4, and the solvent was removed via rotary evaporation. The remaining mixture was distilled under vacuum to yield approximately 29.9 grams of CClF2CClFOCF2CF2C(CH3)(OH)CH2CH2CH=CH2(approximately 70.8% yield). Step 3

[0211] Under nitrogen protection, CClF2CClFOCF2CF2C(CH3)(OH)CH2CH2CH=CH2(about 30 g, 0.0817 mole) and 400 mL of dry acetonitrile were placed in a 1 L three- neck flask equipped with a mechanical stirrer. The mixture was stirred and cooled to about -40°C using a dry ice / acetonitrile bath. Sodium hydride (1.05 equivalents) was added to the solution. The mixture was then stirred vigorously while the cooling bath was slowly warmed to about -10°C which resulted in the formation of fine bubbles. The mixture was subsequently cooled back to about -40°C and 1.1 equivalents of methyl iodide were added. The mixture was stirred overnight and slowly warmed to room temperature in the cooling bath. The progress of the reaction was monitored using GC- MS. Upon completion, the reaction was quenched with approximately 100 mL of water. The majority of the acetonitrile was then removed by rotary evaporation. The remainingliquid was extracted three times with diethyl ether. The combined ether extracts were dried over MgSO4. Solvents were removed via rotary evaporation to obtain the crude product which was purified by vacuum distillation to give about 29 grams of pure CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH=CH2(approximately 93.1% yield). Step 4

[0212] A mixture of CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH=CH2(approximately 30 g, 0.0787 mole), about 400 mL of acetonitrile, and about 100 mL of water were added to a 1 L three-neck flask. The mixture was treated with 2 mL of a 3% aqueous solution of OsO4 followed by the gradual addition of 2 equivalents of NaIO4. The reaction progress was monitored using GC-MS. Upon completion of the reaction, the solids were filtered out, yielding a yellow-red filtrate. The majority of the acetonitrile was then removed via rotary evaporation and the remaining mixture was extracted three times with diethyl ether. The combined organic phases were dried over MgSO4 and concentrated using rotary evaporation. The crude mixture containing CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2C(O)H was used directly in the next step. Step 5

[0213] Under nitrogen protection, crudeCClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2C(O)H from Step 4 was combined with about 300 mL of dry tetrahydrofuran (THF) in a 1 L three-neck flask and stirred using a mechanical stirrer. The mixture was cooled to about -15°C using an ice / sodium chloride bath and then treated with 2 equivalents of a dimethylamine (2M in THF) solution followed by about 5 equivalents of sodium triacetoxyborohydride. The mixture gradually warmed to room temperature. The reaction progress was monitored using GC-MS. Once the reaction was substantially completed, the majority of the THF was removed by rotary evaporation. Then, about 300 mL solution of sodium bicarbonate was added, and the mixture was extracted five times with Et2O. The combined organic phases were dried over MgSO4, concentrated, and the remaining mixture was distilled under vacuum to yield approximately 24.9 grams ofCClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2 (76.8% yield). 1H NMR (600MHz, DMSO) δ 3.26 (s, 3H), 2.22 – 2.16 (m, 2H), 2.11 (s, 6H), 1.84 – 1.74 (m, 1H), 1.67– 1.58 (m, 1H), 1.53 – 1.39 (m, 2H), 1.35 (s, 3H). 19F NMR (565 MHz, DMSO) δ -70.03– -72.19 (m, 2F), -76.89 (dt, J = 22.5, 7.2 Hz, 1F), -80.02 (dt, J = 144.3, 21.9 Hz, 1F), -82.62 (ddd, J = 144.5, 16.4, 8.9 Hz, 1F), -117.57 (dd, J = 276.4, 65.8 Hz, 1F), -119.23(dd, J = 276.5, 89.0 Hz, 1F).Step 6

[0214] Approximately 39.6 grams of dry, fine zinc powder (freshly activated byaqueous HCl solution) were placed in a 500 mL Schlenk flask under nitrogen protection. A mixture of about 50 mL of dry dimethyl sulfoxide and CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2 (approximately 50 g, 0.121 mole) were added, and the mixture was stirred using a magnetic stir bar. The mixturewas heated to 80°C for approximately 2 hours with the reaction monitored by 19F NMRspectroscopy. Once the reaction was complete, the mixture was cooled to room temperature, and about 500 mL of water was added. The pH was slightly adjusted to about 7 to 7.5 using acetic acid and trimethylamine solution, after which the mixture was extracted five times with Et2O. The pH of the water was adjusted again during the extractions. The combined organic phases were dried over MgSO4, concentrated, and the remaining mixture was distilled under vacuum to yield approximately 29.8 grams ofCF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2 (72.2% yield). 1H NMR (600 MHz,DMSO) δ 3.26 (s, 3H), 2.19 (td, J = 6.9, 1.4 Hz, 2H), 2.10 (s, 6H), 1.80 (ddd, J = 14.3,11.8, 4.5 Hz, 1H), 1.62 (ddd, J = 14.6, 12.1, 4.9 Hz, 1H), 1.53 – 1.39 (m, 2H), 1.35 (s,3H). 19F NMR (565 MHz, DMSO) δ -82.36 (dt, J = 16.8, 5.9 Hz, 2F), -113.26 (dd, J =85.9, 62.3 Hz, 1F), -117.16 (d, J = 278.8 Hz, 1F), -118.99 (d, J = 279.0 Hz, 1F), -121.96(dd, J = 110.2, 86.1 Hz, 1F), -134.41 (dd, J = 110.6, 62.3 Hz, 1F).Example 2 Preparation of [CF2=CFOCF2CF2C(CH3)(OCH3)(CH2)3N(CH3)3](O3SCF3)

[0215] A 250 mL three-neck round bottom flask equipped with a PTFE-coatedstirring bar, a thermocouple well, and a condenser topped with a nitrogen bubbler, and a rubber septum was charged with a solution of CF2=CFOCF2CF2C(CH3)(OCH3)(CH2)3N(CH3)2 (approximately 17.84 g, 52.3 mmoles) dissolved in methylene chloride (about 30.1 g). The solution was cooled in an ice-waterbath. A solution of methyl trifluoromethanesulfonate (about 8.98 g, 54.7 mmoles) dissolved in methylene chloride (about 14.5 g) was added to the flask over the course of one hour with ice-water cooling. The ice-water bath was removed and an additional 20 mL of methylene chloride was added to the viscous white mixture to improve mixing. After about 70 minutes, the mixture was treated with about 10 mL of methanol giving a clear solution which was evaporated under vacuum to provide a pale pink powder(25.82 g). 1H NMR (acetone-d6): ^ 3.63 (m, -CH2N), 3.39 (s, C(OCH3)), 3.37 (s,N(CH3)3), ca. 2.09 (-CH2), 1.95 and 1.83 (m, CHaHb), 1.51 (s, C(CH3)); 19F NMR(acetone-d6): ^ -79.03 (s, CF3SO3), -83.45 (m, OCF2), -115.80 (dd, J = 63.5, 88.3 Hz,=CF), -118.63 (d) and -119.79 (d), AB group (J = 280.7 Hz, CFaFb), -123.74 (ddt, J = 6.0, 88.3, 110.7 Hz, =CF), -135.66 (ddt, J = 6.0, 63.5, 110.7 Hz, =CF). Example 3 Preparation of

[0216] Under the10 g, 0.029 mole)and about 150 mL dry Et2O were placed in a three-neck flask. The mixture was stirred using a mechanical stirrer and cooled to about -40°C in a dry ice / acetonitrile bath. Then approximately 1.02 equivalents of EtMgBr (3M in Et2O) was slowly added followed by stirring for four hours at -40°C. A solution of approximately 1.05 equivalents of Cp2ZrCl2dissolved in 10 mL of dry 1,4-dioxane was then added to the reaction mixture. Stirring was continued for an additional four hours while carefully maintaining the cooling bath's temperature below -20°C. The reaction mixture was cooled to about -40oC and a solution of CH3C(O)(CH2)3Cl in dry Et2O was added slowly and the reaction was allowed to warm. The reaction was quenched with about 50 mL water when the temperature reached approximately -10oC. The mixture was washed with five 50 mL portions of water, and the Et2O phase was dried over MgSO4, and the solvent was removed viarotary evaporation. Then the remaining mixture was distilled under vacuum to yield approximately 7.6 grams of the product (74% yield).

