MXPA00011676A - Aromatic polymers with pendant fluorinated ionic groups - Google Patents

Abstract

A class of unsaturated compounds including containing a fluoroether-substituted aromatic ring, polymers, including ionomers, formed therefrom, and processes for forming them. The compositions of the invention have particular suitability for use in electrochemical applications.

Description

AROMATIC POLYMERS WITH PENDING FLUORITE IONIC GROUPS FIELD OF THE INVENTION This invention provides a new class of unsaturated compounds including those containing a substituted fluoroether aromatic ring, polymers, including ionomers, formed thereof, and processes for the formation thereof. The compositions of the invention are suitable for use in electrochemical applications.

BACKGROUND OF THE INVENTION Polymers containing the non-aromatic, pending, non-aromatic fluoroalkyl sulfonic acids and salts thereof with univalent metals are commercially available as the Fluoroionomer Nafion® available from E.l. du Pont de Nemours and Company, Wilmington DE. The polymers containing the fluorosul phonyl suspended non-aromatic imides and fluorosulphide embedded and the salts thereof with Ref. 124740 univalent metals are described in DesMarteau (U.S. Patent 5,463,005) where they are attached to perfluorinated main chains. Narang et al. (US Patent 5,633,098) describes the polysiloxanes and polyacrylates which have poly (alkylene oxide) side chains fluorinated with associated ionic species. In ur aspect, the side chains have the structure - (CH2) x '? (OCH2CH2) yl (OCF2CF2) z? S02R3 wherein R3 is OM, N (M) S02CF3 or C (M) (S02CF3) 2 and M is an alkali metal. Armand et al. (US Patent 5,627,292) describes monomers of the formula AXFCS02Z wherein A is R3 or R3OCF2-, X is F, Cl, H or a perfluoroalkyl group, Z is an ionic group and R3 is a non-perfluorinated polymerizable group. Polymers containing pendant -CH2OCF2CF2S02F groups are described by Hamel and Gard, J. fluorine Chem, volume 68, pages 253-259 (1994). Benrabah et al., J. Power Sources, volume 54, pages 456-460 (1995) describes ionically-conductive polymers of the monomers RXR2NC (O) CF (CF3) S03Li wherein R1 and R2 are allyls or R1 is allyl and R2 It is methyl. The above references do not disclose compounds containing a fluorinated ionic group directly attached to an aromatic ring by a thermally and chemically stable ether linkage. The reactions of the phenol salts with BrCF2CF2Br to form ArOCF2CF2Br are described in Clement et al. (U.S. Patent 5,037,919). The reactions of bromides and iodides of luoroalkyl with sodium dithionite or other sulfurization reagents to form sulfur-alkylated residues are described in Chemical Abstracts 105: 208423j. Conversions of the salts of furoalkyl sulphides to fluoroalkyl sulphonyl chlorides and fluorides are described by Hu and DesMarteau, Inorg. Chem. Volume 32, pages 5007 to 5010 (1993). The synthesis of the sulfonatics of luoroalkyl and the sulfonyl imides of the corresponding halides of luoroalkyl sulphide is also known, as described for example by Waddell et al. (US Patent 5,514,493) and DesMarteau (US Patent 5,463,005).

The reactions of fluorinated vinyl ethers with phenolic compounds in the presence of a base are known, as described for example by Fuss and Hintzer, Ger. Offen DE 3 828 063 (1990) and Meazza et al., European Application Patent EP C 293 943 (1998), and Feiring and Wonchoba (J. Org. Chem. Volume 57, pages 7015-7017). Feiring, US Patent 5,198, 570 (1993) describes the synthesis of aryloxyfluoroeter esters of the structure Ar (OCF2CFHOR1C02R2) p wherein Ar is an organic radical containing one or more aromatic rings, each R1 is a perfluoroalkyl or ether, thioether, chlorine, hydrogen, alkyl or substituted perfluoroalkyl phenyl, and p is from 1 to 5 which are prepared by the reaction of the phenolic compounds with fluoro containing olefins of the structure CF2 = CFOR1C02R2 in the presence of a base. Inukai et al. (JP 3-230169) describes the homopolymers and copolymers having elements of monomers of the formula: where Rf is a per fluoroalqueni what has 3-12 carbons, comonomers that include styrene and ethylene. Polymers are those that are formed by subjecting the polymers having vinyl phenol elements to react with a per-fluoroolefin oligomer in the presence of a basic catalyst in a non-aqueous solvent.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a polymer comprising pendant groups comprising the radical described by the formulas Ia or Ib: O-CF 2-Rf-CF2S02Y (SO 2Rf O 0-CF 2-R (-CF 2 SO 2Y (SO Rf ') n wherein Rf is a bond or is a f-aloroalkylene group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms. Y is N, O, C. Rf 'is a fluoro group from 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or 10 more hydrogen atoms. n = 0, 1 or 2 with the proviso that n = 0 when Y = 0, n = l when Y = N and n = 2 when Y = C, and Z is a hydrogen or a univalent metal. In addition, compounds 15 described by formula (II) are provided < ** & amp; 0-CF2-RrCF2S02Y (SO 2Rf wherein m = 0, 1 or 2 and when m = l R is a polymerizable group or bromine or iodine, and when m = 2, R represents polymerizable groups or groups of bromine or iodine, which are optionally the same, Rf is a bond or is a fluoroalkylene group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, and is N, O, C, Rf 'is a luoroalkyl f-group of 1 to about 10 atoms of? carbon, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, n = 0, 1 or 2, n = 0, 1 or 2 with the proviso that n = C when Y = 0, n = l when Y = N and n = 2 when Y = C, and 2 is hydrogen or a univalent metal. Preferably a polymerizable position group for, a bromo group for or an iodo group for.

Further provided is a process comprising: The reaction of alkali metal salts of substituted phenols described by the formula (III) with 1,2-dibromotet-fluoro-fluoroethylene to produce the compounds described in the formula (IV) JBG wherein m is 0, 1 or 2 and R is bromine, iodine, C02R 'or N02, R' is an alkyl group of 1 to 10 carbon atoms and M is an alkali metal, the reaction of the compound described by the formula ( IV) with a sulphuration reagent to form an alkali metal sulphinate described by the structure (V) .-to.:.;. 2S02 (IV) (V) The reaction of an alkali metal sulphinate of structure (V) with an elemental chlorine or bromine to provide the corresponding sulfonyl chloride or bromide described by structure (VI) wherein X = Cl or Br; OzX In addition, an ionically conductive composition comprising the ionomer of the invention and a liquid absorbed therein is provided. In addition, an ionically conductive composition comprising the compound described by the formula (II) and a liquid is provided.

Further provided is an ion exchange membrane comprising an ionomer comprising pendant groups comprising the radical described by formulas (I) a and (I) b: O-CF 2-Rf; CF2S? 2Y (SO 2 Rf ') n 0-CF2-Rf-CF 2SO 2Y (SO 2Rf wherein Rf is a bond or is a f-alkoalkylene group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, and is N, O, or C, Rf ' is a luoroalkyl group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or Í, -, aÉA_ > more hydrogen atoms, n = 0, 1 or 2 with the proviso that n = 0 when Y = 0, n = l when Y = N, and n = 2 when Y = C, and Z is hydrogen or a univalent metal. Furthermore, electrochemical cells comprising a cathode, an anode and a separator are provided, at least one of which comprises an ionomer comprising pendant groups comprising the radical described by the formulas I (a) and / or I (b). Further provided is an electrochemical cell comprising an anode, a cathode, a separator, and a conductive composition comprising the compound described by formula (II) and a liquid. In addition, an electrode comprising a reactive active material and an ionomer comprising pendant groups comprising the radical described by formula I (a) and I (b) is provided.

DETAILED DESCRIPTION OF THE INVENTION The ionomers of the present invention exhibit a high solubility in numerous organic solvents which facilitates the manufacture of thin films and other molded articles. Relatively low fluoro contents allow the use of low cost starting materials, and stability is improved in highly reduced environments such as is found in high voltage batteries such as lithium batteries. In contrast to the fluorinated ionomers partially shown in the art, the ionomeric group in the ionomers of the present invention is attached to the polymer backbone by aryl-haloalkyl ether bonds which have a high stability for strongly acidic or alkaline conditions. . The preferred styrene-based monomers of the invention are especially versatile materials for the synthesis of ionomers with a wide variety of properties since styrenic monomers can be homopolymers and copolymerized with a wide variety of comonomers and are known to be polymerizable by methods of free radical polymerization, cationic, anionic and coordination. In this way, a person skilled in the art can select ^ ¿^^ - f ^ aa--. of many comonomer and polymer structures, including graft copolymers and block copolymers, to obtain the desired combination of polymer properties. The present invention provides a polymer comprising pendant groups comprising the radical described by the formulas I (a) and I (b): O-CF 2-Rf CF2S02Y (SO 2 Rf ') n 0-CF2-Rf-CF 02Y (SO 2 Rf) n wherein Rf is a bond or is a f-alkoalkylene group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, And it is N, O, or C, Rf 'is a fluoroalqui group of 1 fe¿¡¿¿s,? i - \ _ to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, n = 0, 1 or 2 with the proviso that = 0 when Y = 0, n = l when Y = N, and n = 2 when Y = C, and Z is a hydrogen or a univalent metal. Rf is preferably a bond, CFH0CF2CF (CF3) OCF2 or CFHOCF2; more preferably Rf is a bond. Y is preferably N or 0, which is, n = 0 or 1, and Z preferably is a lithium cation. When Y is N or C, Rf 'is preferably CF3 or C2F5, more preferably CF3. Preferably the polymer is a polyester or polyolefin, more preferably a polyethylene, having pendant groups comprising the radical described by the formula (I). The polymer of the invention is preferably formed by polymerization of a monomer described by the formula 0 CF2-RrCF2S02Y (SO 2R) n wherein m = 0, 1 or 2 and when m = l R is a polymerizable group or bromine or iodine, and when m = 2, P represents polymerizable groups which are optionally the same, Rf is a bond or is a group f-loroalkylene from 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, Y is N, O, C, Rf 'is a luoroalkyl group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, n = 0, 1 or 2 n = 0, what 2, with the proviso that n = 0 when Y = 0, n = l when Y = N and n = 2 when Y = C, and Z is hydrogen or a univalent metal. R is preferably a polymerizable group in the para position, a bromo group for or an iodo group for, Rf is preferably and y ^ -J-a bond, CFHOCF2CF (CF3) OCF2 or CFHOCF2; more preferably Rf is a bond. Y is preferably N or O, which is n = 0 or 1, and Z is preferably a lithium cation. When Y is N, Rf 'is preferably CF3 or C2F5, more preferably CF3. (R) m is preferably 4-CH = CH2 when m = 1 or 3, 5-di-C02CH3 when m = 2. More preferably, R is 4-CH = CH2 and m = l. The preferred aspect of the monomer of the invention, wherein Rf is a bond, is preferably formed by the process of the invention, the process comprising: reacting the alkali metal salts of substituted phenols described by formula (III), with 1, 2 -dibromotet raf luoroethylene to produce compounds described by the formula (IV) wherein in (III), m is 0, 1 or 2 and (R) is a polymerizable group or a precursor thereof and is preferably a bromine, iodine, diester or dinitro compound, and wherein when m = 2, the groups R are optionally the same, and reacting the compound described by the formula (IV) with a sulfurization reagent such as sodium dithionite to form an alkali metal sulfinate described by the formula (V) 2S02 (IV) (V) In one aspect of the invention, the compound described by the formula (V) is converted to the corresponding sulfonyl chloride or bromide by reaction with elemental chlorine or bromine, represented by the formula (SAW) wherein X is chlorine or bromine, preferably chlorine. The compound described by the formula (VI), in turn, may be subjected to hydrolysis under basic conditions to form an alkali metal, preferably lithium, sulfonates described by the formula (VII) (Vile) where M + is an alkali metal. In the composition described by formula (VII) when m = 2 has ester groups, preferably -COOCH3, at positions 3,5, and can be polymerized c copolymerized by condensation polymerization reactions as are known in the art to form a polyester. The bromo and iodo substituents are preferably in a para position. When m = 1, the bromo or iodo substituent can be converted to a polymerizable alkenyl group, preferably vinyl, according to the methods shown in RF Heck, Acc. Chem. Res, volume 12, pages 146-51 (1979), The resulting styrenic monomer is then homo or copolymerized by means known in the art to form an ionomer of the invention. It is possible to fluorinate the brominated or iodated monomer to form the corresponding sulfonyl fluoride prior to hydrolysis, but this additional step is not necessary. In a preferred aspect of the process of the invention, the sulfonyl chloride or bromide described by the formula (VI) is exposed to an ionic fluoride, preferably an alkali metal fluoride, to form the compound described by the formula (VIII). The compound described by the formula (VIII) is then reacted with perfluoroalkylsulfonamides under basic conditions, preferably with an alkali metal containing a base, to form sulfonylimide compounds described by the formula (IX), as 2Rf 'moves In the direct analogy to the case of the compound described by the formula (VII), in the composition described by the formula (IX) when m = 2, the ester groups, preferably -COOOCH3 are placed in the 3-position. , 5, and can be polymerized or copolymerized by condensation polymerization reactions as are known in the art to form a polyester. When m = 1, the bromo or iodo substituents, preferably in the para form, can be converted to a polymerizable alkenyl group, preferably vinyl, according to the methods shown in R.F. Heck, Acc. Chem. Res., Volume 12, pages 146-51 (1979), the resulting styrenic monomer is then homo- or copolymerized to form an isnomer-of the invention. The above processes are directed to form the monomers and polymers described, and finally the ionomers which are preferred in the practice of the present invention, ie those wherein Rf is a bond. Other monomers and polymers of the invention, wherein Rf is not a bond, can be formed by other processes. For example, the phenols can be reacted with fluorinated olefins described by the formula (X) in the presence of a catalytic amount of base according to the following equation: + CF2 * CFORrCF2SO2Y (S02Ri (») OH (X) In the compound described by the formula (X) Rf" is a fluoroalkylene group of one to ten carbon atoms optionally substituted by one or more ether oxygens, M is a alkali metal and (R) m / Y / Rf 'and n are as described above This process provides compounds of structure (II) wherein Rf is CHFORf ", which is Rf contains at least one hydrogen. In another process, a phenolic compound reacts with a substituted fluoroalkylacyl iodine chloride to form an ester described by the formula (XI). The resulting ester is reacted with sulfur sulfur tert to form an ether described by the formula (XII). The reaction of the fluoride iodide with a sulfurization reagent such as sodium dithionite provides a sulphinate salt described by the formula (XIII) which can be converted to the compounds described by the formula (II) by the processes described above.