[0217] Under the protection of N2, CClF2CClFOCF2CF2C(OH)(CH3)CH2CH2CH2Cl(about 1 g, 2.5 mmol) and approximately 7 mL dry Et2O were placed in a 25 mL Schlenk flask. The resulting mixture was cooled to about -20°C and stirred using a magnetic stir bar. NaH (90 %, about 100 mg, 3.8 mmol) was added to the mixture and stirred for approximately 30 min. The mixture was warmed to room temperature slowly and monitored by GC-MS. Once the reaction was substantially finished, the mixture was quenched with about 2 mL water and extracted by Et2O three times. The combined organic phases were dried over MgSO4, and the remaining mixture was distilled undervacuum to yield 740 mg of product (84 % yield). 1H NMR (DMSO) δ 3.98 – 3.90 (m,1H), 3.74 (q, J = 7.7 Hz, 1H), 2.25 (dt, J = 13.0, 8.2 Hz, 1H), 2.02 – 1.89 (m, 2H), 1.88 –1.80 (m, 1H), 1.32 (s, 3H); 19F NMR (DMSO) δ -70.20 – -71.61 (m), -76.85 (ddq, J =84.8, 21.6, 7.5 Hz), -80.77 (ddd, J = 435.3, 144.2, 23.0 Hz), -82.99 (ddd, J = 378.5,144.4, 8.7 Hz), -120.81 (dd, J = 271.9, 83.3 Hz), -123.77 (dd, J = 271.8, 135.8 Hz).Example 4 Preparation of CF2=CFOCF2CF2C(OH)(CH3)C(CH3)2CH2N(CH3)2

[0218] Under the protection (36.1 mmol)and about 200 ml dry Et2O were added in a three-neck flask and stirred with a stir bar. The mixture was cooled to about -40°C using a dry ice / acetonitrile bath and a 3M solution of EtMgBr in ether (approximately 1.02 equivalents) was slowly added and stirred for additional four hours under that temperature. Following this, approximately 2 mL dry 1,4-dioxane and 1.05 eq. of Cp2ZrCl2 were added into the mixture. The mixture was stirred for about an additional four hours and a temperature of under -20°C was maintained. Then a solution of 1 eq. of CH3C(O)(CH3)2CH2NMe2in dry Et2O was added slowly, and the resulting reaction mixture was warmed to room temperature slowly. The reaction was quenched with about 100 mL water and the resulting mixture extracted five times with diethyl ether. The combined organic phase was dried over MgSO4, and the remaining mixture was distilled under vacuum to yield approximately 2.9 g of product(isolated yield of about 22 %). 1H NMR (DMSO) δ 9.09 (s, 1H), 2.87 (dd, J = 14.2, 3.0Hz, 1H), 2.38 (dd, J = 14.2, 3.0 Hz, 1H), 2.29 (s, 6H), 1.31 – 1.27 (d, J = 3.8 Hz, 1H),1.12 (s, 3H), 0.98 – 0.94 (m, 3H). 19F NMR (CDCl3) δ -81.49 – -82.22 (m, 2F), -109.70(d, J = 270.4 Hz, 1F), -115.24 (dd, J = 87.3, 63.0 Hz, 1F), -120.Example 5 Preparation of CClF2CClFOCF2CF2C(CH3)2(CN)

[0219] Under nitrogen protection, a solution containing about 100 mmol ofCClF2CClFOCF2CBrF2and 400 mL of dry diethyl ether was introduced to a 1 L three- neck flask. The resulting mixture was stirred using a mechanical stirrer and cooled to about -40°C using a dry ice / acetonitrile bath. Subsequently, a solution of approximately 34 mL EtMgBr (1.02 eq., 3M in diethyl ether) was slowly added to the mixture followed by stirring for about four hours. A solution of zirconocene dichloride (approximately 30.7 g, 105 mmol) in about 10 mL of dry 1,4-dioxane was added to the mixture. The mixture was stirred for about another four hours while maintaining a temperature below -20°C. The temperature was then lowered to -40°C, and a solution of approximately 16.3grams (1.0 equiv.) of 2-methyl-2-[(methylsulfonyl)oxy]propanenitrile in dry Et2O wasadded. The mixture was stirred overnight while gradually warming to room temperature.Monitoring the reaction by 19F NMR indicated the yield was over 80 %. Water (200 mL)was added to quench the reaction. The ether phase was separated, washed five times with about 100 mL portions of water, concentrated, and distilled under vacuum to obtainCClF2CClFOCF2CF2C(CH3)2(CN). 1H NMR (600 MHz, CDCl3) δ 1.40 (s, 6H). 19F NMR(565 MHz, CDCl3) δ -70.05 – -71.06 (m, 2F), -76.20 – -76.45 (m, 1F), -86.30 (ddt, J =142.0, 22.4, 5.2 Hz, 1F), -87.75 (ddt, J = 142.6, 9.8, 5.3 Hz, 1F), -121.37 (dt, J = 11.2,5.0 Hz, 2F). Example 6 Preparation of a Copolymer of [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3) with TetrafluoroetheneHastelloy™ C shaker tube was charged with[CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3) (13.8 g, 27 mmoles), dichloromethane (approximately 39.8 g, 30 mL), and 1,1,1,2,3,4,4,5,5,5-decafluoropentane (approximately 47.4 g, 30 mL). The tube was sealed, cooled in dry ice, evacuated, and purged with nitrogen three times. The tube was placed in the shaking apparatus and brought to 40 psig by adding tetrafluoroethene at about 24°C.An initiator solution of about 1 weight percent bis[2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)-1-oxopropyl]peroxide dissolved in 1-[1-[difluoro(1,2,2,2-tetrafluoroethoxy)methyl]-1,2,2,2-tetrafluoroethoxy]-1,1,2,2,3,3,3-heptafluoropropane was prepared. The tube was shaken while feeding the initiator solution at about 0.14 mL / minute and maintaining the reactor pressure at about 40 psig by adding tetrafluoroethene. After about 5 hours at about 25°C to 26°C the reaction was shut down; and the tube was vented and purged with nitrogen. The contents of the tube were collected and filtered, and the solid phase was washed with dichloromethane and extracted with acetone to remove unreacted trifluorovinyl quaternary ammonium monomer and solid polymer (approximately 9.75 g) incorporating the co-polymerized trifluorovinyl quaternary ammonium monomer.

[0221] The polymer prepared herein was characterized using a Bruker 3.2 mmMagic Angle Spinning probe and a Bruker Avance II NMR spectrometer having anexternal magnetic field strength of 9.4 Tesla; the spinning speed was 20 kHz. The 19FNMR spectrum, represented in Figure 1, featured a strong -CF2CF2- resonance at -122 ppm, weak resonances attributed to CF3and OCF2groups around -80 ppm, as well as a resonance at -131 ppm for the CFO group on the polymer backbone, and a very small -CF-O- peak at about -139 that may correspond to unpolymerized monomer. The 13CNMR spectrum (Figure 2) showed resonances at 82 ppm for the quaternary carbon, at 69 ppm for the CH2 adjacent to the quaternary carbon, a strong overlapping resonance at 56 ppm for the OCH3 and NCH3 groups, and 19 ppm for overlapping CH3 and CH2 groups. The infra-red spectrum of a KBr pellet sample of the polymer displayed a broad,weak C-H band around 3,000 cm-1. Integration of the 19F NMR spectrum indicated thepolymer contained about 2.2 mole% of the co-polymerized quaternary vinyl ether monomer.Example 7 Preparation of a Copolymer of [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3) with Tetrafluoroethene reaction was performed in a substantially similar manner to12.4 g (24 mmoles) of [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3) and with a tetrafluoroethene, and pressure of about 20 psig which resulted in approximately 4.09 g of polymer incorporating the co-polymerized trifluorovinyl quaternary ammoniummonomer. The solid-state Magic Angle Spinning 19F NMR spectrum and DSC(differential scanning calorimetry) scan of the copolymer prepared herein arerepresented in Figure 3 and Figure 4, respectively. Integration of the 19F NMR spectrumindicated the polymer contained about 2.9 mole% of the co-polymerized quaternary vinyl ether monomer.

Claims

We claim:

1. A trifluorovinyl tertiary amine having a structure represented by theformula CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22wherein x = 0 or 1; y = 1 to 7; z = 0 to 4; R1is selected from CH3and CF3; R2are independently selected from CH3, C2-C8 straight chain or branched alkyl, C5-C8 cycloalkyl, or together with nitrogen comprise a 5- to 8-membered ring; and Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2 provided that there are no oxygen-oxygen bonds in the trifluorovinyl tertiary amine.

2. The trifluorovinyl tertiary amine of claim 1, having the formulaCF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2.

3. The trifluorovinyl tertiary amine of claim 1, having the formulaCF2=CFCF2C(CH3)(OCH3)CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2N(CH3)2, CF2=CFCF2CF2C(CF3)(OCH3)CH2N(CH3)2, CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2N(CH3)2, CF2=CFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3), CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2N(CH3)2, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CF3)(OCH3)CH2N(CH3)2, or CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2N(CH3)2.

4. A trifluorovinyl bis(tertiary amine) having a structure represented by the formula CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22]2 wherein x = 0 or 1; z = 0 to 4; each y is independently 1 to 7; R2are independently selected from CH3, C2-C8straight chain or branched alkyl, C5-C8cycloalkyl, or together with nitrogen comprise a 5- to 8-membered ring; and Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the trifluorovinyl bis(tertiary amine).

5. The trifluorovinyl tertiary amine of claim 4, having the formulaCF2=CFCF2C(OCH3)[CH2CH2N(CH3)2]2, CF2=CFCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2, CF2=CFCF2CF2C(OCH3)[CH2CH2CH2N(CH3)2]2, CF2=CFCF2CF2C(OCH3)[CH2N(CH3)2]2, CF2=CFCF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CF2=CFOCF2CF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2N(CH3)2]2, CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2, CF2=CFOCF2CF2C(OCH3)[CH2CH2N(CH3)2]2, CF2=CFOCF2CF2C(OCH3)[CH2N(CH3)2]2, or CF2=CFOCF2CF2CF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2]2.

6. A trifluorovinyl quaternary ammonium salt having a structure represented by the formula [CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22R3]+1[Q-n]1 / n wherein x = 0 or 1; z = 0 to 4; each y is independently 1 to 7; R3is selected from CH3, C2-C8straight chain or branched alkyl and C5-C8cycloalkyl; Q is a monovalent anionselected from Cl, Br, I, OH, HCO3, HSO4, H2PO4, BF4, PF6, O3SR4 wherein R4 isselected from C1-C3 alkoxy, C1-C6 straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl, or a divalent anion selected from CO3, SO4or HPO4, or PO4; n is the charge on Q; R1is selected from CH3and CF3; R2are independently selected from CH3, C2-C8 straight chain or branched alkyl, C5-C8cycloalkyl, or together with nitrogen comprise a 5- to 8-membered ring; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the trifluorovinyl quaternary ammonium salt.

7. The trifluorovinyl quaternary ammonium salt of claim 6, having the formula[CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3).

8. A copolymer comprising the trifluorovinyl quaternary ammonium salt of claim 6 with at least one comonomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3, CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo- OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3)-, CF2=CFOCF2CF2CF=CF2, and cyclo-[OCF=C(OCF3)OCF2]-.

9. The copolymer of claim 8, wherein the comonomer is CF2=CF2.

10. A trifluorovinyl bis(quaternary ammonium) salt having a structure represented by the formula {CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22R3]2}+2[Q-n]2 / nwherein x = 0 or 1; z = 0 to 4; each y is independently 1 to 7; R2are independently selected from CH3, C2-C8 straight chain or branched alkyl, C5-C8 cycloalkyl, or together with nitrogen comprise a 5- to 8-membered ring; Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the trifluorovinyl bis(quaternary ammonium) salt; R3are independently selected from CH3, C2-C8straight chain or branched alkyl, and C5-C8cycloalkyl; Q is a monovalent anion selected from Cl, Br, I, OH, HCO3, HSO4, H2PO4, BF4, PF6, O3SR4where R4is selected from C1-C3 alkoxy, C1-C6 straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl, or a divalent anion selected from CO3, SO4, or HPO4, or PO4, wherein n is the charge on Q.

11. The trifluorovinyl bis(quaternary ammonium) salt of claim 10, having the formula {CF2=CFOCF2CF2C(OCH3)[CH2N(CH3)3]2}(O3SCF3)2.

12. The trifluorovinyl bis(quaternary ammonium) salt of claim 10, having the formula {CF2=CFCF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SOCH3)2, {CF2=CFCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2(C2H5)]2}(I)2, {CF2=CFCF2CF2C(OCH3)[CH2CH2CH2N(CH3)3]2}(O3SCH3)2, {CF2=CFCF2CF2C(OCH3)[CH2N(CH3)2(C2H5)]2}(O3SCF3)2, {CF2=CFCF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SC6H4-4-CH3)2, {CF2=CFOCF2CF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SCF3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2N(CH3)3]2}(O3SCF3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)3]2}(O3SCH3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2(C2H5)]2}(O3SCF3)2, {CF2=CFOCF2CF2C(OCH3)[CH2CH2N(CH3)3]2}(O3SCH3)2, {CF2=CFOCF2CF2C(OCH3)[CH2N(CH3)3]2}(Cl)2, or {CF2=CFOCF2CF2CF2CF2C(OCH3)[CH2CH2CH2CH2N(CH3)2(C4H9)]2}(Br)2.

13. A copolymer comprising the trifluorovinyl bis(quaternary ammonium) salt of claim 10, with at least one comonomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3,CF2=CFOCF3, CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3),CF2=CFOCF2CF2CF=CF2, and cyclo-[OCF=C(OCF3)OCF2]-.

14. The copolymer of claim 13, wherein the comonomer is CF2=CF2.

15. A trifluorovinyl alkyl chloride compound of the formula CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R5)(CH2)rCl wherein R5is selected from CH3, (CH2)rCl, and CF3; r is an integer from 1 to 7; x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound.

16. The trifluoro alkyl chloride compound of claim 15, having the formula CF2=CFCF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2Cl, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2Cl, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2Cl, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2CH2Cl, CF2=CFOCF2CF2C(OCH3)(CH2CH2Cl)2, CF2=CFOCF2CF2C(OCH3)(CH2Cl)2, CF2=CFCF2CF2C(OCH3)(CH2CH2Cl)2, CF2=CFCF2CF2C(OCH3)(CH2Cl)2, CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2CH2Cl, or CF2=CFOCF2CF(CF3)OCF2CF2C(CF3)(OCH3)CH2CH2CH2Cl.