(XII) (XII) + sulfinization reagent xn > In the formulas (XII) Rf is a per-fluorofluoroalkylene group having from 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens. The group (s) R in the compound described by the formula (II) of the present invention imparts polymerization to the monomers of the invention, or are precursors of groups which impart polymerization. The goal is to provide the ionomer described by formula (I) by homo- or copolymerization of one or other of the monomers of the invention preceded by or followed by all the necessary reactions described hereinabove in order to carry out one or the other of the ionomers of the invention. The choice of R for the start is described not only for the desired end product, but also for the stability of that choice for the reactions that intervene between the starting material and the final ionomer. Ester groups, for example, are stable for the reaction of the substituted phenol (III) with dibromotet hydrochloride and the subsequent sulphination of the product thereof (IV) to the sulphinated metal (V). However, vinyl groups are not stable in these reactions. Thus, if a polyvinyl ionomer is the desired final product, it is desirable to start with the structure (III) wherein R is a convenient precursor for the vinyl group such as bromine or iodine which can be converted, then the formation of the structure (VII or IX), to the vinyl group by the reaction of Heck, op. cit. In other ^ - ^ - », ..- example, the structure (II) with R = 3,5-dinitro can be reduced to R = 3, 5-diamino for the synthesis of polyamides and with R = 4-cyano it can be converted to R = 4 - (2 -oxazoline) for the synthesis of polyoxazolines. The compounds of structure (II) with R = 3-or 4-ethenyl, which are substituted styrene monomers, are especially preferred. The 3-or 4-hydroxies of trienes are known compounds and can react with the compound (X) to form the desired derivatives. However, 3- and 4-hydroxystyrenes are expensive and are not readily available and the olefinic group can intervene with the steps in the process using intermediates IV, V, VI and VII. In this way, it may be preferable to conduct the above reactions on the more readily available 3- or 4-bromo or iodo phenols and subsequently convert the bromine or iodine groups to CH = CH2 by means of the reaction with ethylene and a palladium catalyst. . The polymers containing the radical described by the formula (I) are prepared from the ^^ V3 &- ^^^ j? ¿J ^ monomers (II) by a variety of well-known techniques which depend on the exact structure of the monomeric compound and the properties desired for the final product. Thus, monomers (II) 'wherein R is -CH = CH-: are especially preferred since such styrene compounds are readily homopolymerizable by free radical, anionic, cationic or coordination polymerization techniques. Such styrene derivatives can also be copolymerized with other monomers to produce the copolymers wherein the structure units (I) comprise about 1% to about 99% of the repeating units in such polymers. Examples of other monomers include styrene, substituted styrenes, acrylonitrile, alkyl and aryl methacrylates, alkyl and aryl acrylates, acrylamides, isoprene, chloroprene, butadiene, vinyl acetate, N-vinyl idinone, and mixtures of such comonomers. Both blocking and random co-termers can be produced by the application of well-known polymerization techniques. The ionomers of the present invention may optionally be degradable by techniques known to those skilled in the art. The degradation can be advantageous by allowing the article of the formed polymer, such as a film, to expand but not dissolve in various solvents. To prepare the degradable materials, the monomers (II) where R is -. 10 -CH = CH2, for example, can be mixed with a di or trifunctional monomer, such as poly (ethylene glycol) diacrylate or trimethylolpropane triacrylate, an initiator and, optionally, other chromonomers. A solvent such as, DMF, can be added to form a homogeneous mixture that can be emptied and heated to cause polymerization to a film of the degradable polymer. Degradable films can also be obtained by mixing the monomers (II) wherein R is -CH = CH2 with a polymer containing unsaturated groups and an initiating radical. The ingredients can be combined in the mixture or in a solvent like DMF, -'-. formed in a film or other articles molded and heated to thereby effect the degradation. A representative polymer with unsaturated groups is Hydrin T, a terpolymer of ethylene oxide, an epichlorohydrin and an allylic glycidyl ether available from Zeon Chemicals Incorporated, Hattiesburg, MS. The monomers (II) wherein the R groups are two methyl ester units that will be subjected to the condensation polymerizations with diols to form polyesters containing units of the structure (I). Suitable diols include ethylene glycol, 1,3-propanediol, 1,4-but-anodiol, polyethylene glycols, poly (tet ramethyl ether) glycols, hydroquinone and substituted hydroquinones. Mixtures of the diols can be used. In addition, other diester monomers, such as dimethyl terephthalate, can be used with the diester monomer (II) to produce the copolymers. It is apparent that the wide variety of condensation polymers, which include polyesters, polyamides and polycarbonates can Jb ** Z > &&£ £ l l l l l l l l l l ser ser ser ser ser ser ser ser ser ser ser ser &&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&. While there is no limit to the proportions form of an article formed of the ionomers of the present invention, the thin films or membranes are of particular utility as spacers in electrochemical cells, preferably in lithium ion batteries. In some cases it may be possible to extrude the films using a screw extruder press and a flat nozzle. Alternatively, the films can be pressed by melting. In a further aspect, the films can be cast from solutions or dispersions of the polymers upon emptying onto a substrate and a coagulant. No particular method is preferred over another, and the specific method will be selected according to the needs of the particular professional. The additives can be included to improve the property of the separating materials and the separators can also be formed by the addition of the ionomers of the porous substrates. The ionomers of the present invention exhibit a high ionic conductivity at room temperature of ca. 10 ~ 7-10 ~ 6 S / cm dry. However, it has been found in the practice of the invention that numerous liquids, when absorbed in the ionomer of the invention, increase the conductivity by orders of magnitude. In this manner it has been found desirable in order to carry out the most useful aspects of the present invention to form the conductive compositions wherein the liquids are absorbed in an ionomer of the invention. The liquid used will be dictated by the application. In general terms, it has been found in the practice of the present invention that the ionomer conductivity containing the liquid increases with the increase in% of the weight absorbed, increasing the increasing dielectric constant, and the Lewis basicity of the liquid, while the Conductivity has been observed to decrease with the increase in viscosity and the increase in the molecular size of the liquid used. In this way, a highly basic solvent of low viscosity and a small molecular size but with a low dielectric constant can provide a higher conductivity in a given membrane than a less basic solvent, more viscous and larger than a much higher dielectric constant. Of course, other considerations can also be taken into account. For example, an excessive solubility of the ionomer in the liquid may be undesirable or the liquid may be electrochemically unstable in the proposed use. A particular preferred aspect comprises the lithium ionomer combined with aprotic solvents, preferably organic carbonates or diesters, including mixtures thereof, which are useful in lithium batteries. More preferably the liquid is a mixture of ethylene carbonate and dimethyl succinate. Among the uses for the present invention are fuel cells, sensors, electrochemical capacitors, primary and rechargeable batteries w ^^^^^^^^^^^^ j ^^^ g ^^^^^^^^^^^^^^^^^^^^^^^^^^^ and other applications of electrochemical devices. It has further been found in the practice of the present invention that useful conductive compositions are formed by forming salt solutions described by the formula (II). Rf is preferably a bond CFHOCF2CF (CF3) OCF2 or CFHOCF2; more preferably Rf is a bond. Y is preferably N u 0, which is, n = 0 or 1, and Z is preferably a lithium cation. When Y is N, Rf is preferably CF3 or C2F5, more preferably CF3. Suitable solvents for use in forming the conductive solutions herein include water, alcohols, and aprotic organic liquids. Preferably, the solvents are organic carbonates, with mixtures of ethylene carbonate and dimethyl carbonate EC / DMC more preferable. The preferred electrode of the present invention comprises a mixture of one or more active materials of the electrode in particulate form, an ionomer of the invention, at least one electron additive conductive, and at least one organic carbonate. Examples of useful active anode materials include, but are not limited to, carbon (graphite, coke, mesocarbons, polyacenes, and the like) and intercalated lithium carbon, lithium metal nitrides, such as Li2.6Co0. N, glasses based on tin oxide, lithium metal, and lithium alloy with aluminum, tin, magnesium, silicone, tin, manganese, iron and zinc. Lithium intercalation anodes that use carbon are preferred. Useful active cathode materials include, but are not limited to, transition metal oxides and sulfides, lithium transition metal oxides and sulfides, and organosulfur compounds. Examples of these are cobalt oxides, manganese oxides, molybdenum oxides, vanadium oxides, titanium sulfides, molybdenum and niobium, lithiated oxides, such as lithium manganese oxides spinel Li? + XMn2_x04, manganese oxides of lithium spinel covered with chrome LixCryMnz04, LiCo02, LiNixC ?? - x02 where X is 0 < X < 1, with a preferred range of 0.5 < X < 0.95, LiCoV0, and mixtures thereof. LiNixC _ x02 is preferred. A highly preferred electron conductive auxiliary is carbon black, preferably Super P carbon black, available from MMM S.A. Carbon, Brussels, Belgium, in the concentration range of 1-10%. Preferably, the fraction of the volume of lithium ionomer in the finished electrode is between 4 and 40%. The preferred electrode of the invention can conventionally be made by dissolving all the polymeric components in a common solvent and mixing them together with the carbon black particles and the active particles of the electrode. For cathodes the active material of the preferred electrode is LiNixC - x02 where 0 <X < 1, while for the anodes the active material of the electrode are graphitized mesocarbon microbeads. For example, a preferred lithium battery electrode of the invention can be manufactured by dissolving the ionomer of the invention in a mixture of acetone and dimethylformamide, followed by the addition of particles of the active material of the electrode, and carbon black, followed by the deposition of a film on a substrate and drying. The resulting preferred electrode will comprise the active material of the electrode, the conductive carbon black, and the ionomer of the invention, wherein preferably, the weight ratio of the ionomer to the active material of the electrode is between 0.05 and 0.8 and the proportion of the black of Coal with the active material of the electrode is between 0.01 and 0.2. More preferably, the weight ratio of the ionomer to the active electrode material is between 0.1 and 0.25 and the weight ratio of the carbon black to the active material of the electrode is between 0.02 and 0.1. This electrode can then be emptied of. the solution on a suitable support such as a glass plate or a common metal leaf collector, and formed into a film using techniques, well known in the art. The electrode film produced in this way can then be incorporated into a multilayer electrochemical cell structure by lamination, as described below. Other aspects can be realized by methods known to those skilled in the art. See, for example, descriptions of the manufacturing methods of the lithium ion cells in U.S. Pat. No. 5,658,683 (Sony Corp. Aug. 19, 1997) and U.S. Pat. No. 4,668,595 (Asahi May 26, 1987), which are both incorporated herein by reference. It may be desirable to incorporate such auxiliaries into the composition of the electrode of the invention as may be useful for such purposes as they may improve the binding of the components thereof, or provide improved structural integrity of an article manufactured therefrom. This improvement can be carried out by incorporating 2-5% by weight of a polymeric binder substance. A particularly preferred additional material is polyvinylidene fluoride, which can be incorporated simply by dispersing the particles thereof in the same solution where the electrode is being formed, as described above.

In an alternative process, the dispersion of the active material of the electrode and the optional carbon black and other auxiliaries can first be emptied into a surface followed by the addition of the ionomer of the invention in an organic carbonate solution. In a preferred aspect of the battery of the present invention, a battery is formed from one or more electrochemical cells formed by laminating together in the form of the film the separator, cathode and anode compositions of the present invention, all of which they have been rigorously dried before the addition of a liquid selected from the group of organic carbonates and mixtures thereof, a mixture of ethylene carbonate and dimethyl carbonate are preferred. The relatively high solubility of the ionomers of the present invention provides a benefit in the ease of the process during the manufacture of the components of a battery but can be problematic during the final assembly of the desired battery product. Organic carbonates not only expand the ionomeric polymer, but can also dissolve the polymer depending on the composition thereof, the primary determining factor is the degree of crystallinity, which in turn describes the concentration of the ionic comonomer in the polymer. The challenge is to dilate the ionomer with a solvent while minimizing the dissolution of the polymer. It may be desirable to increase the physical properties of the grown solvent membrane. The means available to improve the mechanical properties include: 1) incorporation into the polymer by means known in the art of a nonionic comonomer that is less sensitive to the solvent: 2) the formation by known means of a mixture of polymers with a polymer nonionic that is less sensitive to the solvent; 3) the mixture by known means of the ionomer of the invention with an inert filler; 4) the mixture of compositions different from the ionic copolymers; and 5) degradation. A preferred method is to mix the ionomer with an inert filler before forming the separating membrane or separating film. Suitable inert fillers include Si02, A1203, Ti02 or CaF2, with Si02 being preferred. Particles with a large or small surface area of less than 1.0 micron in diameter are desired, as are available for the preferred grade of Si02 under the trade name of silica Cab-o-sil® TS-530. Loads of up to 50% by weight of the filler are preferred. Another approach comprises the dissolution of the ionomer in the preferred organic carbonate solvents, followed by the introduction of the resulting solution or gel into the pores of an inert porous polymeric support such as the porous propylene Celgard®, available from Hoechst-Celanese, or PTFE Microporous Gore-Tex, available from WL: Gore Associates Newark, DE. In alternative aspects of the invention a non-polymeric salt described by the formula (II) can be used in addition to or in place of the ionomer of the present invention as the aspects described above are employed. The invention is further described in the following specific aspects.

EXAMPLES For purposes of the present invention, the term "conductivity" used herein specifically refers to the ionic conductivity as determined using the so-called four-point test technique, described in the article entitled "Proton Conductivity os Nafion® 117 As Measured by to Four Electrode, AC Impedance Method "by Y. Soné et al., J. Electrochem. Soc., 143, 1254 (1996). The method as described applies to aqueous electrolyte membranes. The method is modified for the purposes of obtaining the measurements reported here for non-aqueous solvents by placing the described apparatus in a glove box purged with dry nitrogen in order to minimize any exposure to water. The method is also modified by substituting the parallel linear probes that traverse the full width of the test specimen for the point probes employed in the published method. A film of 1.0 cm by 1.5 cm is stained dry and placed in the conductivity cell. The impedance of the cell is determined over the range of 10Hz to 100, 000 Hz, and the value with the zero phase angle in the higher frequency range (usually 500-5000 Hz) is attributed to the resistance of the block sample in ohms. The value of the raw strength is then converted to conductivity, in S / cm, using the cell constant and the thickness of the film. The absorption of the solvent is determined from the equation% of absorption = (Ww - Wd) / Wd where Wd is the weight of the membrane before the contact of the solvent and Ww is the weight of the membrane after contact with the solvent determined after the first removal of the solvent membrane and then dry using a paper towel to remove excess surface solvent. All chemicals are used as received until otherwise indicated. The 19F NMR spectra are recorded using a Bruker AVANCE DRX 400 spectrometer. The 1H NMR spectra are recorded using a Bruker AVANCE DRX 500 spectrometer.