17. A copolymer comprising the trifluorovinyl alkyl chloride compound of claim 15, and at least one monomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3,CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3),CF2=CFOCF2CF2CF=CF2, and cyclo-[OCF=C(OCF3)OCF2]-.

18. The copolymer of claim 17, wherein the comonomer is CF2=CF2.

19. A trifluorovinyl cyclic ether having a structure represented by the formulawherein p = x = or z = a or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branchedperfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound; and R1is CH3 or CF3.

20. The trifluorovinyl cyclic ether of claim 19, having a formula selected from CF2=CFCF2-cyclo-[C(CH3)OCH2-], CF2=CFCF2CF2-cyclo-[C(CH3)OCH2-], CF2=CFOCF2CF2-cyclo-[C(CH3)OCH2-], CF2=CFOCF2CF2-cyclo-[C(CF3)OCH2-], CF2=CFCF2CF2-cyclo-[C(CH3)OCH2CH2-], CF2=CFCF2CF2-cyclo- [C(CH3)OCH2CH2CH2-], CF2=CFOCF2CF2-cyclo-[C(CH3)OCH2CH2CH2CH2-], CF2=CFOCF2CF2-cyclo-[C(CH3)OCH2CH2CH2-], CF2=CFOCF2CF2-cyclo- [C(CF3)OCH2CH2CH2CH2-], CF2=CFOCF2CF2CF2CF2-cyclo-[C(CH3)OCH2CH2CH2-], CF2=CFOCF2CF(CF3)OCF2CF2-cyclo-[C(CH3)OCH2CH2-], CF2=CFCF2-cyclo- [C(CH3)OCH2CH2CH2-], and CF2=CFCF2-cyclo-[C(CH3)OCH2CH2-].

21. A copolymer comprising the trifluorovinyl cyclic ether of claim 19, and at least one monomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3,CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3, CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3),CF2=CFOCF2CF2CF=CF2, and cyclo-[OCF=C(OCF3)OCF2]-.

22. The copolymer of claim 21, wherein the comonomer is CF2=CF2.

23. A trifluorovinyl tertiary amine having a structure represented by the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2wherein x =consisting of CH3 and CF3; R7are both CH3 or both H; and Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein I = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the trifluorovinyl tertiary amine.

24. The trifluoro tertiary amine of claim 23, having the formula CF2=CFCF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2,CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2or CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2.

25. A trifluorovinyl quaternary ammonium salt having a structure represented by the formula {CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2R3}+1[Q-n]1 / n wherein x = 0 or 1; z = 0 to 4; a = 0 to 4; b = 0 or 1; R1is CH3 or CF3; R7are both H or both CH3; R3is CH3, C2-C8straight chain or branched alkyl or C5-C8cycloalkyl; Q is a monovalent anion selected from Cl, Br, I, OH, HCO3, HSO4, H2PO4, BF4, PF6, O3SR4where R4 is selected from C1-C3 alkoxy, C1-C6 straight chain or branched alkyl,fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl, or a divalent anion selected from CO3, SO4, or HPO4, or PO4, wherein n is the charge on Q; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound.

26. The trifluorovinyl quaternary ammonium salt of claim 25, wherein the formula is [CF2=CFCF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)3]I, [CF2=CFCF2CF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2(C4H9)]Br, [CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)3]Br, [CF2=CFCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)3](O3SOCH3), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2(C4H9)](Br), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)3](O3SOCH3), [CF2=CFOCF2CF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)3](O3SCF3), [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)3](O3SOCH3), or [CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)3](O3SC6H4-4-CH3).

27. A copolymer comprising the trifluorovinyl quaternary ammonium salt of claim 25, with at least one monomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3,CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3), CF2=CFOCF2CF2CF=CF2,and cyclo-[OCF=C(OCF3)OCF2]-.

28. The copolymer of claim 27, wherein the comonomer is CF2=CF2.

29. A trifluorovinyl alkyl nitrile having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(R6)(CH2)mCN wherein m = 0 to 5; x = 0 or 1; z = 0 to 4; R1is CH3 or CF3; R6is CH3 or OCH3 provided that when R6= CH3then m = 0; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound.

30. The trifluorovinyl alkyl nitrile of claim 29, having the formulaCF2=CFCF2C(CH3)(OCH3)CH2CH2CN, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2CN,CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CN, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2CN, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CN, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CN, CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CN, CF2=CFOCF2CF(CF3)OCF2CF2C(CH3)(OCH3)CH2CH2CH2CH2CN, CF2=CFOCF2CF2C(CF3)(CH3)CN, CF2=CFOCF2CF2C(CH3)2CN, or CF2=CFCF2CF2C(CH3)2CN.

31. A copolymer comprising the trifluorovinyl alkyl nitrile of claim 29, with at least one monomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3,CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3),CF2=CFOCF2CF2CF=CF2, and cyclo-[OCF=C(OCF3)OCF2]-.

32. The copolymer of claim 31, wherein the comonomer is CF2=CF2.

33. A fluoroalkyl nitrile of the formula Rf1CF2C(CH3)(R1)CN wherein R1= CH3or CF3, and Rf1is a straight or branched chain perfluoroalkyl, chlorofluoroalkyl, or fluoroalkyl group, optionally containing ether linkages, CeHfClgF2e+1-f-gOh wherein e = 1 to 6, f = 0 to 4, g = 0 to 2, and h = 0 to 2 provided that no O-O bonds are present.

34. A fluoroalkenyl nitrile of the formula Rf2CF2C(CH3)(R1)CN wherein R1= CH3 or CF3; and Rf2is a straight or branched chain perfluoroalkenyl, chlorofluoroalkenyl, or fluoroalkenyl group, optionally containing ether linkages, CeHfClgF2e-1-f-gOh wherein e = 1 to 6, f = 0 to 4, g = 0 to 2, and h = 0 to 2, provided that no O-O bonds are present.

35. A copolymer of a trifluorovinyl quaternary ammonium salt having the formula [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3) and at least one comonomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3, CF2=CFOCF3,CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3)-,CF2=CFOCF2CF2CF=CF2, or cyclo-[OCF=C(OCF3)OCF2]-.

36. A trifluorovinyl cyclic methoxyamine compound represented by a structure selected fromwherein l is 3, 4, or 5; l1 and l2 are 1 to 3 provided that l1 + l2 = 3 to 5; x= 0 or 1; z =0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkj = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound.

37. A trifluorovinyl cyclic quaternary ammonium salt represented by a structure selected from orwherein l is 3, 4, or 5; l1 and l2 are 1 to 3 provided that l1 + l2 = 3 to 5; x= 0 or 1; z =0 to 4; R3is CH3, C2-C8 straight chain or branched alkyl or C5-C8 cycloalkyl; Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound;and Q is a monovalent anion selected from Cl, Br, I, OH, HCO3, HSO4, H2PO4,BF4, PF6, O3SR4 wherein R4 is selected from C1-C3 alkoxy, C1-C6 straight chain orbranched alkyl, fluoroalkyl, perfluoroalkyl, aryl, and substituted aryl, a divalent anion selected from CO3, SO4or HPO4, or PO4.

38. The trifluorovinyl cyclic quaternary ammonium salt of claim 37, represented by a structure wherein x = 1; z39. The trifluorovinyl cyclic quaternary ammonium salt of claim 37, represented by a structurewherein x = 0; z = 0; l = 3 to 5; and Rf= (CF2)iwhere i = 1 to 3.salt of claim 37, represented by a structurewherein x = 1; z = 0 to 2; l1 = 1 to 3 and l2 = 1 to 3, provided l1 +l2 = 3 to 5, or l1 = 2 and l2 = 2; and Rf= (CF2)iwhere i = 1 to 3.

41. The trifluorovinyl cyclic quaternary ammonium salt of claim 37, represented by a structure wherein x = 0;i where i = 1 to 3.

42. The trifluorovinyl cyclic quaternary ammonium salt of claim 37, represented by a structurewherein x = 1; z = 0 to 2; l1 = 1 and l2 =2, or l1 = 2 and l2 = 2; Rf= (CF2)iwhere i = 1 to 3; and R3= C4H9 or cyclo-C6H11.

43. The trifluorovinyl cyclic quaternary ammonium salt of claim 37, represented by a structure wherein x = 0; zi = 1 to 3; and R3= C4H9or cyclo-C6H11.

44. A process for making a fluoroalkyl hydroxyalkene compound comprising: (a) (i) reacting a polyfluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2Y wherein Y is selected from Br or I; x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group, CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, with an alkyl or aryl magnesium halide compound having the formula RMgZ, wherein R = C1-C6 alkyl, or aryl, and Z = Cl, Br or I; and a bis(cyclopentadienyl)zirconium dichloride compound, to obtain an organometallic reactive intermediate solution; and (ii) reacting the organometallic reactive intermediate solution with an alkenyl ketone having the formula R1C(O)(CH2)qCH=CH2 wherein R1is CH3or CF3,and q= 0 to 4, to produce a fluoroalkyl hydroxyalkene compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)qCH=CH2.

45. The process of claim 44, further comprising(b) reacting a fluoroalkyl hydroxyalkene compound with a methylating reagent to produce a fluoroalkyl methoxyalkene compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH=CH2) wherein q, x, z, Rfand R1are as defined above.

46. The process of claim 45, wherein the fluoroalkyl methoxyalkene is CClF2CClFCF2C(CH3)(OCH3)CH=CH2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH2CH=CH2, CClF2CClFCF2CF2C(CH3)(OCH3)CH2CH=CH2, CClF2CClFCF2CF2C(CH3)(OCH3)CH=CH2, CClF2CClFCF2CF2C(CF3)(OCH3)CH=CH2, CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH2CH=CH2, CClF2CClFCF2CF2C(CF3)(OCH3)CH2CH=CH2, CClF2CClFOCF2CF2CF2C(CH3)(OCH3)CH2CH2CH=CH2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH2CH=CH2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH2CH=CH2, CClF2CClFOCF2CF2C(CH3)(OCH3)CH=CH2, CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH2CH=CH2, CClF2CClFOCF2CF2C(CF3)(OCH3)CH2CH=CH2, CClF2CClFOCF2CF2C(CF3)(OCH3)CH=CH2, CClF2CClFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH=CH2, or CClF2CClFOCF2CF(CF3)OCF2CF2C(CH3)(OCH3)CH2CH2CH=CH2.

47. The process of claim 45, further comprising (c1) reacting the fluoroalkyl methoxyalkene compound with a borane followed by hydroxylamine-O-sulfonic acid to produce a fluoroalkyl primary amine compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2NH2wherein q, x, z, Rf, and R1are as defined above.

48. The process of claim 47, further comprising(d1) reacting the fluoroalkyl primary amine with a methylating agent to produce a fluoroalkyl tertiary amine compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2N(CH3)2 wherein z, x, q, Rfand R1are as defined above.

49. The process of claim 47, further comprising (d2) alkylating the fluoroalkyl primary amine with a halocompound having the formula R3Z, wherein R is a C1-C8straight chain or branched alkyl halide group or C5-C8cycloalkyl halide group and Z is Cl, Br, or I, to produce a fluoroalkyl tertiary amine compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2NR32wherein z, x, q, Rf, and R1are as defined above, and R3is a C1-C8 straight chain or branched alkyl or C5-C8 cycloalkyl group.

50. The process of claim 45, further comprising (c2) aminomethylating the fluoroalkyl methoxyalkene compound with dimethylamine in the presence of carbon monoxide, water, and a rhodium catalyst, to produce a fluoroalkyl dimethylamino compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2CH2N(CH3)2wherein z, x, q, Rfand R1are as defined above.

51. The process of claim 45, further comprising (c3) converting the fluoroalkyl methoxyalkene compound by reacting with a borane and then reacting with carbon monoxide and an aluminum hydride to produce a fluoroalkyl aldehyde compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2CH2C(O)H wherein z, x, q, Rfand R1are as defined above.

52. The process of claim 45, further comprising (c4) oxidizing the fluoroalkyl methoxyalkene compound by Wacker oxidation to produce a fluoroalkyl aldehyde having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH2C(O)H wherein z, x, q, Rfand R1are as defined above.

53. The process of claim 45, comprising (c5) oxidizing the fluoroalkyl methoxyalkene compound by osmium tetroxide- catalyzed reaction with sodium periodate to produce a fluoroalkyl aldehyde compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qC(O)H wherein z, x, q, Rfand R1are as defined above.

54. The process of claims 51, 52, and 53 further comprising reacting at least one fluoroalkyl aldehyde compound with dimethylamine and a reducing agent to produce a fluoroalkyl tertiary amine compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)q(CH2)tN(CH3)2 wherein z, x, q, Rfand R1are as defined above, and t = 1 to 3.

55. The process of claim 54, further comprising reacting a fluoroalkyl tertiary amine compound with a dechlorinating agent to produce a trifluorovinyl tertiary amine compound of formula CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yN(CH3)2 wherein x = 0 or 1; y = 1 to7; z = 0 to 4; R1is selected from CH3and CF3; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, or a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound.

56. The process of claim 44 wherein the polyfluoroalkyl halide is CClF2CClFCF2Br, CClF2CClFCF2I, CClF2CClFCF2CF2Br, CClF2CClFCF2CF2I, CClF2CClFOCF2CF2CF2I, CClF2CClFOCF2CF2Br, CClF2CClFOCF2CF2I, CClF2CClFOCF2CF2CF2CF2I, or CClF2CClFOCF2CF(CF3)OCF2CF2I.

57. The process of claim 44, wherein for the compound of formula RMgZ, R = C1-C6 alkyl, phenyl, or p-tolyl and Z = Cl or Br.

58. The process of claim 44, wherein the alkyl or aryl magnesium halide is C1- C3alkyl magnesium chlorides or C1-C3alkyl magnesium bromides.

59. The process of claim 44, wherein the alkyl or aryl magnesium halide is methyl magnesium bromide, ethyl magnesium bromide, ethyl magnesium chloride, isopropyl magnesium chloride, phenyl magnesium chloride, or p-tolyl magnesium bromide.

60. The process of claim 44, wherein the alkenyl ketone is CH3C(O)CH=CH2, CF3C(O)CH=CH2, CH3C(O)CH2CH=CH2, CH3C(O)CH2CH2CH=CH2, CF3C(O)CH2CH=CH2 or CF3C(O)CH2CH2CH=CH2.

61. The process of claim 44, wherein the alkenyl ketone is CH3C(O)CH2CH2CH=CH2.

62. The process of claim 44, wherein the bis(cyclopentadienyl)zirconiumdichloride compound is ((^5-C5H5)2ZrCl2).

63. A process for the manufacture of a trifluorovinyl tertiary amine compound comprising the steps of (a) reacting a fluoroalkyl hydroxyalkene compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)qCH=CH2 wherein x = 0 or 1; z = 0 to 4; q= 0 to 4; Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound; and R1is selected from the group CH3and CF3; with a methylating agent to provide a fluoroalkyl methoxyalkene having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)qCH=CH2 wherein q, x, z, Rfand R1are as defined above; (b) oxidizing the fluoroalkyl methoxyalkene compound to produce a fluoroalkylaldehyde compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)q(CH2)t-1C(O)H; wherein z, x, q, Rfand R1are defined as above, and t = 1 to 3; (c) reacting the fluoroalkyl aldehyde compound with dimethylamine and a reducing agent to produce a fluoroalkyl tertiary amine compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)q(CH2)tN(CH3)2; wherein z, x, q, Rf, R1and t are defined as above; and (d) dechlorinating the fluoroalkyl tertiary amine compound to produce a trifluorovinyl tertiary amine compound having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yN(CH3)2 wherein z,64. The process of claim 63, further comprising reacting the trifluorovinyl tertiary amine compound with an alkylating reagent having the formula R3Q to produce a trifluorovinyl quaternary ammonium salt having the formula {CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yN(CH3)2R3}(Q) wherein z, x, y, Rf, and R1are as defined above; R3is CH3, C2-C8straight chain orbranched alkyl and C5-C8 cycloalkyl; and Q = Cl, Br, I, or O3SR4 wherein R4 = C1-C3alkoxy, C1-C6 straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl.