EXAMPLE 1 Synthesis of 2- (4-phenoxy) -tetrafluoroethanesulfonyl chloride The 4-bromophenol (Aldrich Chemicals 348.4 g, 2.01 mole) is dissolved in 1.95 L of 1.033N potassium hydroxide in methanol. This solution is evaporated to dryness in a rotary evaporator and the resulting solid is dried at 140 ° C and 0.1 mm. The solid is mixed with 600 ml of DMSO under nitrogen. The 1, 2 -dibromotet raf luoroethane (571.6 g, 2.2 mol) is added dropwise at a temperature of 30-40 ° C. The resulting mixture is heated at 60 ° C for 6 hours. This is cooled to room temperature and diluted to 3L with ice and water. The organic layer is separated and the aqueous solution is extracted with 2 X 75 ml of methylene chloride. The methylene chloride extracts are concentrated in a rotary evaporator and the residue is combined with the original organic layer. This material is washed with 2 X 400 ml of water, dried with anhydrous magnesium sulfate and filtered. The filtrate is distilled providing 641.2. g (92%) of l-bromo-2- (4-bromophenoxy) tetraf luoroethane. Mp 57 ° C to 6 mm.

This product of a similar preparation shows H NMR (d, CDCl 3), 7.1 (d, 2 H), 7.5 (d, 2 H) 19.

NMR (d, CDCl 3), -68.6 (2F), -86.6 (2F). Anal. Calculated for C8H F40Br2: C, 27.30; H, 1.15; Br, 45.41; F, 21.59. Found: C, 27.27; H, 1.16; Br, 44.85; F, 20.87. A portion of 366.5 (1.04 mol) of the above product is added under a nitrogen atmosphere to a stirred mixture of 1026 L of distilled and deoxygenated water, 186.5 g of sodium bicarbonate, 500 ml of dimethylformamide and 357.6 g of sodium dithionite. . This mixture is heated to 65 ° C resulting in rapid gas evolution. The evolution of the gas ceases after 1 hour and the mixture is heated to 70-75 ° C for 3 hours. Cool to about 10 ° C in a melting ice bath and add ethyl acetate. The mixture is filtered and the solid is washed with ethyl acetate. The combined filtrates are separated into aqueous and organic layers and the organic layer is washed with 4 X 50 ml of a saturated aqueous sodium chloride solution. The organic layer is concentrated in a rotary evaporator to about 1/4 of its initial volume and filtered. The solid is washed with ethyl acetate. The combined organic solutions are concentrated to dryness in a rotary evaporator to yield 362.6 g (97%) of a white solid of 2- (4-bromophenoxy) t et raf luoroetanosulfinat or sodium. XH NMR (d, CD30D) 7.2 (d, 2H), 7.6 (d, 2H); 19 F NMR (d, CD30D) -132.8 (2F), -81.9 (2F).

The above product is dissolved in a mixture of 600 ml of deoxygenated water and 300 ml of 1,1,2-trichlorotr and fluoroethane in a round bottom flask equipped with a dry ice condenser and cooled to 5-15 ° C. The chlorine gas (134 g) is bubbled into this mixture for about 1 hour. The resulting yellow mixture is stirred for 1 hour without external cooling. Warm to 20 ° C and an additional 200 ml of 1, 1, 2- trichlorotrif luoroethane are added. The organic layer is separated and the aqueous solution is extracted with 100 ml of 1,1,2-t riclorotri fluoroethane. The combined organic solutions are dried over anhydrous magnesium sulfate and concentrated in a rotary evaporator. The residue is distilled through a short Vigreux column to yield 361.1 g (97%) of 2- (4-bromophenoxy) tet-fluoro-fluorosulfonyl chloride, boiling point 71 ° C at 0.3 mm. ? NMR (d, CDC13) 7.1 (d, 2H), 7.6 (d, 2H); 19 F NMR (d, CDC13) -79.0 (2F), -107.9 (2F). A sample of a similar preparation is submitted for elemental analysis. Anal. Cale, for C8H4F BrClS03: C, 25.86; H, 1.08; F, 20.46; S, 8.63. Found: C, 26.07; H, 1.17; F, 18.74; S, 8.59.

EXAMPLE 2 Synthesis of Lithium 2- (4-bromophenoxy) tertrafluoroethanesulfonate (600 g, 1,365 mole) of lithium hydroxide monohydrate in 600 ml of deoxygenated distilled water. THF (150 ml) is added and this solution is heated to 35 ° C. The hot source is removed and 237 g (0.64 mol) of 2- (4-bromo-phenoxy) -ethene-1-fluoro-25-chloroethanesulfonyl chloride are added dropwise about 45 minutes at a rate so that the Fr **** exotherm maintain the solution at about 55 ° C. After the addition is complete, the solution is maintained at 55 ° C for an additional 1.5 hours. The solution is cooled to room temperature. Its pH is adjusted to 7 by the addition of about 3 ml of concentrated hydrochloric acid and the aqueous solution is evaporated to dryness in the rotary evaporator. The solid is mixed with ether and filtered. The ether solution is treated with three volumes of hexane resulting in the precipitation of a white solid. The solid is filtered and washed with hexane. The filtrate is evaporated and the residue is again precipitated from the ether solution by the addition of hexane. The combined precipitates are recrystallized from acetonitrile with cooling in the refrigerator with the concentrated filtrate several times to collect the additional fractions. The combined recrystallized product is dissolved in ether, filtered and concentrated in a rotary evaporator. The product is dried at 100 ° C and 0.1 mm and yields 173.9 g (76%) of the title compound as a white solid. A NMR (d, CD30D) 7.2 (d, 2H), 7.6 (d, 2H); 19 F NMR (d, CD30D) -116.9 (2F), -81.6 (2F). -ÁJ-ÜLa A sample of a similar preparation is submitted for elementary analysis. Anal Cale. for C8H4F4BrLiS03: C, 26.76; H, 1.12; F, 17.83; S, 8.93. Found: C, 26.57; H, 1.26; F, 18.94; S, 8.77.

EXAMPLE 3 Synthesis of lithium 2- (4-ethenylphenoxy) tetrafluoroethanesulfonate An autoclave of IS is charged with 69 g (0.19 mol) of lithium 2- (4-bromophenoxy) tetrafluoroethanesulfonate, 200 ml of acetonitrile, 0.88 g of Pd (0Ac) 2, 2.48 g of t-ri-o-1-ol and 1-phosphine and 200 ml of triethylamine. The autoclave is closed, cooled, evacuated and loaded with ethylene at 110 psi. The mixture is heated with stirring at 85 ° C for 2 hours, the gas pressure is maintained at 120-125 psi by venting or the addition of ethylene as needed. The mixture is cooled to room temperature and vented at atmospheric pressure. The contents of the autoclave are recovered using a mixture of acetonitrile and ether for washing. The mixture is treated with 8.9 g of hydroxide monohydrate of lithium in 150 ml of water with vigoroza agitation and filtered through celite. The celite is washed with acetonitrile and ether. The combined filtrates are evaporated to dryness at 75-80 ° C and 5 mm. The residue is extracted with 0.5 L of ether and filtered. The filtrate is diluted with 0.5 L of hexane and the resulting precipitate is collected, precipitated a second time from a mixture of ether and hexane and dried at 65 ° C and 0.05 mm to yield 20.6 g of product. An additional 12.8 g of product are obtained by the concentration of the above ether and the hexane filtrates and the reprecipitation of the residue for a total production of 33.4 g (58%) of the title product. A NMR (d, CD3CN) 5.27 (d, 1H), 5.80 (d, 1H), 6.78 (dd, 1H), 7.27 (d, 2H), 7.51 (d, 2H); 19 F NMR (d, CD3CN) -116.6 (2F), -80.8 (2F). Anal Cale. for C? 0H7 F4Li0 S: C, 39.23; H, 2.30; F, 24.82; Li, 2.27; S, 10.47. Found: C, 38.18; H, 2.78; F, 22.23; Li, 2.10; S, 9.55. EXAMPLE 4 Synthesis of 2- (4-bromophene loxy) tet fluorine-2-fluoride 2- (4-bromophenyloxy) tetrafluoroethanesulfonyl chloride (130 g, 0.35 mol) is added dropwise to a stirred mixture of 105 g (1.8 mol) ) on dry potassium fluoride and 500 ml of acetonitrile under a nitrogen atmosphere at room temperature. After 24 hours at room temperature, an NMR spectrum of fluoro shows about 80% conversion of sulfonyl chloride to fluoride. The mixture is heated to 30-35 ° C and then allowed to stir for 3 days at room temperature. This is filtered and the solid washed with acetonitrile. The combined filtrates are concentrated in a rotary evaporator at 40 ° C and 150 mm and the residue is distilled in a Kugeirohr at 80-85 ° C and 5 mm in a vessel cooled with dry ice. The liquid distillate is distilled through a 12"Vigreux column and 111.5 g (90%) of the title product is produced as a colorless liquid with a boiling point of 81-82 ° C at 4.5 mm. A NMR (d, CDC13 ) 7.1 (d, 2H), 7.5 (d, 2H); 19F NMR (d, CDC13) -81.7 (2F), -111.5 (2F) Anal Cale for C8H4F5BrS03: C, 27.06; H, 1.14; F, 26.75; S, 9. 03; Br, 22.5. Found: C, 27.13; H, 1.05; F, 26.88; S, 8.94; Br 22.35.

EXAMPLE 5 Synthesis of N- (trif luoromet anosul foni 1) -2- (4-bromo fexoni) tet ra f luoroet anosul lithium phonamide Tri f luoromet anosulfonamide just sublimated (15.51 g, 0.104 mol) is added to 240 ml of triethylamine which is freshly distilled from the lithium aluminum hydride. The mixture is heated to 40 ° C to dissolve the solid, then cooled to room temperature. Fluoride of 2- (4-bromo-phenoxy) tertiary-fluorosulphonic acid (35.7 g, 0.101 mol) is added and the solution is heated at 70-75 ° C for 18 hours. An F NMR spectrum of the solution shows a trace of a sulfonyl fluoride remnant, then the mixture is heated with an additional 1 g of trifluoromethoxide and heated for 16 hours at 70-75 ° C. The resulting red mixture is concentrated in the rotary evaporator. The residue is dissolved in methylene chloride, washed three times with water, dried over anhydrous magnesium sulfate and concentrated in a rotary evaporator. 46. 24 g of red oil, which is the triethylammonium salt of the title product. 1 H NMR (d, CDC13) 1.32 (t, 9H), 3.20 (q, 6H), 7.13 (d, 2H), 7.5 (m, 3H (+ aromatic NH)); 19 F NMR (d, CDC13) - 79.38 (3F), -81.0 (2F), -116.9 (2F). This salt is dissolved in 100 ml of methanol under a nitrogen atmosphere and treated with 79.95 ml of 0.9908 M aqueous lithium hydroxide. After stirring for 1 !: minutes, the solution is evaporated to dryness at 65-75 ° C under empty. The solid is dissolved in methanol, concentrated in vacuo and dried at 0.1 mm. The resulting solid is dissolved in 175 ml of ether and hexane and slowly added until a red oil precipitates leaving a colorless top coat. The top layer is decanted and evaporated to yield 30.9 g of the crude title salt. The salt is twice recrystallized from the ether and hexane mixtures to provide 29.7 g (60%) of the title product as a white powder. XH NMR (d, CD3OD) 7.2C (d, 2H), 7.60 (d, 2H); 19 F NMR (d, CD3OD) -79.02 (3F), -80.21 (2F), -115.5 (2F). Anal Cale. for C9H4BrF7LiN05S2: C, 22.06; H, 0.82; N. 2.86; F, 27. 14; S, 13.08; Br, 16.30; Li, 1.42. Found: C, 22.16; H, 0.83; N, 2.85; F, 25.66; S, 12.57; Br 16.14; Li, 1.34.

EXAMPLE 6 Synthesis of N- (tri f luoromet anosulfoni 1) -2 - (4-et en 1-phenoxy) tet lithium fonfluoroethansphonamide A pressurized 1 L vessel is charged under a nitrogen atmosphere with 73.5 g (0.15 mol) of N- (tri fluoromethanesul foni 1) -2- (4-bromophenoxy) tet lithium trifluoroethanesulphonamide, 300 ml of acetonitrile, 1.15 g of Pd (OAc) 2, 3.09 g of t-o-tolyl-phosphine and 120 ml of triethylamine. The autoclave is closed, cooled, evacuated and charged with ethylene at 100 psi. The mixture is heated with stirring at 85 ° C for 14 hours, maintaining the ga pressure at 125 psi for venting or for the addition of ethylene if necessary. The mixture is cooled to room temperature and vented at atmospheric pressure. The contents of the autoclave are recovered using a mixture of acetonitrile and water for washing. The mixture is treated with 6.3 g of lithium hydroxide monohydrate and 100 ml of water with vigorous stirring. Ether (300 ml) is added and the mixture is filtered through celite. A trace of 4-tert-but-ilcatecol remnant is added to the filtrate which is concentrated to a solid. The residue is dissolved in ether. A small aqueous layer is separated and the ether is dried over anhydrous sodium sulfate. This solution is filtered and concentrated to an oil in a rotary evaporator. Methylene chloride (50 ml) is added and the mixture is filtered. Hexane is added at the turbulence temperature and the mixture is filtered. The filtrate is concentrated under vacuum resulting in the separation of an oil. The trituration of the oil with hexane causes crystallization. The crystals are collected and dried to yield 53.1 g (81%) of the title product. A trace of 4-tert-but i read tecol is added to prevent polymerization. 1ti NMR (d, acetone d-6) 5.25 (d, 1H), 5.80 (d, 1H), 6.80 (dd, 1H), 7.30 (d, 2H), 7.55 (d, 2H); 19 F NMR (d, acetone d-6) -78.78 (3F), -79.77 (2F) -115.52 (2F). Anal Cale, for CnH7F7N05S2Li * 2.4 H20: C, 27.49; H, 2.48; N, 2.91; F, 26.67; Li, 1.44; S, 13.34.

Finding: C, 27.48; H, 2.24; N, 3.03; F, 28.55; Li, 1.47; S, 15.26.