65. A process for making a fluoroalkyl hydroxy diene compound suitable for use in making a trifluorovinyl bis(tertiary amine) compound comprising(a) reacting a polyfluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2Y wherein Y is selected from Br or I; x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, with a compound having the formula RMgZ, wherein R = C1-C6alkyl, or aryl, and Z = Cl, Br or I, and a bis(cyclopentadienyl)zirconium dichloride compound, to obtain an organometallic reactive intermediate solution; and (b) reacting the organometallic reactive intermediate solution with a dialkenyl ketone having the formula C(O)[(CH2)uCH=CH2]2 wherein each u is independently selected from 0 to 4, to produce a fluoroalkyl hydroxy diene compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(OH)[(CH2)uCH=CH2]2 wherein z, x, u and Rfare defined as above.

66. The process of claim 65, further comprising the step (c) contacting the fluoroalkyl hydroxy(bis)alkene compound with a methylating reagent to produce a fluoroalkyl methoxy diene compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)uCH=CH2]2 wherein u, x, z, and Rfare as defined above; (d) converting the fluoroalkyl methoxy(bis)alkene compound to a fluoroalkyl bis(tertiary amine) compound of the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)u(CH2)tN(CH3)2]2wherein u, x, z, and Rfare defined as above, and t = 1 to 3; and (e) reacting the fluoroalkyl bis(tertiary amine) with a dechlorinating reagent to form a trifluorovinyl bis(tertiary amine) compound having the formulaCF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yN(CH3)2]2wherein x, z67. The process of claim 65, wherein the dialkenyl ketone is CH2=CHCH2C(O)CH2CH=CH2, CH2=CHCH2CH2C(O)CH2CH2CH=CH2, CH2=CHC(O)CH2CH=CH2, CH2=CHC(O)CH=CH2or CH2=CH(CH2)4C(O)CH2)4CH=CH2.

68. A process for making a trifluorovinyl bis(tertiary amine) compound comprising the steps of (a) reacting a polyfluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2Y wherein Y is selected from Br or I; x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein I = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, with a compound having the formula RMgZ, wherein R = C1-C6 alkyl, or aryl, and Z = Cl, Br or I, and a bis(cyclopentadienyl)zirconium dichloride compound, to obtain an organometallic reactive intermediate solution; and (b) reacting the organometallic reactive intermediate solution and a dialkenyl ketone of formula C(O)[(CH2)uCH=CH2]2 wherein each u is independently 0 to 4, to produce a fluoroalkyl hydroxy diene compound having the formula CClF2CClF(CF2)z(O)xCF2(Rf)C(OH)[(CH2)uCH=CH2]2 wherein x, z, and Rfare as defined above; (c) methylating the fluoroalkyl hydroxy diene compound to produce a fluoroalkyl methoxy diene compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)uCH=CH2]2wherein u, x, z, and Rfare as defined above; (d) oxidizing the fluoroalkyl methoxy diene compound to produce a fluoroalkyl bis(aldehyde) compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)u(CH2)t-1C(O)H]2wherein u, z, x, and Rfare defined as above, and t = 1 to 3; (e) converting the fluoroalkyl bis(aldehyde) compound to a fluoroalkyl bis(tertiary amine) compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)u(CH2)tN(CH3)2]2,wherein u, x, z, and Rfare defined as above, and t = 1 to 3; and (f) dechlorinating the fluoroalkyl bis(tertiary amine) compound to produce atrifluorovinyl bis(tertiary amine) compound having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yN(CH3)2]2 wherein z, x and Rfare defined as above, and each y = u + t.

69. The process of claim 68, further comprising reacting the trifluorovinyl bis(tertiary amine) compound with an alkylating agent having the formula R3Q to produce a trifluorovinyl bis(quaternary ammonium) salt having the formula {CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yN(CH3)2R3]2}(Q)2wherein z, x, and Rfare as defined above; y = 1 to 7; R3is CH3, C2-C8straight chain orbranched alkyl and C5-C8 cycloalkyl; and Q is Cl, Br, I, or O3SR4 wherein R4 = C1-C3alkoxy, C1-C6 straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl.

70. A process for making a trifluorovinyl quaternary ammonium salt, comprising: (a) reacting a trifluorovinyl tertiary amine compound having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22wherein x = 0 or 1; y = 1 to 7; z = 0 to 4; Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branchedperfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2 provided that there are no oxygen-oxygen bonds in the compound; R1is CH3 or CF3; and R2are independently selected from CH3, C2-C8 straight chain or branched alkyl, C5-C8 cycloalkyl, or together with nitrogen comprising a 5- to 8-membered ring, with an alkylating agent, R3Q; and (b) producing a trifluorovinyl quaternary ammonium salt of formula [CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22R3]+1[Q-n]1 / nwherein x, z, y and R1are defined above; R3is CH3, C2-C8straight chain or branchedalkyl or C5-C8 cycloalkyl; and Q = Cl, Br, I, or O3SR4 wherein R4 = C1-C3 alkoxy, C1-C6straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl.

71. A process for making a trifluorovinyl bis(quaternary ammonium) salt, comprising: (a) reacting a trifluorovinyl bis(tertiary amine) compound having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22]2wherein x = 0 or 1; y = 1 to 7; z = 0 to 4; Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2 provided that there are no oxygen-oxygen bonds in the compound; and R2are independently selected from CH3, C2-C8 straight chain or branched alkyl, C5-C8 cycloalkyl, or together with nitrogen comprising a 5- to 8-membered ring, with an alkylating agent, R3Q, wherein R3and Q are defined above; and (b) producing a trifluorovinyl bis(quaternary ammonium) salt of the formula {CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22R3]2}+2[Q-n]2 / n wherein R3is CH3, C2-C8straight chain or branched alkyl and C5-C8cycloalkyl; and Q =Cl, Br, I, and O3SR4 wherein R4 = C1-C3 alkoxy, C1-C6 straight chain or branched alkyl,fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl.

72. A process for making a trifluorovinyl tertiary amine, comprising(a) reacting (i) an organometallic reactive intermediate solution and (ii) an aminoketone having the formula R1C(O)(CH2)a[C(R7)2]bCH2N(CH3)2 wherein a = 0-4, b = 0 or 1, R7are both H or both CH3, to produce a producing a fluoroalkyl hydroxy tertiary amine compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)a[C(R7)2]bCH2N(CH3)2wherein x = 0 or 1; z = 0 to 4; R1 is selected from CH3 or CF3; and Rf is a straight chainor branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound; (b) reacting the fluoroalkyl hydroxy tertiary amine compound of step (a) with a methylating agent to produce a fluoroalkyl methoxytertiary amine compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2 or a fluoroalkyl quaternary ammonium salt having the formula [CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)3]Q wherein a, b, x, z, Rf, R1, and R7are as defined above and Q = Cl, Br, I, and O3SR4wherein R4 = C1-C3 alkoxy, C1-C6 straight chain or branched alkyl, fluoroalkyl,perfluoroalkyl, aryl, or substituted aryl; and (c) dechlorinating the compound of step (b) to produce a trifluorovinyl tertiary amine compound having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2or a trifluorovinyl quaternary ammonium salt having the formula {CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)3}Q wherein a, b, x, z, Rf, R1, R7and Q are as defined above.