EXAMPLE 7 Synthesis of homopolymerization of N-_ (lithium trifluoromethanesulfonyl) -2 (4-ethenylphenoxy) tetrafluoroethanesulfonimide A 400 ml pressure vessel is flushed with nitrogen and charged with 32.8 g (0.067 mol) of N- (trifluoromethanesulfonyl) -2- (4-bromophenoxy) - Lithium tetrafluoro-ethansulphonamide, 200 ml of acetonyl rile, 80 ml of triethylamine, 0.47 g of palladium acetate and 1.32 g of tri-1-olyphosphine. The container is closed, cooled, evacuated and charged with ethylene at 100 psi. The vessel is heated to 85 ° C and the internal pressure is maintained at 120 psi with ethylene gas for 22 hours. The vessel is cooled to room temperature and vented. The contents of the vessel are washed with a mixture of ether and water and treated with 2.82 g of lithium hydroxide in water. This mixture is filtered through celite and filtered and concentrated under vacuum. The residue is dissolved in ether, filtered and * ¿^ ". concentrate under vacuum for 35.9 g of a paste. This material is dissolved in ether and treated with hexane to precipitate a dark oil. The solution is decanted and the oil is extracted again with ether and treated with hexane to precipitate a solid which is discarded. The combined ether / hexane solutions are concentrated and the residue is recrystallized from ether hexane to yield 17.6 g of a white solid in three crops. A NMR (d, CD3CN) 5.3 (d, 1H), 5.8 (d, 1H), 6.78 (q, 1H), 7.25 (d, 2H), 7.50 (d, 2 H); 19 F NMR (d, CD3CN) -78.9 (3F), -79.6 (2F), -115.5 (2F). A weak peak in both the spectra NMR of the proton and fluorine suggest the presence of a small amount of the starting material. In an attempt of further purification, the product is dissolved in ether in the air and hexane is added to precipitate a gummy solid. It is recognized the different solubility characteristics and the loss of olefinic resonances in the NMR spectrum of the proton in which the product has been polymerized. The solid is dissolved in 50 ml of deionized water and dialyzed for several days against 2 X 2 L of deionized water in a cutting dialysis tube of 3500 MW. The solution in the tube is concentrated and dried at 100 ° C and 0.1 mm pressure to produce 10.9 g of a white solid polymer. A NMR (d, CD30D) 1.5 (broad, 3H), 6.5 and 6.9 (broad, 5H); 19 F NMR (d, CD30D) -78.81 (3F), -79.47 (2F), -114.8 (2F). Anal Cale. for CnH7F7S205NLi «2H20: C, 27.92; H, 2.34; N, 2.96; F, 28.10; Li, 1.47; S, 13.55. Finding: C, 27.98; H, 2.37; N, 2.97; F, 26.65; Li, 1.40; S, 13.84.

EXAMPLE 8 Synthesis of 4-CN-Ph-OCF2CFHOCF2CF (CF3) OCF2CF2S03Li A solution of 4-cyanophenol (7.15 g, 0.06 mol) in 80 ml of DMF is treated with 0.24 g (0.002 mol) of lithium tert-butoxide at room temperature. ambient. After stirring for 5 minutes, CF2 = CFOCF2CF (CF3) 0CF2CF2S03Li (28.4 g, 0.063 mol) is added in a portion resulting from an exotherm at 36 ° C. The resulting solution is stirred for 24 hours at room temperature. Concentrated hydrochloric acid (3 ml) is added and the mixture is concentrated in a rotary evaporator to a solid which is dried at 140-145 ° C and 0.05 mm to provide 35.2 g of a white solid. H NMR (d, acetone-D6) 6.95 (d, 1H), 7.5 (d, 2H), 7.9 (d, 2H); 19F NMR (d, acetone-d6) -78 to -80 (5F, CF3 and CF2), -81 to -89 (4F, of CF2), -117.3 (2F, CF2S03), -144.2 (1F, tertiary F) , -145.0 (1F, ddt, CHF).

EXAMPLE 9 Synthesis of Dissolve dimethyl-5-hydroxy-softalate (28.76 g, 0.0121 mol) in 200 ml of anhydrous DMF under an argon atmosphere. Tert-butyl lithium oxide (0.749 g) is added and the mixture is heated to 40 ° C, then cooled to room temperature. CF2 = CFOCF2CF (CF3) OCF2CF2S03Li is added solid (51.3 g, 0.114 mol) and the solution is heated to 40 ° C. A slight exotherm is noticed. The solution is stirred by Then, let it stir for 3 days at room temperature, 2 hours at 40 ° C. Hydrochloric acid (9.5 ml of 1.0 M) is added and the solution is concentrated in a rotary evaporator. The residue is dried at 145-150 ° C and 0.05 mm on a Kugeirohr. The dry solid is dissolved in 500 ml of ether. Hexane is added dropwise until a gummy precipitate is formed. The mixture is filtered and the filtrate is concentrated and dried at 100 ° C and 0.1 mm providing 74.0 g of a white solid. Anal Cale, for C? 7H? OF? 3O? OSLi: C, 30.92; H, 1.53; F, 37.41; S, 4.86; Li, 1.05. Found: C, 30.77; H, 1.77; F, 38.89; S, 4.69; Li, 0.99.

EXAMPLE 10 Synthesis of 5- (1, 1, 2,2-tetrafluoro-2-bromoe toxy) dimethyl isofatlate A solution of 70.5 g of 95% potassium methoxide (0.956 mol) in 500 ml of dry methanol is added to the suspension of 200.97 g (0.956 mol) of 5-hydroxyisophthalate or of dimethyl in 400 ml of dry methanol cooled to 0-5 ° C. The mixture is allowed to warm to room temperature and decanted from * ^^ .. ^ ¿^ A ^ ~. ^ Fc- * - "a small amount of a white solid. The methanol solution is concentrated in an evaporated]: rotary and the solid is dried at 150 ° C and 0.1 mm to yield 226.4 g. This salt is dissolved in 600 ml of dry DMSO and heated to 65 ° C. 1, 2-dibromothetlufluoroethane (259.8 g, 1 mol) is added dropwise resulting in an exotherm at 80 ° C. After the addition is complete, the mixture is maintained at 75-85 ° C for 4 hours. This is cooled to room temperature and diluted in 2L with ice water. The aqueous solution is decanted from a viscous gum and extracted with 200 ml of methylene chloride. The methylene chloride extract is concentrated and the residue combined with the viscous gum and washed with water. The organic material is taken up in methylene chloride, dried over anhydrous sodium sulfate and concentrated in a rotary evaporator. The residue is distilled in a Kugeirohr apparatus at 140 ° C and 0.2 mm to provide 257.6 g of a material which is 93% purified by glpc. Chromatography on silica gel, elute with hexane and then 1 -, < -4% ethyl acetate in hexane gives the desired product in the first fractions. The combined fractions are concentrated on a rotary evaporator and the residue is distilled in a Kugeirohr at 125 ° C and 0.1 mm to provide 239.6 g (62%) of the title product. A NMR (d, CDC13) 3.98 (s, 6H), 8.05 (m, 2H), 8.60 (m, 1H); 19 F NMR (d, CDC13) -68.7 (2F), -86.4 (2F). Anal Cale. for C? 2H9F4Br05: C, 37.04; H, 2.33; F, 19.53; Br, 20.54. Found: C, 36.95; H, 2.08; F, 19.34; Br, 20.57.

EXAMPLE 11 Synthesis of 3, 5-di (CQ2CH3) - Ph-0CF2CF2S02C1 To a 5 L round bottom flask is charged with 109.2 g of sodium bicarbonate, 600 ml of deionized water, 226.4 g of sodium dithionite and 300 ml of DMF. The mixture is heated to 65 ° C and 5- (1, 1, 2, 2-t and rafluoride-2-bromo-ethoxy) isoft alat or dimethyl (316.2 g, 0.81 mol) is added in about 15 minutes. After the addition is complete, the mixture is heated to 80-85 ° C for 4 hours and then kept at 50 ° C overnight. The mixture is cooled to room temperature and filtered. The solid is washed with ethyl acetate which is added to the filtrate. The lower aqueous layer is extracted with 2 X 100 ml of methylene chloride and 2 X 100 ml of ethyl acetate. All the organic layers are combined, washed with 3 X 50 ml of brine, dried over anhydrous sodium sulfate and concentrated in a rotary evaporator. The residue is dried at 120 ° C and 0.1 mm to provide an orange-yellow solid which is used in the next step without further purification. A NMR (d, DMSO-d6) 3.95 (s, 6H), 7.97 (m, 2H), 8.40 (m, 1H); 19 F NMR (d, CDCl 3) -80.9 (2F), 131.3 (2F). This solid is dissolved in 1 L of deionized water and 300 ml of CFC-113 are added. The flask is adjusted with the dry ice condenser. The chlorine gas is bubbled into the mixture until an excess is present. A formed precipitate which is not completely soluble in CFC-113 is added in 500 ml of methylene chloride. The excess chlorine is vented inside a scrubber, the organic layer is separated and the aqueous layer is extracted with 3 X 250 ml of methylene chloride. The combined organic layers are washed with 100 ml of brine, dried over anhydrous sodium sulfate, concentrated in a rotary evaporator and distilled using a Kugeirohr at 150 ° C and 0.2 mm to yield 277.3 g of a weakly yellow solid. This material is recrystallized from CFC-113 to provide in three crops, 257.4 g (78%) of a white solid. A NMR (d, CDC13) 3.95 (s, 6H), 8.10 (m, 2H), 8.70 (m, 1H); 19 F NMR (d, CDC13) -79.0 (2F), -108.0 (2F). Anal Cale, for C12H9C1 F407S: C, 35.26; H, 2.22; Cl, 8.67; F, 18.59, S, 7.84. Finding: C, 35.39; H, 2.05; Cl, 8.95; F, 18.29; S, 7.66.

EXAMPLE 12 Synthesis of 3, 5-di (CQ2CH3) - Ph-OCF2CF2S02Li To a suspension of 262 g (0.64 mol) of 3,5-di (C02CH3) -Ph-0CF2CF2S02C1 in 1 L of anhydrous methanol are added 52.1 g (0.71 g). mol) of anhydrous lithium carbonate. This mixture is heated to 40 ° C, then allowed to stir at room temperature for 96 hours. The solution is filtered and concentrated in a rotary evaporator. The solid is recrystallized from 6L acetonitrile, two cultures are collected. The combined solid is dried at 180 ° C and 0.1 mm to provide 179.1 g (71%) of the product. 1 H NMR (d, DMSO-d 6) 3.95 (s, 6H), 7.95 (m, 2H), 8.40 (m, 1H); 19 F NMR (d, CDC13) -80.9 (2F), 116.5 (2F). Anal Cale, for C? 2H9F4S08Li: C, 36.38; H, 2.29; F, 19.18, S, 8.24; Li 1.75. Finding: C, 36.29; H, 2.47; F, 19.08; S, 8.24; Li: 1.69.

EXAMPLE 13 Homopolymerization of lithium 2- (4-e-thi-1-phenoxy) tet-rafluoroethanesulfonate 2- (4-ethenophenoxy) -tetrafluoroethanesulfonate (12.24 g, 0.04 mol) is dissolved in 75 ml of deionized water. This solution is concentrated under vacuum to remove about 60 ml of water in addition to remove any remaining traces of organic solvent complexes for the salt. Deionized water (40 ml) is added to the residue and its solution is deoxygenated by two cycles of freezing, evacuation, and liquefaction. Ammonium persulfate (0.018 g, 0.00008 mol) is added and the solution is reoxygenated by freezing, evacuated and liquefied cycles. The solution under an argon atmosphere is then heated in an oil bath at 61-63 ° C for 26 hours. The solution is cooled to room temperature and transferred to a blocking dialysis tube of 3500 MW and dialyzed against three IL loads of deionized water over several days. The aqueous solution in the dialysis tube is concentrated in a rotary evaporator and the residue is dried at 100 ° C and 0.1 mm to yield 9.33 g (76%) of a weakly yellow solid polymer. H NMR (d, D20) 1.50 (bs, 3H), 6.5 and 7.0 (bs, 5H); 19, NMR (d, D20) -82.02 (2F), -117.58 (2F). Mw, determined by the light scattering in water containing 0.25% LiCl, is measured to be 156,000. Anal Cale, for Ci0H7O4 F4SLi »l .67 H20: C, 35.73; H, 3.08; F, 22.61; Li, 2.06; S, 9.54. Finding: C, 35.72; H, 3.17; F, 19.43; Li, 2.27; S, 10.03. A film of the polymer is fused with water followed by drying with air is amber light and is freestanding but somewhat fragile.

EXAMPLE 14 Copolymerization of 2- (4- et eni 1 phenoxy) tet rafluoroethanesulphonate of lithium and styrene A polymer tube is charged with 4.59 g (0.015 mol) of 2- (4-ethene-1-phenoxy) -ethenefluoroethanesulfonate. lithium, 8.0 ml of DMF, 8.84 g (0.085 mol) of freshly purified styrene and 0.05 g of benzoyl peroxide. The solution is frozen, evacuated, purged with argon and liquefied several times and then heated under an argon atmosphere in an oil bath at 60 ° C for 66 hours. After cooling to room temperature, the solid mass is dissolved in 50 ml of DMF and precipitated in excess ether. The ether is decanted and the gummy residue is washed with hexane and dried at 100 ° C and 0.5 mm to produce 11. 8 g (88%) of a white copolymer. A colorless, clear film can be formed from a mixture of THF with 2% DMF. A NMR (d, DMF-d7) 1.65 and 2.0 (broad), 6.8 and 7.2 (broad); 19 F NMR (d, DMF-d7) - 80.9 (2F), -116.4 (2F). 13C NMR (d, DMF-d7) 118.3 and 114.09 (of CF2), 147.77 (aromatic C close to O), 146.05 (aromatic C close to CH2) 122.09 (C aromatic ortho to O), 128.7-128.2 (C aromatic remaining ), 40.97 (CH) and 42-48 (CH2). From the integration of the appropriate resonances in the unbound 13C spectrum F and H, he calculates that the polymer contains 88% styrene and 12% functionalized styrene. DSC shows a Tg at 135.8 ° C in the second heating. Anal. Found: c, 71.52; H, 5.81; F, 8.76; Li, 0.72; EXAMPLE 15 Thermopolymerization of 2- (4-ethylhexyphenoxy) tet lithium furan fluoride with styrene and acrylonitrile Styrene and acrylonitrile are passed through short columns of basic alumina and then distilled from calcium hydride immediately before use. A polymer tube is charged with 3.06 g (0.011 mol) of 2 (4-ethenylphenoxy) tet raf luoroet anosul fonato lithium and 8 ml of DMF. The solution is placed under vacuum for 1 hour at room temperature and the volatile impurities. Then 5.41 g (0.052 mol) of styrene, 2.01 g (0.038 mol) of acetonitrile and 0.048 g of benzoyl peroxide are added. The solution is frozen, evacuated, purged with argon and liquefied several times and then heated under an argon atmosphere in an oil bath at 60 ° C for 22 hours. After cooling to room temperature, the solid mass is dissolved in DMF, filtered and slowly poured into excess ether. The sticky precipitate is dried under vacuum at 95 ° C to yield 10.7 g of a white polymer. 1H NMR (d, THF-d8) 1.70-2.2 (broad), 6.8 and 7.05 (broad) and 2.0 (broad); 19 F NMR (d, THF-d8) -81.5 (2F), -117.2 (2F): IR 2237 cm_1 (CN). 13C NMR (d, DMF-d7) 118.3 and 114.09 (of CF2), 122.08 (aromatic carbon ortho to 0 and CN of acetonitrile), 147.77 (aromatic carbon adjacent to 0) 146.0 to 140 (quaternary carbons), 128.4-127.1 ( Remaining aromatic carbons), 38.83 (aliphatic styrene CH) 28.5 to 26.6 (aliphatic acetonitrile CH) and 43 to 40 (CH2). From the carbon integration of the NMR spectrum, the polymer is calculated and contains 52.2 mol% of styrene, 38.8 mol% of acrylonitrile and 9.0 mol% of lithium trifluoroethanesulfonate 2- (4-ethenyl phenoxy) tet. Anal. Found C, 69.03; H, 6.00; N, 6.37; F, 6.59; S, 2.95; Li, 0.52.