73. The process of claim 72, wherein the ketone is selected from CH3C(O)C(CH3)2CH2N(CH3)2, CH3C(O)CH2C(CH3)2CH2N(CH3)2, and CH3C(O)CH2CH2C(CH3)2CH2N(CH3)2, CH3C(O)CH2N(CH3)2, CH3C(O)CH2CH2N(CH3)2,CH3C(O)CH2CH2CH2N(CH3)2, CF3C(O)CH2CH2CH2N(CH3)2, CH3C(O)CH2CH2CH2CH2N(CH3)2, and CH3C(O)(CH2)5N(CH3)2.

74. The process of claim 72, wherein the methylating agent is selected from dimethyl sulfate, methyl methanesulfonate, methyl trifluoromethanesulfonate, methyl p- toluenesulfonate, or iodomethane.

75. The process of claim 72, wherein the trifluorovinyl tertiary amine compound is CF2=CFCF2C(CH3)(OCH3)C(CH3)2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2, CF2=CFCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2, CF2=CFOCF2CF2C(CF3)(OCH3)CH2CH2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2C(CH3)2CH2N(CH3)2, CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2C(CH3)2CH2N(CH3)2, or CF2=CFOCF2CF2CF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)2.

76. The process of claim 72, wherein the organometallic reactive intermediate solution is generated from a reaction of RMgZ and intermediate compound CF2=CF(CF2)z(O)x(Rf)CF2Y, and a bis(cyclopentadienyl)zirconium dichloride compound, wherein R = C2-C6alkyl, or aryl; Z = Cl, Br or I; Y = Br or I; x= 0 or 1; z = 0 to 4; Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound.

77. A process for making fluoroalkyl halide compound, comprising (a) hydroboration of a fluoroalkyl methoxyalkene having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R8)(OCH3)(CH2)vCH=CH2 wherein x = 0 or 1; z = 0 to 4; R8is CH3, CF3, or (CH2)vCH=CH2, and each v is independently an integer from 0 to 5, and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, producing an intermediate boranederivative, and contacting with hydrogen peroxide and sodium hydroxide to produce a fluoroalkyl alcohol having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R9)(OCH3)(CH2)vCH2CH2OH wherein R9is CH3, CF3, or (CH2)vCH2CH2OH; and (b) reacting the fluoroalkyl alcohol formed in (a) with a halogenating agent selected from PBr3, PCl3, POCl3, PCl5, SOCl2 or aqueous HCl promoted with ZnCl2, HBr, or HI, to produce an fluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R10)(OCH3)(CH2)vCH2CH2X wherein R10= CH3, CF3, and (CH2)v+2X, wherein each v is independently an integer from 0 to 5,and X = Cl, Br or I.

78. A process for making a trifluorovinyl alkyl chloride compound, comprising (a) (i) obtaining an organometallic reactive intermediate solution made from the reaction of a polyfluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2Y wherein Y is selected from Br or I; x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, with a compound having the formula RMgZ, wherein R = C1-C6 alkyl, or aryl, and Z = Cl, Br or I, and a bis(cyclopentadienyl)zirconium dichloride compound and (ii) reacting the organometallic reactive intermediate solution with a chloroketone having the formula R5C(O)(CH2)rCl wherein R5is selected from CH3, CH2Cl, CH2CH2Cl, or CF3, and r = 1 to 7, to produce a fluoroalkyl hydroxyalkyl chloride having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R5)(OH)(CH2)rCl wherein z, x, r, Rfand R5are as defined above; and(b) methylating the fluoroalkyl hydroxyalkyl chloride formed in (a) with a methylating agent to produce a fluoroalkyl methoxyalkyl chloride compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R5)(OCH3)(CH2)rCl wherein z, x, r, Rfand R5are as defined above; and (c) dechlorinating the fluoroalkyl methoxyalkyl chloride compound with reducing metal selected from zinc, magnesium, or cadmium to produce a trifluorovinyl alkyl chloride having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R5)(OCH3)(CH2)rCl wherein z, x, r, Rfand R5are as defined above.

79. A process for making a trifluorovinyl cyclic ether, comprising (a) (i) obtaining an organometallic reactive intermediate solution by the reaction of a polyfluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2Y wherein Y is selected from Br or I, x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, with a compound having the formula RMgZ, wherein R = C1-C6alkyl, or aryl, and Z = Cl, Br or I, and a bis(cyclopentadienyl)zirconium dichloride compound and (ii) reacting the organometallic reactive intermediate solution with a chloroketone having the formula R1C(O)(CH2)pCl wherein R1is selected from CH3or CF3and p = 1 to 4, to produce a fluoroalkyl hydroxy alkyl chloride having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)pCl wherein z, x, p, Rfand R1are as defined above; (b) contacting the fluoroalkyl hydroxy alkyl chloride formed in (a) with a base in a solvent wherein the base is selected from alkaline and alkaline-earth metal hydrides where the alkaline metal is a Group 1A metal of the Periodic Table excluding hydrogenand the alkaline-earth metal is a Group 2A metal of the Periodic Table excluding beryllium, to produce a fluoroalkyl cyclic ether represented by the structureand (c) dechlorinating the fluoroalkyl cyclic ether compound of step (b) to produce a trifluorovinyl cyclic ether represented by the structurewherein z, x, p, Rf, and R1are as defined above.

80. A process for making a trifluorovinyl tertiary amine compound, comprising (a) reacting a fluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R10)(OCH3)(CH2)vCH2CH2X wherein x = 0 or 1; z = 0 to 4; Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound; v is an integer from 0 to 5; R10= CH3, CF3, and (CH2)v+2X, each v is independently an integer from 0 to 5, and X = Cl, Br or I, with a secondary amine having the formula NHR132 wherein R13are CH3, C2-C8 straight chain or branched alkyl, C5-C8 cycloalkyl, or together with nitrogen comprise a 5- to 8-membered ring, to produce a fluorinated dialkylamino compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R14)(OCH3)(CH2)vCH2CH2NR132wherein R14is CH3, CF3, or (CH2)vCH2CH2NR132;and (b) dechlorinating the fluorinated tertiary amine compound of step (a) to produce a trifluorovinyl dialkylamino compound having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R14)(OCH3)(CH2)vCH2CH2NR132wherein81. A process for manufacturing a trifluorovinyl quaternary ammonium salt, comprising (a) reacting a trifluorovinyl tertiary amine compound having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2 wherein x = 0 or 1; z = 0 to 4; Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein I = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2 provided that there are no oxygen-oxygen bonds in the compound; R1is selected from CH3 and CF3; a = 0 to 4, b = 0 or 1, R7are both H or both CH3, with an alkylating agent, R3Q; and (b) producing trifluorovinyl quaternary ammonium salt of the formula {CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2R3}+1[Q-n]1 / n whereinis Cl, Br, I, and O3SR4 wherein R4 = C1-C3 alkoxy, C1-C6 straight chain or branchedalkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl.

82. A process for manufacturing a trifluorovinyl compound, comprising (a) (i) obtaining an organometallic reactive intermediate solution from the reaction of a polyfluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2Y wherein Y is selected from Br or I, x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, with a compound having the formula RMgZ, wherein R = C1-C6alkyl, or aryl, and Z = Cl, Br or I, and a bis(cyclopentadienyl)zirconium dichloride compound and (ii) reacting theorganometallic reactive intermediate solution with a cyanoketone having the formulaR1C(O)(CH2)mCN wherein m = 1 to 5, and R1 is CH3 or CF3, to produce a fluoroalkylhydroxynitrile compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OH)(CH2)mCN; (b) methylating the fluoroalkyl hydroxynitrile compound of step (a) to produce a fluoroalkyl methoxynitrile compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)mCN; and (c) dechlorinating the compound of step (b) to produce a trifluorovinyl nitrile having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R1)( OCH3)(CH2)mCN.