EXAMPLE 16 Thermopolymerization of 2- (4 et eni 1 phenoxy) tet raf luoroet anosul fonate lithium with styrene and butyl acrylate The procedure of example 15 is followed using 3.06 g (0.01 mol) of 2- (4-et eni 1 phenoxy) tet raf luoroet lithium anosulfonate, 6.55 g (0.063 mol) of styrene and 3.46 g (0.027 mol) of butyl acrylate. The crude product is dissolved in DMF, precipitated by the addition of an excess of ice water in a mixer. After drying in a vacuum around 50 ° C, 7.10 g of a polymer are obtained. A NMR (d, DMF-d7) 1.05 (broad), 1.3-2.6 (broad), 3.8 (broad), 6.95 and 7.40 (broad); 19 F NMR (d, DMF-d7) -81.0 (2F), -116.6 (2F). 13C NMR (d, DMF-d7) 118.4 and 114.1 (of CF2), 122.2 (aromatic carbon ortho to O), 148.5 (aromatic carbon adjacent to O) 143.0 to 146.9 (quaternary carbons) 125.0 to 130.0 (remaining aromatic carbons), 38.85 (aliphatic styrene CH), 42 to 48 (styrene CH2), 175. S (carbonyl ester), 64.06 (OCH2), 14.06 (CH3), 19.75 and 13.03 (of ester CH2 remnants). From the integration of the carbon NMR spectrum, the calculated polymer contains 66.4 mol% of styrene, 26.5 mol% of butyl acrylate and 7.1% of 2- (4- et eni 1 phenoxy) tet lithium trifluoroethanesulfonate.

EXAMPLE 17 Copolymerization of 2- (4-etheno-1-phenoxy) tet raf luoroet anosul-fonate of lithium and methyl methacrylate The methyl methacrylate is passed through a short column of basic alumina and distilled under vacuum in a cooled vessel. with dry ice. A polymer tube is charged with 3.06 g (0.01 mol) of 2- (4- et eni-1-phenoxy) tet raf luoroet anosul fonate lithium, 9.0 g (0.09 mol) of freshly purified methyl methacrylate and 0.05 g of initiator 2 , 4-d? Methyl-2, 2 '-azobis (pentanit ri lo) (Vazo® 52).

The solution is frozen, evacuated, purged with argon and liquefied several times. The polymer tube is sealed and heated in an oil bath at 50 ° C for 22 hours. After cooling to room temperature, the solid mass is dissolved in 250 ml of acetone with heating and filtration. The acetone is evaporated and the solid polymer is dried at 100 ° C and 0.05 mm to provide 11.6 g of the product. 1 H NMR (d, acetone d-6) 0.6-3.0 (m), 3.65 (s), 6.8-7.5 (m). For the integration of the appropriate peaks, the polymer contains 88 mol% of methyl methacrylate and 12 mol% of lithium 2- (4- et eni 1 phenoxy) tetrafluoroethanesulfonate. 19 F NMR (d, acetone d6) -80.9 (2F), -116.6 (2F). Anal. Found. C, 54.39; H, 6.77; F, 4.86; Li, 0.50; S, 2.62. A flexible and clear film of the polymer can be formed from the acetone solution. EXAMPLE 18 Copolymerization of lithium and acrylonitrile 2- (4-ethene-1-phenoxy) -tetrafluoroethanesulfonate Acrylonitrile is passed through a short column of basic alumina and distilled under vacuum immediately before use. A 50 ml polymer tube is charged with 3.06 g (0.01 mol) of lithium 2- (4-ethenylphenoxy) tetrafluoruroethanesulfonate, 10 ml of DMF, 4.77 g (0.09 mol) of acrylonitrile and 0.050 g of a 2-initiator. , 4-dimet il-2, 2 '-a zobis (pentanonityl) (Vazo® 52). The contents of the container are deoxygenated by four cycles of freezing / evacuated / liquefied and the container is sealed. The contents are heated in an oil bath at 50 ° C for 22 hours resulting in the formation of a white mass. The solid is dissolved in 50 ml of DMF, filtered and precipitated in a large excess of ether. After they are dried at 100 ° C and 0.05 mm, 7.59 g (97%) of a white polymer is isolated. A NMR (d, DMF-d7) 2.30 (b), 3.32 (b), 7.3-7.5 (b) more absorptions require small amounts of DMF. By the integration of the aromatic peaks against the peaks of the aliphatics, the calculation of the polymer shows that it contains 12 mol% of 2- (4- ^^ ai ^ ethenylphenoxy) lithium tetrafluoroethanesulfonate and 88 mol% acrylonitrile. Anal. Found: C, 54.72; H, 4.51; N, 15.55; F, 8.36; Li, 0.81; S, 4.04.

EXAMPLE 19 Copolymerization of 2- (4-et-1-phenoxy) tet of lithium fluoroetanesulphonate and α-methylene-β-butyrolactone A polymer tube is charged with 1.53 g (0.005 mol) of 2- (4-ethyl) phenoxy) tet rafluoroet lithium anosulfonate, 4.4 g (0.045 mol) of a-methylene-γ-butyrolactone and 0.025 g of Vazo® 52. The salt dissolves almost completely with stirring. DMF (100 μL) is added to produce a completely homogeneous solution. The contents of the vessel are deoxygenated by 5 cycles of freezing, evacuation / liquefied and the solution is heated for 22 hours at 50 ° C under an argon atmosphere to provide a solid yellow mass. This material is dissolved in 30 ml of DMF with heating, filtering and precipitating for an excess of ether. Dry at 109 ° C and 0.1 mm to yield 5.24 g (88%) of a white polymer. A NMR (d, DMF-d7) 2.25 (b), 2.5 (b), 7.3-7.5 (b). From the integral peaks, the composition of the polymer is calculated to be 11 mol% of lithium 2- (4-ethenylphenoxy) tetrafluoroethanesulfonate. 19 F NMR (d, DMF-d7) -80.61 (2F), -116.31 (2F). DSC: Tg = 220 ° C. Anal. Found. C, 53.40; H, 5.53; F, 6.11; Li, 0.54; S, 2.75.

EXAMPLE 20 Copolymerization of 2- (4- e dye-1-phenoxy) tet of lithium fluoroetanesulphonate with ethyl ether methacrylate of poly (ethylene glycol). In a handling box with gloves combine 1.21 g (0.00395 mol) of 2- (4- et eni 1 phenoxy) -tet raf luoroet lithium anosulfonate and 8.79 g (0.0357 mol) of ethyl ether poly (ethylene glycol) methacrylate in a Schlenk tube. Then 48 mg (1.93 X 10"4 mol) of Vazo® 52 is added and stirred until dissolved The flask is heated under an argon atmosphere at 40 ° C for 28 hours The resulting polymer is flexible and rubbery, but insoluble and not prensable. More likely, difunctional methacrylate occurs and results in a degradable material. The polymer is dried at 70 ° C under vacuum and 9.7 g (97%) of the recovered material. Movies are not obtained.

EXAMPLE 21 Copolymerization of 2- (4-et-1-phenoxy) tet raf luoroet anosul fonate lithium with butyl acrylate In a handling box with gloves combine 2.10 g (0.0069 mol) of 2- (4-eti-1) phenoxy) tet raf luoroet anosul fonato lithium and 8.0 g (0.062 mol) of butyl acrylate in a Schlenk tube with a stir bar. Approximately 10 ml of DMF are added, followed by 48 mg (1.93 X 10"4 mol) of Vazo® 52 and stirred until dissolved The flask is placed under an argon atmosphere and heated at 40 ° C for 24 hours. The resulting polymer is dissolved in DMF, precipitated as an oil in hexane (3x) .The polymer is then dissolved in acetone and «Mfe '-6feJ¿jfc jt-aE precipitates in water (2x). The resulting polymer is dried under vacuum at 75 ° C, to produce 1.6 g (16%) of product. 19 F NMR (d-acetone) -82.4 (2F), 118.0 (2F) ppm. TGA (N2, 10 ° C / min): the beginning of the decomposition is at 250 ° C. Molecular weight (SEC, Zytel 101 standard, solvent HFIP + 0.01 V sodium triflate): Mn = 186,800; Mw = 324,700; Mw / Mn = 1.74; Mn = 182,500; Mw = 316,800; Mw / Mn = 1.74.

EXAMPLE 22 Copolymerization of 2- (4-et en 1-phenoxy) tet raf luoroet anosul fonate lithium with ethylhexyl acrylate. In a glove box, 1.56 g (0.0051 mole) of 2- (4-ene-en-1-phenoxy) is dissolved in 20 ml of DMF and added to 8.44 g (0.046 mol) of lithium acrylate. ethylhexyl in a Schlenk tube with a stir bar, followed by the addition of 48 mg (1.93 X 10"4 mol) of Vazo® 52. The initiator is stirred until dissolved, the flask is placed under an argon atmosphere and heated at 40 ° C for 24 hours The resulting polymer is dissolved with additional THF and precipitated in water, followed by THF precipitations with an oil in hexane (3x) The polymer is dried under vacuum at 65 ° C to produce 3.2 g (32%) of the product.The films will be melt compressed by placing the polymer between the Teflon® pressure sheets, preheating 2 minutes at 150 ° C, at a pressure of 2000 lbs / in2, and then cooling under pressure. The polymer quickly absorbs moisture from the air and becomes a rubber. n be in the solution form by dissolving 0.5 g of the polymer in 15 ml of THF and melting the solution in a Teflon® petri dish of 5.5 cm in diameter. 19 F NMR (d-acetone) d: -84.4 (2F), -120.0 (2F) ppm. A NMR (d-THF) d: 7.1 (b), 3.95 (b), 3.8 (b), 2.9-2.3 (b), 1.8-2 (b), 1.5-1.7 (b), 1.4, 1.2 (b) ), 0.9 ppm. The ratio of the styrene signal to a methyl signal of the ethylhexyl acrylate indicates approximately 10 mol% of incorporation of lithium 2- (4-ethenylphenoxy) tetrafluoroethanesulfonate. 13C NMR (d-THF) d: 172.4, 127.4, 120.3, 40.1, 37.4, 28.9, 27.5, 22.7, 12.1, 8.2 ppm. TGA (N2 10 ° C / min): the initiation of the decomposition is at 250 ° C. DSC (N2, -100 at 200 ° C, 10 ° C / min): Tm not detected. Anal. Found:% C 65.62, 65.51; % H 9.48, 9.69; % F 3.82; % Li 0.34; % S 1.86. Molecular weight (SEC, Zytel 101 standard, solvent HFIP + 0.01M sodium triflate); Mn = 161,500, Mw = 315,000, Mw / Mn = 1.95; Mn = 140,300, Mw = 318,100, Mw / Mn = 2.27.

EXAMPLE 23 Copolymerization of 2- (4-ethynylphenoxy) tet raf 1'uorcyosulphonate of lithium with butyl acrylate and carbonate glycide metocarbonate Carbonate glycidal methacrylate (1.23 g, 0.0066 mol), butyl acrylate (6.76 g, 0.0528 mol), and 2- (4-et en 1-phenoxy) tet fluoroethanesulphonate lithium (2.02 g, 0.0066 mol) are combined in a flask in a glove box. Vazo® 52 (45 mg, 1.8 X 10 ~ 4 mol) is added with stirring until dissolved. The flask is placed under an argon atmosphere and heated at 45 ° C for 24 hours. The resulting polymer is insoluble in a variety of solvents and can not be pressed into a film. The polymer is dried under vacuum at 65 ° C to produce 9.4 g (94%) of the polymer.

EXAMPLE 24 Copolymerization of 2- (4 et enylphenoxy) tet raf luoroet anosul fonate de litic with butyl acrylate In a glove box, 2.10 g (0.0069 mol) of lithium 2- (4- ethenylphenoxy) tetrafluoroethanesulfonate and 7.9 g (0.062 mol) of butyl acrylate are combined in a Schlenk tube with a stir bar, followed by the addition of 45 mg (1.81 X 10 ~ 4 mol) of Vazo® 52 is stirred until dissolved. The flask is placed under an argon atmosphere and heated at 40 ° C for 24 hours, and 45 ° C for 24 hours. The resulting polymer is dissolved in THF, precipitated in water (2x) and hexane (2x) as an oil. The polymer is dried under vacuum to provide 0.2 g (2% yield) of the polymer. 13C NMR (d-THF) d: 175.1, 67.5, 64.9, 42. 6, 31.8, 25.8, 20.2, 14.3 ppm. TGA (N2, ° C / min): the initiation of the decomposition is at 250 ° C.

EXAMPLE 25 Copolymerization of Lithium 2- (4-ethenylphenoxy) -tetrafluoroethanesulfonate and butyl acrylate In a glove box, 3.74 g (0.0122 mol) of lithium 2- (4-ethenylphenoxy) tetrafluoroethanesulfonate and 6.26 g (0.0489 mol) are combined. ) of butyl acrylate in ur Schlenk tube with a stir bar, followed by the addition of 45 mg (1.81 X 10"4 mol) of Vazo® 52 and stirring until dissolved. The flask is placed under an argon atmosphere and is heated at 45 ° C for 24 hours The resulting polymer is dissolved in acetone / THF and precipitated in water The polymer is then precipitated from acetone / THF in hexane (2x) The polymer is dried to obtain 4.8 g ( 48%) Can films be formed by dissolving 0.5? The polymer was dissolved in THF and the solution melted in a Teflon® petri dish of 5.5 cm in diameter. 19 F NMR (d-acetone) d: -82.4 (2F), -118.1 (2F) ppm 13C NMR (d-acetone) d: 175.5, 130.3, 123.1, 65.3, 42.8, 36.6 (b), 31.9, 20.3, 14.5 ppm. A NMF (d-acetone) d: 7.1 (b), 4.1, 3.9 (b), 3.2, 3.1, 2.4, 1.9-1.2, 0.9 ppm. Anal. Found% C 54.34, 54.29; % H 6.95, 6.91; % F 9.46, 9.31; % Li 0.71, 0.80; % S 4.40, 4.47 TGA (N2, 10 ° C / min): the initiation of the decomposition is at 275 ° C, DSC (N2, -100 at 225 ° C, 10 ° C / min): Tm is not detected. Molecular weight (SEC, Zytel 101 standard, HFIP + 0.01 M sodium triflate): Mn = 432,000, Mw = 1,271,000, Mw / Mn = 2.94, Mn = 980,700, Mw = 1,415,000, Mw / Mn = 1.44.

EXAMPLE 26 Copolymerization of 2- (4-eti-1-phenoxy) -tetra fluoroethanesulphonate of lithium and methyl acrylate In a handling box with gloves, 2.8 g (0.0091 mol) of 2- (4-ethenophenoxy) are combined. tet raf lithium lithosilane sulfonate and • * - nf > - To 7.2 g (0.0827 mol) of methyl acrylate in a Schlenk flask with a stir bar, followed by the addition of 35 mg (1.41 X 10"4 mol) of Vazo® 52 and stir until dissolved. Place under an argon atmosphere and heat at 35 ° C for 48 hours, followed by 65 ° C for 24 hours.The separate polymerization phase.The polymer portions are hardened to dissolve these others, and some insolubles are present. The resulting polymer is dissolved in DMF / acetone and precipitated in hexane (2x) .The polymer is then dissolved in DMF and dialyzed in a dialysis pipe (MWCO = 3500) with water for 10 days, followed by the polymer collection, it is dissolved in DMF, and precipitated in water The polymer is dried under vacuum to yield 3.14 g (31.4%) of the product 19 F NMR (d-DMF) d: -81.9 (2F), -117.6 (2F) ppm.

EXAMPLE 27 Copolymerization of lithium methyl acrylate 2- (4-et en 1-phenoxy) tetra-fluoroethanesulfonate fonate -j,, < na? »& afetnft .. "'wJ <M? jjB In a handling box with gloves combine 2.8 g (0.0091 mol) of lithium 2- (4-ethenyl phenoxy) -tetrafluoroethanesulfonate, 7.2 g (0.082" mol) of methyl acrylate and 20 ml of DMF in Ur Schlenk tube with a stir bar, followed by the addition of 35 mg (1.41 X 10"4 mol) of Vazo® 52. The contents of the flask are stirred, to dissolve. The flask is placed under an argon atmosphere and heated at 35 ° C for 48 hours.The resulting polymer is dissolved in DMF / acetone and precipitated in water (3x) .The polymer is then dissolved in acetone and precipitated in water. The final polymer is dried under vacuum at 70 ° C to produce 4.85 g (48.5%) of the product.The films are formed by dissolving 0.54 g of the polymer in acetone and melting the solution in a Teflon® petri dish of 5.5 cm in diameter 19 F NMR (d-acetone) d: -82.4 (2F), 118.1 (2F) ppm iJC NMR (d-acetone) d: 174.9, 129.2, 12.1, 51.2, 41.3, 35.1 (b) ppm. H NMR (d-acetone) d: 7.2 (b), 3.6, 2.9, 2.8, 2.1, 3.5, 2.4 (b), 1.9 (b), 1.7 (b), 1.7-1.5 (b) ppm. The proton NMR indicates 4 mol percent of ionomeric groups based on the integration of an aromatic signal and a methyl group of methyl acrylate signal. Molecular weight (SEC, Zytel 101 standard, HFIP + 0.1 M sodium triflate): Mn = 77,200, Mw = 216,100, Mw / Mn = 2.8; Mn = 56,500, Mw 203,600, Mw / Mn = 3.6. Anal. Found:% C 53.16, 53.13, 52.78; % H 6.77, 6.79, 6.36; % F 3.24, 3.07, 4.81; % Li 0.28, 0.47, 0.38; % S 1.91, 1.98, 2.39. Elemental analysis indicates 5-6 percent in mol of present 2- (4-ethenylphenoxy) tetraf luoroet anosul fonate.

EXAMPLE 28 Copolymerization and degradation of 1-thio-2- (4-etheno-phenoxy) -tetrafluoroethanesulfonate, methylmethacrylate, trimethylolpropanetriacrylate Degradable methylmethacrylate and 2 - (4-etheno-1-phenoxy) tertiary fluoroethanesulphonate films are manufactured as follows. Methylmethacrylate (7.5 g, 7.5 X 10"2 moles) and a sulfonate monomer (2.5 g), 8.2 X 10 ~ 3 mol) sor preme zclados. Film A: An aliquot of 3.33 g of the monomer mixture is placed in a small flask, 0.041 g (0.00014 mol) of triacrylate and 20-24 mg of Vazo® 52 initiator are added and stirred until dissolved. The mixture is poured into a small dish of Teflon® melting and heated on a hot plate under a nitrogen atmosphere. Film B: An aliquot of 3.33 g of the monomer mixture is added to 0.16 g (0.00054 mol) of triacrylate and 20-24 mg of the Vazo® 52 initiator in a small flask and stirred until dissolved. The mixture is poured into a small Teflon® casting plate and heated in a hot plate under a nitrogen atmosphere. Film C: An aliquot of 3.22 g of the monomer mixture is added to 0.41 g (0.0014 mol) of triacrylate and 20-24 mg of the Vazo® 52 initiator in a small bottle and stirred until dissolved. The mixture is poured into a small Teflon® casting pan and heated on a hot plate under a nitrogen atmosphere. After 30 minutes, the temperature of the hot plate rises to 49.6 ° C and it appears that polymerization occurs very rapidly. Bubbles and cracks form in films B and C. The heat is reduced and no additional bubbling or cracking is observed. The films are heated for 4 hours, left at room temperature overnight, then heated at 45 ° C for 3 hours. The resulting films are inflated in acetone but do not dissolve and can not be pressed by fusion. The films are dried under vacuum at 70 ° C. TGA (N2, 10 ° C / min): the initiation of the decomposition is at 260 ° C (A and B), 300 ° C (C).

EXAMPLE 29 Copol ime ri cation and degradation of 2- (4-et en 1-phenoxy) tet raf luoroet lithium anosulfonate, ethyl ether methacrylate of poly (et i lengl i col) and poly (ethylene glycol) diacrylate. The degradable films of polyethylene glycol ethyl ether methacrylate and lithium 2- (4-ethenylphenoxy) tetrafluoroethanesulfonate are manufactured in the following manner. The ethyl ether methacrylate of poly (ethylene glycol) (8.79 g, 3.6 X 10"2 mol) and the sulfonate monomer (1.21 g, 4.0 X 10" 3 mol) are premixed. Film A: An aliquot of 3.33 g of the monomer mixture is placed in a small vial with 0.038 g (6.6 X 10"5 mol) of poly (ethylene glycol) diacrylate and 16 mg (6.45 X 10" 5 mol) of Vazo® 52 and stir until dissolved. The mixture is poured into a small Teflon® casting plate and heated between 35-40 ° C on a hot plate under a nitrogen atmosphere for five hours. Film B: An aliquot of 3.33 g of the monomer mixture is placed in a small vial with 0.076 g (1.32 X 10 ~ 4 mol) of poly (ethylene glycol) diacrylate and 16 mg (6.45 X 10"5 mol) of Vazo® 52 and stirred until dissolved The mixture is poured into a small Teflon® casting plate and heated to between 35-40 ° C on a hot plate under a nitrogen atmosphere for five hours Film C: An aliquot of 3.15 g of the monomer mixture is placed in a small bottle - - * - * -. & ** & with 0.15 g (2.61 X 10"4 mol) of poly (ethylene glycol) diacrylate and 16 mg (6.45 X 10" 5 mol) of Vazo® 52 and stir until dissolved. The mixture is poured into a small Teflon® casting plate and heated between 35-40 ° C on a hot plate under a nitrogen atmosphere for five hours. The films are left at room temperature overnight and then heated at 37 ° C for 6 hours. Some gelification of the films under heating are observed. The films are insoluble, soft, and flexible. The. Films are dried at 75 ° C under vacuum. Acetone is used to extract small portions of the. Diluent films fused to the plate are sent for 13C NMR and do not show a monomer signal. The acetone used to extract the if thick films from the casting plates shows some residual monomer. TGA (N2, 10 ° C / min): the initiation of decomposition is i 225 ° C (A, B) and 200 ° C (C). DSC (N2, -100 at 200 ° C, 10 ° C / min) Tm not detected. Anal. Found: Film A:% C 56.49; % H 8.17; % F 2.87; % S 0.74; ash 1.74; % Li 0.22. Film B:% C 56.45; % H 8.16; % F 2.33; % S 0.50; ash 1.83; % Li 0.23. Film C:% C 56.79; % H 8.24; % F 2.44; % S 0.57; ash 1.83; % Li 0.23.

EXAMPLE 30 Copolymerization and degradation of lithium 2- (4-ethenyl phenoxy) tetra-fluoroethanesulfonate, butylacrylate and carbonateglycide methacrylate In a glove box, 1.23 g (0.0066 mol) of methacrylate are combined carbonate glycolate, 6.76 g (0.0528 mol) of butyl acrylate and 2.02 g (0.0066 mol) of 2- (4-eti-1-phenoxy) tet raf luoroetanosul-fonate lithium are combined in a small flask. Vazo® 52 is added (40 mg, 1.61 X 10 ~ 4 mol) and stirred until dissolved. The solution is pipetted into two small Teflon® petri dishes to adjust the bottom cover. The remaining solution is pipetted into cells in a piece coated with Teflon® glass. The solutions are heated to 35 ° C in a slide heater in the glove box for 2 hours, are left to ~ «.fr a'?¡ ... L ...

At room temperature overnight, it is heated at 35 ° C for 8 hours, cooled to room temperature overnight and then heated at 42 ° C for 8 hours. Hygroscopic films are fragile when they are dry, but manageable when they are wet 19, NMR (d-acetone) d: -82.7 (2F), -118.5 (2F) ppm. TGA (N2, 10 ° C / min): the initiation of the decomposition is at 200 ° C. DSC (N2, -100 at 175 ° C, 10 ° C / min): Tm not detected. Anal. Found:% C 50.64, 50.49, 50.66; % H 5.62, 5.58, 5.61; % F 9.84, 9.43, 9.24; % L i 0.38, 0.90, 0.84; % S 4.38, 3.83, 4.09; % N 0.22, 0.18.

EXAMPLE 31 Copolymerization and degradation of 2- (4-etheno-1-phenoxy) tet of lithium fluoroetanesulphonate and polyethylene glycol ethyl methacrylate In a glove box, 8.79 g (0.0357 mol) of ethyl ether are combined Poly (ethylene glycol) methacrylate, 1.21 g (0.00395 mol) of 2- (4-et eni 1 phenoxy) is charged with fluoroethanesulphonate of lithium, and 45 mg (1.81 X 10"4 mol) of Vazo® 52. The solution is pipetted into two small Teflon petri dishes ® to adjust the bottom cover, and the rest is pipetted into boxes on a piece of glass coated with Teflon®.The films are heated to 35 ° C in a heater slide for 4 hours, they are left at room temperature throughout the night, and then heated to 35 ° C for 8 hours.The phase-separated films in the polymerization provide flexible films that are crystalline in appearance with granular inclusions.These phases are insoluble in THF.TGA (N2, 10 ° C / min): the initiation of decomposition is at 225 ° C. DSC (N2, -100 at 175 ° C, 10 ° C / min), TB is not detected Anal Found:% C 56.58, 56.33;% H 8.34 , 8.33;% F 2.78, 2.63;% S 1.27, 1.30;% Li 0.23, 0.23 Elemental analysis indicates approximately 8 percent by mole of monomer 1 incorporated.

Inata EXAMPLE 32 Copolymerization and degradation of 2- (4-ethenophenoxy) tet rafluoroethanesulphonate lithium and ethyl ether methacrylate poly (ethylene glycol) Ethylether methacrylate poly (ethylene glycol) (7.63 g, 0.31 mol) and 2 - (4-et eni 1 phenoxy) tet raf luoroet anosul fonato lithium (2.37 g, 0.0077 ml) are combined with 45 mg (1.81 X 10 ~ 4 mol) of Vazo® 52 in a small bottle in the handling box with gloves The solution is pipetted into two small Teflon® petri dishes to adjust the bottom, and the rest is pipetted into boxes on a piece of glass coated with Tefion®. The films are heated to 35 ° C in a slide heater for 4 hours, left at room temperature overnight, and then heated at 35 ° C for 8 hours. In the polymerization of the separated phase films. Flexible films appear flexible with granular inclusions. Both phases are insoluble in THF. TGA (N2, 10 ° C / min): the initiation of the decomposition is at 225 ° C. DSC (N2, -100 at 200 ° C, 10 ° C / min): Tm not detected.

Anal. Found:% C 53.85, 53.92; % H 7.55, 7.51; % F 5.00, 5.20; % S 2.36, 2.21; % L i 0.47, 0.46.

EXAMPLE 33 Copolymerization and degradation of lithium 2- (4-ethenyl phenoxy) tetraf luoroethanesulfonate and poly (ethylene glycol) methacrylate In a glove box 8.79 g (0.0357 mol) of polyethylene methacrylate ether are combined. ethylene glycol) and 1.21 g (0.00395 mol) of 2- (4-et eni-1-phenoxy) tet rafluoroet anosul fonato lithium with 45 mg (1.81 X 10"4 mol) of Vazo® 52. The solution is pipetted into two small Petri dishes of Teflon® for adjust the bottom, and the rest is pipetted into boxes on a piece of Teflon®-coated glass.

° C in a heater slidable for 5 hours, left at room temperature overnight, and then heated at 45 ° C for 8 hours.

Some of the films of separate phases with other homogeneous remnants.

EXAMPLE 34 Copolymerization of N- (trifluoro-ethanesulfonyl) -2- (4-et-en-1-phenoxy) -ethe-fluoro-lithium-fonimide of lithium and methyl methacrylate The procedure of example 17 is still using 4.36 g of N- (trifluoromet anosul fonil) -2 - (4-et eni 1 phenoxy) tet raf luoroet lithium anosulfonimide in place of 2- (4-ethenyl phenoxy) tetra fluoroethanesulfonate lithium to provide 12.4 g of the polymer. 1H NMR (d, acetone D6) 0.6-3.1 (m), 3.65 (s), 6.9-7.7 (m). For the integration of the appropriate peaks, the polymer contains 88 mol% methyl methacrylate and 12 mol% monomer sulfonimide. 19 F NMR (d, acetone-d 6), -78.8 (s, 3 F), -79.7 (m, 2 F), -115.5 (s, 2 F). Anal. Found: C, 49.77; H, 6.06; N, 1.03; F, 9.93; S, 5.08; Li, 0.50.

EXAMPLE 35 Copolymerization of N- (Trifluoromethanesulfonyl) -2- (4-ethenylphenoxy) tetrafluoroethanesulfonimide lithium styrene The procedure of Example 14 is continued using 4.37 g (0.01 mol) of N- (trifluoromethanesulfonyl) -2- (4- et. eni 1 phenoxy) tet lithium rfluoroethanesulfonimide, 9.36 g (0.09 mol) of styrene, 8.0 ml of DMF and 0.048 g of bezoyl peroxide. The polymerization is conducted for 96 hours. The solid mass is dissolved in additional DMF and filtered. The polymer is precipitated in 1 L of ice water, filtered and dried at 96 ° C and 0.05 mm to yield 8.38 g. Anal. Found: C, 70.31; H, 6.07; N, 1.75; F, 8.69; S, 4.63; Li, 0.44.