83. A process for manufacturing trifluorovinyl alkyl nitrile, comprising (a) reacting an alcohol having the formula R1C(OH)(CH3)CN wherein R1is CH3 or CF3, with a sulfonyl chloride compound having the formula R4SO2Cl, wherein R4is C1-C6 straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl, to form a reactive ester having the formula R1C(OT)(CH3)CN wherein T = SO2R4; (b) (i) obtaining an organometallic reactive intermediate solution made from the reaction of a polyfluoroalkyl halide compound having the formula CClF2CClF(CF2)z(O)x(Rf)CF2Y wherein Y is selected from Br or I, x = 0 or 1; z = 0 to 4; and Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOk wherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound, with a compound having the formula RMgZ, wherein R = C1-C6alkyl, or aryl, and Z = Cl, Br or I, and a bis(cyclopentadienyl)zirconium dichloride compound organometallic reactive intermediate solution and (ii) reacting the organometallic reactive intermediate solution with the reactive ester formed in (a) to produce a fluoroalkyl nitrile compound having the formulaCClF2CClF(CF2)z(O)x(Rf)CF2C(R1)(CH3)CN; and (c) dechlorinating the fluoroalkyl nitrile compound of step (b) to produce a trifluorovinyl nitrile having the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(CH3)CN.

84. A process for preparing a fluoroalkyl nitrile compound comprising (a) reacting an alcohol of the formula R1C(OH)(CH3)CN wherein R1is CH3or CF3, with a sulfonyl chloride compound having the formula R4SO2Cl, wherein R4is C1-C6straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl, or an anhydride selected from (CF3SO2)2O and (CH3SO2)2O, to form a cyanosulfate ester of formula R1C(OT)(CH3)CN wherein T = SO2R4; and (b) reacting the cyanosulfate ester compound of step (a) with an organometallic reactive intermediate, wherein the organometallic reactive intermediate is formed by contacting a perfluoroalkyl halide compound of the formula Rf1CF2Y, wherein Y = Br or I, and Rf1is a straight or branched chain perfluoroalkyl, chlorofluoroalkyl, or fluoroalkyl group, optionally containing ether linkages having the formula CeHfClgF2e+1-f-gOhwherein e = 1 to 6, f = 0 to 4, g = 0 to 2, and h = 0 to 2 provided that no O-O bonds are present, with a compound having the formula RMgZ, wherein R = C1-C6 alkyl, or aryl, and Z = Cl, Br, or I, in the presence of a bis(cyclopentadienyl)zirconium dichloride compound; and, (c) producing a fluoroalkyl nitrile compound of the formula Rf1CF2C(CH3)(R1)CN.

85. A process for making a copolymer comprising, (a) providing (i) a trifluorovinyl quaternary ammonium salt of having a formula [CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)(R1)(CH2)yNR22R3]+1(Q-n)1 / n ; {CF2=CF(CF2)z(O)x(Rf)CF2C(OCH3)[(CH2)yNR22R3]2}+2[Q-n]2 / n ; or{CF2=CF(CF2)z(O)x(Rf)CF2C(R1)(OCH3)(CH2)a[C(R7)2]bCH2N(CH3)2R3}+1[Q-n]1 / nwherein a = 0 to 4, b = 0 or 1, x = 0 or 1; y = 1 to 7; z = 0 to 4; R1is CH3 or CF3; R2is independently selected from CH3, C2-C8 straight chain or branched alkyl, C5-C8 cycloalkyl, or together with nitrogen comprising a C5-C8membered ring; R3is CH3, C2- C8straight chain or branched alkyl or C5-C8cycloalkyl; R7are both H or both CH3;Rfis a straight chain or branched perfluoroalkylene group, CiF2i wherein i = 1 to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds; Q is a monovalent anion selected from Cl, Br, I, OH, HCO3, HSO4, H2PO4, BF4, PF6, O3SR4where R4is selected from C1- C3 alkoxy, C1-C6 straight chain or branched alkyl, fluoroalkyl, perfluoroalkyl, aryl, or substituted aryl, or a divalent anion selected from CO3, SO4, or HPO4, or PO4, wherein n is the charge on Q; (ii) a solvent; and (iii) an initiator; (b) providing at least one comonomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3,CF2=CFOCF3, CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3)-,CF2=CFOCF2CF2CF=CF2, or cyclo-[OCF=C(OCF3)OCF2]- ;(c) initiating the copolymerization reaction at a temperature suitable to form a copolymer of the comonomer and the trifluorovinyl quaternary ammonium salt; and (d) isolating the copolymer.

86. The process of claim 85, wherein the trifluorovinyl quaternary ammonium salt has the formula [CF2=CFOCF2CF2C(CH3)(OCH3)CH2CH2CH2N(CH3)3](O3SCF3).

87. The process of claims 85 and 86 wherein the comonomer is CF2=CF2.

88. A process for making a trifluorovinyl fluoroalkyl chloride compound, represented by the formula CF2=CF(CF2)z(O)x(Rf)CF2C(R5)(OCH3)(CH2)rCl wherein x = 0 or 1; z = 0 to 4; R5is selected from CH3, CH2Cl, CH2CH2Cl, or CF3; and ris 1 to 7, by dechlorinating the fluoroalkyl methoxy alkyl chloride compound representedby the formula CClF2CClF(CF2)z(O)x(Rf)CF2C(R5)(OCH3)(CH2)rCl.

89. A process for making a copolymer comprising, (a) providing (i) a trifluorovinyl quaternary ammonium salt of having a structure selected from ; orwherein l is 3, 4, or 5, l1 and l2 are 1 to 3 provided that l1 + l2 = 3 to 5; x= 0 or 1; z =0 to 4; R3is selected from the group CH3, C2-C8straight chain or branched alkyl or C5-C8cycloalkyl; Rfis a straight chain or branched perfluoroalkylene group, CiF2iwherein i = 1to 5, a straight chain or branched perfluorooxyalkylene group CjF2jOkwherein j = 1 to 5 and k = 1 or 2, provided that there are no oxygen-oxygen bonds in the compound; and Q is a monovalent anion selected from Cl, Br, I, OH, HCO3, HSO4, H2PO4, BF4, PF6,O3SR4 wherein R4 is selected from C1-C3 alkoxy, C1-C6 straight chain or branched alkyl,fluoroalkyl, perfluoroalkyl, aryl, and substituted aryl, a divalent anion selected from CO3, SO4 or HPO4, or PO4; (ii) a solvent; and (iii) an initiator; and (b) providing at least one comonomer selected from CF2=CF2, CF2=CHF, CF2=CClF, CF2=CH2, CH2=CHF, CH2=CH2, CF2=CFCF3, CH2=CFCF3, CH2=CHCF3,CF2=CFOCF3, CF2=CFOC2F5, CF2=CFOC3F7, cyclo-OC(CF3)2OCF=CF-, cyclo-OC(=CF2)OCF2CF(CF3)-, cyclo-OC(=CF2)OCF(CF3)CF(CF3)-,CF2=CFOCF2CF2CF=CF2, or cyclo-[OCF=C(OCF3)OCF2]- ;(c) initiating the copolymerization reaction at a temperature suitable to form a copolymer of the comonomer and the trifluorovinyl quaternary ammonium salt; and (d) isolating the copolymer.

90. The process of claim 89, wherein the comonomer is CF2=CF2.

Images