EXAMPLE 36 Copo 1 Imaging of N- (tri fluoromethanesulfonyl) -2- (4-ethenylphenoxy) tet raf luoroethanesulfonimide lithium and methyl acrylate This is an assay to produce a blocked polymer by allowing methyl acrylate to polymerize to a material viscous and then add the ionomeric monomer In a glove box, 7.2 g (0.0827 mol) of methyl acrylate are dissolved in 10 ml of DMF and 35 mg (1.41 X 10 ~ 4 mol) of the Vazo® 52 initiator is added. The flask is heated to 35 ° C. . After one hour when the solution becomes very viscous, add 10 ml of additional DMF together with 2.8 g (0.0064 mol) of N- (trifluoromet anosul fonyl) -2- (4-et en 1-phenoxy) tet rafluoroet anosulfonimide in 10 ml of DMF. The heating is summarized at 35 ° C for 48 hours, 45 ° C for 24 hours, and 65 ° C for 24 hours. The resulting polymer is dissolved in DMF / acetone and precipitated in hexane (2x). The polymer is then dissolved in DMF and precipitated in water (2x). The polymer is dried under vacuum at 75 ° C to produce 5.6 g (56%) of the material. The films are obtained by dissolving 0.5 g of the polymer in DMF and melting the solution in a Petri dish of Teflon® of 5.5 cm. 19 F NMR (d-DMF) d, -79.8 (3F), -80.7 (2F), -116.5 (2F) ppm. 13 C NMR (CDC 13) d: 174.8 (C = 0), 51.7 (OCH 3), 41.2 (CH 2 CH), 35.3 (CH 2 CH). Only methyl acrylate signals were detected in the 13 C NMR. A NMR (CDCI3) d: 7.3, 3.6, 2.9, 2.8, 2.3, 1.9, 1.7, 1.5 (b) ppm. The aromatic ratio for the peak of OCH3 (MA) indicates the integration of 0.6 mol percent of the ionomeric groups. TGA (N2, 10 ° C / min): the initiation of the decomposition is at 300 ° C. DSC (N2, -100 at 200 ° C, 10 ° C / min): Tm, Tg = 12 ° C (1st heating), 17 ° C (20 heating) are not detected. Anal. Found:% C 54.24, 54.35; % H 6.89, 6.62; % N < 0.1, < 0.1; % F 1.02, 1.27; % Li 0.042, 0.058; % S 0.84, 0.83. Molecular weight (SEC, Zytel 101 standard, HFIP + 0.01 M sodium triflate): Mn = 124,100; Mw = 370,300; Mw / Mn = 2.98; Mn = 134,400; Mw = 380,300; Mw / Mn = 2.83.

EXAMPLE 37 Copolymerization of N- (tri fluoromethanesulfonyl) -2- (4-et en-1-phenoxy) tet raf luoroetanosul fonimide of lithium with butyl acrylate In a glove box are combined 2.75 g (0.0063 mol) of N- (trifluoromethanesulfonyl) -2- (4-et eni-1-phenoxy) te trao-fluoroethansulimide and 7.25 g ^^^ (0.057 mol) of butyl acrylate in a Schlenk tube with a stir bar, followed by the addition of 45 mg (1.81 X 10 ~ 4mol) of Vazo® 52 and stirred until dissolved. The flask is placed under an argon atmosphere and heated at 40 ° C for 24 hours, followed by 45 ° C for 24 hours. The resulting polymer is dissolved in THF, precipitated in water (2x). The polymer is then dissolved and precipitated in hexane (2x). The polymer is dried under vacuum to yield 2.4 g (24%) of the polymer. The film is formed by dissolving 0.5 g of the polymer in THF / acetone 1: 1 and melting the solution in a Teflon® petri dish of 5.5 cm in diameter. A small amount of undissolved gelled material is present. 19F NMR (d-THF) d: -80.4 (2F) -81.4 (2F) -117.2 (2F) ppm. 113JC, NMR (d-THF) d: 175. 130.1, 122.7, 64.9, 42.6, 36.1, 31.8, 20.2, 14.3 ppm. A NMR (d-THF) d: 7.1 (b), 4.0, 3.1, 2.0-3.0 (b), 1.1-1.8 '(b), 0.8 ppm. The ratio of the aromatic peak to the methyl peak of the butyl acrylate indicates approximately 15 mol% of the incorporated ionomer monomer. TGA (N2, 10 ° C / min): the initiation of the decomposition is at 275 ° C. DSC (N2, -100 at 250 ° C, 10 ° C / min): Tm is not detected. Anal. Found:% C 52.49, 54.24; % H 6.90, 6.84; % N 1.19, 1.19; % F 10.02, 9.83; % S 4.82, 4.93; % Li 0.48, 0.51. The elemental analysis indicates 12 mol% of incorporation in the ionic monomer. Molecular weight (SEC, Zytel 101 standard, HFIP + 0.01 M sodium triflate); Mn = 250,200, Mw = 1,024,000, Mw / Mn = 4.09; Mn = 203,700, Mw = 893, 100, Mw / Mn = 4.38.

EXAMPLE 38 Copolymerization degradation of 1 N- (trifluoromethanesulfonyl) -2- (4 et eni 1 phenoxy) tet raf luoroetanosul fonimide of lithium and ethyl ether methacrylate of poly (ethylene glycol) In a glove box are combined 1.64 g ( 0.00376 mol) of N- (trifluoromethanesulfonyl) -2- (4-ethenyl phenoxy) tetra fluoroethanesulfimide lithium and 8.36 g (0.02296 mol) of PEEGMA in a small flask with 5 ml of DMF. The Vazo® 52 (48 mg, 6.45 X 10"5 mol) are added and stirred until dissolved.

A portion of the solution is used to coat the bottom of a 5.5 cm Teflon® petri dish. The plate is heated in a sliding heater in the glove box at 39 ° C for 6 hours, allowed to settle at room temperature overnight, followed by heating at 40 ° C for 8 hours. The films are soft and flexible. TGA (N2, 10 ° C / min): the initiation of the decomposition is at 225 ° C. DSC (N2, 10 ° C / min): Tm is not detected. Anal. Found:% C 54.39; % H 7.57; % N 0.57; % F 3.87; % S 1.22; % Li 0.21; ash 1.64. The elemental analysis indicates approximately 9 mol% of the incorporation of the ionic monomer.

EXAMPLE 39 Copolymerization and degradation of N- (trifluoromethanesulfonyl) -2- (4-et en-1-phenoxy) tet raf luoroetanosul fonimide of lithium, ethyl ether methacrylate of poly (ethylene glycol) and diacrylate of poly (ethylene glycol). 8.36 g (0.03396 mol) of polyethylene glycol ethyl ether methacrylate, 1.64 g (0.00376 mol) of N- (t-rifluoromethanesulfonyl) -2- (4-ethenylphenoxy) tetrafluoroethanesulfonimide are combined in a glove box. of lithium, and 5 ml of DMF are combined in a small jar and shaken to mix. Three films of different amounts of degraders are manufactured as described below: Film 1: 4.33 g (3.33 g of monomers, 1 g DMF) of the monomer mixture is placed in a small vial with 0.036 g (6.26 X 10"5 mol ) of diacrylate Vazo® 52 (16 mg, 6.45 X 10"5 mol) is added and stirred until dissolved. The films are pipetted onto a piece coated with Teflon® glass and heated in a heater slidable at 39 ° C. Film 2: 4.33 g (3.33 g of monomers, 1 g DMF) of the monomer mixture are placed in a small vial with 0.071 g (1.24 X 10"4 mol) of diacrylate and 16 mg, (6.45 X 10" 5 mol ) of Vazo® 52 and stirred until the mixture. The films are pipetted onto a piece of glass coated with Teflon® and heated in a heater slidable at 39 ° C.

Film 3: approximately 3.8 of the mixture of the monomer / DMF 0.14 g (2.44 X 10"4 mol) of diacrylate and 16 mg, (6.45 X 10" 5 mol) of Vazo® 52 are placed in a small bottle and shaken to mingle. The films are formed as previously mentioned and heated in a heater slidable at 39 ° C.

The films are heated for 6 hours at 39 ° C, cooled to room temperature overnight, then heated 8 hours at 40 ° C. Flexible films are formed. TGA (N2, 10 ° C / min): the initiation of the decomposition is at 200 ° C for the three films. DSC (N2, -100 at 200 ° C, 10 ° C / min); Tm is not detected. Anal. Found film 1:% C 54.29; % H 7.72; % N 0.55; % F 4.02% S 1.29; Film 2:% C 54.20; % H 7.68; % N 0.57 F 4.40 S 1.29; Film 3:% C 54.46; % H 7.75 % N 0.57% F 3.84; % S 1.06. Elemental analysis indicates that approximately 9 percent mole of monomer 2 incorporated.

EXAMPLE 40 Copolymerization and degradation of the IAA (trifluoromethanesulfonyl) -2- (4- et enylphenoxy) tet lithium fonifluoroethane fonimide, polyethylene glycol ethyl ether methacrylate and poly (ethylene glycol) diacrylate. Film A: in a glove box with the PEGEEMA (2.75 g, 1.12 X 10"2 mol), diacrylate (0.036 g, 6.26 X 10" 5 mol, and N-trifluoromethanesulfonyl) -2- (4-ethenyl-1-phenoxy) ) Lithium tetrafluoroethanesulfonimide (0.55 g, 1.26 X 10"3 mol) are combined with 16 mg (6.45 X 10"5 mol) of Vazo® 52. The film is emptied into a small Teflon® petri dish and heated at 40 ° C for 6 hours in a slide heater. gloves the PEGEEMA (2.76 g, 1.12 X 10"2 mol), diacrylate (0.018 g, 3.13 X 10" 5 mol, and N-trifluoromethanesul fonyl) -2- (4-ethenylphenoxy) tetraf luoroetanosul fonimide lithium (0.55 g, 1.26 X 10"3 mol) are combined with 16 mg (6.45 X 10"5 mol) of Vazo® 52. The film is emptied into a small petri dish of Teflon® and ? K. heat at 40 ° C for 6 hours in a deflatable heater. Film C: in a glove box the PEGEEMA (2.77 g, 1.13 X 10"2 mol), diacrylate (0.009 g, 1.57 X 10" 5 mol, and N-trifluoromethanesulfonyl) -2- (4-ethenylphenoxy) tetrafluoroethanesulfonimide of lithium (0.55 g, 1.26 X 10"3 mol) are combined with 16 mg (6.45 X 10" 5 mol) of Vazo® 52. The film is emptied into a small Teflon® petri dish and heated to 40 ° C for 6 hours in a s1 i sable heater. Film D: the PEGEEMA (2.72 g, 1.10 X 10"2 mol), diacrylate (0.071 g, 1.24 X 10" 4 mol, and N-trif luoromethanesulfonyl) -2- (4-ethenyl phenoxy) tetrafluoroethanesul fonimide lithium (0.54 g, 1.23 X 10 ~ 3 mol) are combined with 16 mg (6.45 X 10"5 mole) of Vazo® 52. The film is emptied into a small Petri dish of Teflon® and heated in a slide heater at 40 ° C for 6 hours, left at room temperature overnight, and then it is heated at 50 ° C for 8 hours.

The films are dried at 85 ° C under vacuum. TGA (N2, 10 ° C / min): the initiation of the decomposition is at 250 ° C (A, B, D) and 230 ° C (C). DSC (N2, -100 at 200 ° C, 10 ° C / min); Tm is not detected. Anal. Found: Film A:% C 53.99; % H 7.97; % N 0.58; % F 4.70; % S 2.33; % Li 0.22; Film B:% C 54.11; % H 8.20; % N 0.58; % F 4.67; % S 2.82; % L i 0.21; Film C:% C 54.42; % H 8.29; % N 0.54; % F 4.53; % S 2.59; % Li 0.22; Film D:% C 54.17; % H 7.96,% N 0.55; % F 4.3; % S 2.36; % L i 0.19. The elementary analysis of the films extracted and then dried are close to the analysis of the films not extracted and the calculated values (10% in mol of N- (trif luoromet anosul foni 1) -2 - (4 -et eni 1 phenoxy) incorporated fluoroetanosulimimide lithium).

EXAMPLE 41 Copolymerization and degradation of N- (trifluoromethanesulfonyl) -2- (4-ethenylphenoxy) tet raf luoroet anosul fonimide of lithium, methyl acrylate and diallyl carbonate. For each film the following is done. The acrylate, lithium N- (trifluoromethanesulfonyl) -2- (4-ethenylphenoxy) tetrafluoroethanesulfonimide, and the carbonate monomers are placed in a small flask with 1 ml of DMF and a stir bar. The initiator is added and stirred until dissolved. The solution is pipetted into a Teflon® petri dish and into boxes on a piece of glass coated with Teflon®. The films are heated in a slide heater at 40 ° C for several hours, left at room temperature overnight, and then heated at 45 ° C for 8 hours. The amount of the monomers and the initiator of each film are provided below. Film A: methyl acrylate (3.13 g, 0.036 mol), N- (trifluoromethanesulfonyl) -2- (4-et eni-1-phenoxy) tetrafluoroethanesulfonium fonimide (1.76 g, 0.00403 mol), diallyl glycol carbonate (0.111 g, 4.05 X 10"4 mol), Vazo® 52 (15 mg, 6.04 X 10" 5 mol). Film B: methyl acrylate (3.17 g, 0.036 mol), N- (trifluoromethanesulfonyl) -2- (4-et en 1-phenoxy) tetra-fluoroethanesulphonimide fonimide (1.78 g, 0.00407 mol), diallyl glycol carbonate (0.0557 g, 2.03) X 10"4 mol), Vazo® 52 (15 mg, 6.04 X 10" 5 mol). Film C: methyl acrylate (3.18 g, 0.0365 mol), N- (trifluoromethanesul fonyl) -2- (4-ethenylphenoxy) tetrafluoroethanesulfonimide lithium (1.78 g, 0.00407 mol), diallyl glycol carbonate (0.028 g, 1.02 X 10"4 mol), Vazo® 52 (15 mg, 6.04) X 10"5 mol) Film D: methyl acrylate (3.20 g, 0.0368 mol), N- (trifluoromethanesulfonyl) -2- (-etenylphenoxy) tetraf luoroethanesulfonimide lithium. (1.76 g, 0.0041 mol), diallyl glycol carbonate (0.014 g, 5.11 X 10"5 mol), Vazo® 52 (15 mg, 6.04 X 10" 5 mol). The films are dried under vacuum at 85 ° C. TGA (N2, 10 ° C / min): the initiation of decomposition is at 140 ° C for all films. DSC (N2, -100 at 180 ° C, 10 ° C / min); Tm was not detected. Anal. Found: Film A:% C 33.88, 33.80; % H 3.31, 3.24; % N 5.35, 5.36; % F 22.50, 22.36; % S 11.20, 10.89; % Li 1.09, 1.10; Film B:% C 34.12, 34.31; % H 3.43, 3.31; % N 5.67, 5.78; % F 22.04, 22.'33; % S 11.03, 10.97; % Li 1.13, 1.15; Film C:% C 33.21, 33.28; % H 3.20, 3.18; % N 5.75, 5.78; % F 23.44, 23.10; % S 10.97, 10.99; % Li 1.14, 1.18; Film D:% C 33.72, 33.79; % H 3.22, 3.25; % N 5.56, 5.55; % F 23.36, 23.23; % S 12.76, 12.52; % L i 1.18, 1.14.

EXAMPLE 42 Copolymerization and degradation of IA (trifluoromethanesulfonyl) -2- (4-et en 1-phenoxy) tet raf luoroethanesul fonimide of lithium, methyl acrylate and diallyl diglycol carbonate The films are prepared as follows. The methyl acrylate, the N- (trifluoromethanesulfonyl) -2- (4-ethenyl phenoxy) tetrafluoroethanesulphonimide lithium, and the carbonate monomers are placed in a small flask with 1 ml of DMF and with a stir bar. The initiator is added and stirred until dissolved. The solution is pipetted into a Teflon® petri dish and into boxes on a piece of Teflon®-coated glass. The films are heated in a slide heater ~. ~ - £ i £ ¡na * a¿álWÉ? .. j?. "A > y ^. * i A ^ fj », ^ tf,, ~». • .ag ae ^ -. -? at 40 ° C for 6 'hours, they are left at room temperature overnight, and then heated at 45 ° C for 8 hours. The amounts of the monomers and the initiator are given below. Film A: methyl acrylate (3.13 g, 0.036 mol), lithium N- (trifluoromethanesulfonyl) -2- (4-ethenylphenoxy) tetrafluoroethanesulfonimide (1.76 g, 0.00403 mol), diallyl glycol carbonate (0.111 g, 4.05 X 10"4 mol) ), Vazo® 52 (15 mg, 6.04 X 10"5 mol). Film B: Methyl acrylate (3.17 g, 0.036 mol), N- (trifluoromethanesulfonyl) -2- (4-ethenyl-1-phenoxy) -tetrafluoroethanesulphonimide (1.78 g, 0.00407 mol), diallyl glycol carbonate (0.0557 g, 2.03 X 10"4 mol), Vazo® 52 (15 mg, 6.04 X 10" 5 mol). Film C: methyl acrylate (3.18 g, 0.0365 mol), N- (trifluoromethanesulfonyl) -2- (4-ethenyl phenoxy) tet raf luoroet anosul fonimide lithium (1.78 g, 0.00407 mol), diallyl glycol carbonate (0.028 g, 1.02 X 10"4 mol), Vazo® 52 (15 mg, 6.04 X 10" 5 mol).

Film D: methyl acrylate (3.20 g, 0.0368 mol), N- (trifluoromethanesulfonyl) -2- (4-ethenylphenoxy) tetrafluoroethanesulfonimide lithium (1.76 g, 0.0041 mol), diallyl glycol carbonate (0.014 g, 5.11 X 10 ~ 5 mol), Vazo® 52 (15 mg, 6.04) X 10"5 mol) The films are dried under vacuum TGA (N2, 10 ° C / min): the initiation of the decomposition is at 150 ° C for all the films DSC (N2, -100 a 100 ° C, 10 ° C / min): Tm is not detected.

EXAMPLE 43 Copo 1 ime rization of 2- (4- et eni 1 phenoxy) tet raf luoroet lithium anosulfonate, N- (trifluoromethanesulfonyl) -2- (4-ethenyl phenoxy) tet rafluoroethanesulfimide of lithium and butyl acrylate In a glove box are combined 1.0 g (0.00327 mol) of 2- (4-ethenophenoxy) -tetrafluoroethanesulfonate lithium, 1.43 g (0.0033 mol) of N- (trifluoromethanesulfonyl) -2- (4-et en 1-phenoxy) tet raf luoroet anosul fonimide, and 7.56 g -j-3-. . ... j »H < - Jt ... - < £ * .. . .; 5 ¡¿¡¡¡¡3adft &-a ... -a-.V J., - (0.059 mol) of butyl acrylate in a Schlenk tube with a stir bar, followed by the addition of 45 mg (1.81 X) 10"4 mol) of Vazo® 52 and stirred until dissolved The flask is placed under argon and heated at 40 ° C for 24 hours followed by 45 ° C for 24 hours The resulting polymer is dissolved in acetone / THF , precipitate in water (2x) .The polymer is then dissolved in acetone / THF (3: 1) and precipitated in hexane (2x) .The polymer is dried under vacuum at 60 ° C to obtain 3.3 g (33%). The films will be obtained by dissolving 0.5 g of the polymer in 20 ml of acetone / THF 3: 1 and melting the solution in a Teflon® petri dish of 5.5 cm in diameter TGA (N2, 10 ° C / min) : the initiation of the decomposition is at 300 ° C. DSC (N2, -100 at 250 ° C, 10oC / min), T was not detected, 19 F NMR (d-THF) d: -80.2 (3F), - 81.2 (2F), -82.6 (2F), -117.1 (2F), -118.4 (2F) ppm. The 19 F NMR integration indicates equal amounts of 1 and 2. 13 C NMR (d-THF) d: 175.0, 64.9, 42.5, 36.2 (b), 31.9, 20.2, 14.3 ppm. A NMR (d-THF) d: 7.1, 4.0, 2.9, 2.3, 1.8, 1.7-1.2 (b), 0.9 ppm. The H NMR integration indicates 7 mol% of the ionomeric content based on the integration of the aromatic signal to the butyl acrylate methyl signal. Anal. Found:% C 8.24, 58.52; % H 8.32, 8.12; % N 0.48, 0.41; % F 5.69, 5.89; % L i 0.33, 0.35; % S 3.70, 3.47.

EXAMPLE 44 Synthesis of (ar-vinylbenzyl) trimethylammonium 2- (4-ethenyl phenoxy) tetrafluoroethanesulfonate Dissolve 2- (4-et en-1-phenoxy) tet lithium phosphonates (3.06 g, 0.01 mol) in 10 ml of deionized water. To this is added a solution of 2.12 g (0.01 mol) of (ar-vini lbenzyl) trimethylammonium chloride (Aldrich, mixture of meta and para isomers) in 10 ml of deionized water. An oily gum precipitates instantaneously which becomes a crystalline solid with additional agitation. The solid is collected, washed with 20 ml of water and dried at 40 ° C under vacuum to yield 4.52 g (95%) of the title salt which is soluble in THF, DMF and methanol. A NMR (d, CD3OD): 3.08 (s, 9H), 4.50 (s, 2H), 5.25 (d, 1H), 5.35 (d, 1H), 5.5 (d, 1H), 5.88 (d, 1H), 6.60-6.80 (2dd, 2H), 7.23 (d, 2H), 7.55 (m, 6H); 19F NMR (d, CD30D) -81.07 (2F), -116.66 (2F). Anal. Calculated for C22H25F4N04S: C, 55.57; H, 5.30; N, 2.95; S, 6.74; F, 15.98. Found: C, 54.27; H, 5.09; N, 2.83; S, 7.19; F, 15.79.

EXAMPLE 45 Synthesis of the synthesis of N- (trifluoromethanesul fonyl) -2- (4-ethene-1-phenoxy) -ethe-fluoroethanesulfonide of (ar-vinylbenzyl) trimethylammonium N- (trifluoromethanesulfonyl) -2- (4 - et eni 1 phenoxy) te t rafluoroet anosul fonimida de lithio (8.75 g, 0.02 mol) in 20 ml of deionized water and cooled in a bath of ice water. To this is added a solution of 4.24 g (0.02 mol) of (ar-vinylbenzyl) trimethylammonium chloride (Aldrich, mixture of meta and para isomers) in 20 ml of deionized water. A clear gum is immediately deposited. The aqueous solution is decanted and the gum washed with water. Drying under vacuum at 30 ° C occurs with severe foaming. The product is dissolved in 50 ml of methanol, filtered in a 300 ml round bottom flask and concentrated in a rotary evaporator for a clear syrup which is dried for 16 hours at 30 ° C and 0.05 mm. The product weighs 11.5 g (95%). A NMR (d, CD3OD): 3.1 (s, 9H), 4.47 (s, 2H), 5.25 (d, 1H), 5.35 (d, 1H), 5.76 (d, 1H), 5.87 (d, 1H), 6.68-6.81 (2dd, 2H), 7.20 and 7.50 (quartet AB, 4H), 7.42-7.50 (m, 4H); 19 F NMR (d, CD30D) -78.91 (3F), -79.77 (2F), -115.27 (2F).

EXAMPLE 46 Copolymerization of lithium 2- (4- e ten i-1-phenoxy) -tetrafluoroethanesulfonate, 2- (4-ethenyl phenoxy) -tetra-fluoroethanolamide of (arvinylbenzyl) trimethylammonium and methacrylate methacrylate A polymer tube is charged with 3.06 g (0.01 mol) of 2- (4- et eni-1-phenoxy) -tetra fluoroethanesulfonate lithium, 2.38 g (0.005 mol) of the product of Example 44 and ml of DMF. This solution is placed under a vacuum pump until about 1 ml of the solvent has evaporated to remove traces of methanol from the salts. The methyl methacrylate (8.5 g, 0.085 mol) and 0.05 g of Vazo® 52 are added to the solution and subjected to three cycles of freezing, evacuation and liquefying. Then it is heated for 20 hours in an oil bath at 50 ° C. The solution is cooled, and diluted with 80 ml of DMF and poured into water. This provides a gel which can not be filtered. The solvents are removed at 49 ° C and filled with a vacuum pump to produce 16.5 g of residue. This material is washed with 2 X 100 ml of water, stirred for several hours with each portion. The water-insoluble material is dried under high vacuum at 48 ° C to produce 9.92 g of the polymer. This material is soluble in methanol, acetone, DMF and DMSO and a clear brittle film will be melted from the DMF. From the 13C NMR spectrum of the polymer in DMF, it is calculated that it contains 81 mol% of MMA units, 14 mol% of OCF2CF2S03 units and 5 mol% of CH2NMe3 units of the integration of the peaks at 17 ppm (MMA of methyl), 118.4 + 122.3 (CF2) and 68.8 (CH2N) Anal. Found: C, 52.98; H, 6.26; F, 7.56; Li, 0.45; S, 3.66.

EXAMPLE 47 Copo 1 embodiment of lithium N- (trifluoromethanesulfonyl) -2- (4-ethenylphenoxy) tetrafluoroethanesulfonimide, N- (trifluoromethanesulfonyl) -2- (4-ethenyl phenoxy) tet ra f 1 or pyrolysulfonimide of (ar-vini lbenci 1) trimethamium and methyl methacrylate A tube for 50 ml polymer is cooled in ice water and charged with 2.19 g (0.005 mol) of N- (trifluoromethanesulfonyl) -2- (4-et en 1-phenoxy) tet raf luoroet anosulimimide lithium and 10 ml of ice water. After the salt dissolves, a solution of 1.06 g (0.005 mol) of chloride (a r-vini lbenci 1) t rime t ammonium in 10 ml of ice water are added resulting in the immediate precipitation of a sticky gum. The water is decanted and the gum is stirred with 10 ml of ice water with a spatula. The gum is dried briefly under a vacuum pump, then dissolved in 20 ml of DMF. The lithium N- (trifluoromethanesulfonyl) -2- (4-ethenyl phenoxy) -tetrafluoroethanesulfonimide (4.37 g, 0.01 mol) is added followed by 8.5 g of methyl methacrylate and 0.05 g of Vazo® 52. The solution is deoxygenated by four cycles freezing / pumping / liquefied, then heated in an oil bath for 22 hours at 50 ° C. An additional 20 ml of DMF is added and the mixture is heated to produce a clear solution. The polymer is precipitated by the addition of the DMF solution with an excess of ether. The precipitate is washed in a mixture with ether, then dried at 100 ° C and 0.1 mm to yield 14.86 g of a white solid. The NMR shows that the solid still contains DMF so that it precipitates from the acetone in ether and drying produces 12.45 g (78%) of a white solid. 1 H NMR (d, acetone-d6) 0.6 - 3.8 (multiplets), 4.60 (bs), 7.2-7.5 (b). By the integration of the aliphatic against the benzyl against the aromatic peaks, it is calculated that the polymer contains N- (trifluoromethanesulfonyl) -2- (4-ethenyl phenoxy) tetra fluoroethanesulphonimide of lithium (9.8 mol%), N- (ßki fluorometanosul foni 1) - 2- (4-ethenylphenoxy) -tetrafluoroethanesulfonimide of (ar, vinylbenzyl) -trimet-ammonium (4.6% by mol) and MMA (85.5% by mol). 19 F NMR (d, acetone-d 6) -78.69 (3F), -79.47 (2F), -115.30 (2F). Anal. Found: C, 48.79; H, 5.52; N, 2.06; F, 12.22; Li, 0.40; S, 6.30. A melted film of acetone is clear and rigid. EXAMPLE 48 10 Co-cure of lithium 2- (4-eti-1-phenoxy) -tetrafluoroethanesulfonate with the Hydrin®T elastomer A mixture of 2.5 g of lithium 2- (4-ethenophenoxy) tet-fluoro-fluoroethylene fonate, 5.0 g of Hydrin®T and 50 ml of DMF are mixed in a roller glass jar until the solution is homogeneous. The benzoyl peroxide (0.3 g) is added and the mixture is continued for 2 hours. A portion (15 ml) of this solution is poured into each one of the three casting molds (Teflon®, 27/16 square inches). The molds are placed in a vacuum oven under a nitrogen purge at room temperature throughout the entire ** > overnight, then it was heated at 70 ° C for 48 hours under vacuum with a slight nitrogen purge. The resulting films are quickly peeled from the mold and are slightly yellow, slightly flexible, firm and without visible phase separation. A film is weighted and immersed in THF for 24 hours at room temperature. This film is observed to be inflated several times its size but retains its shape. This is removed from the THF, peeled dry with paper towels and weighed. The original weight (1.95 g) has an increase to 7.77 g (% expansion = 298). After drying the film returns to its original size. The THF solution is concentrated in a rotary evaporator to produce 0.17 g (8.7%) of extractables. Anal. Found: C, 43.46; H, 5.64; F, 7.05; S, 2.69; Li, 0.62. For the analysis of% S, the equivalent weight is calculated to be 1190. EXAMPLE 49 Co-curing of N- (tri-fluoroethanesul foni 1) -2- (4-ethenyl phenoxy) tetra fluoroethanesulphonimide with the Hydrin®T elastomer The procedure of Example 48 is still using 2.5 g of the sulfonimide salt in place of the lithium sulfonate. A film weighs 1.80 g. After completely in THF for 24 hours, the film weighs 12.01 g (567% expansion). The concentration of THF solution produces 0.57 g (29% extractables). Anal. Found: C, 40.40; H, 5.66; F, 5.77; Li, 0.27; S, 3.24. For the% S analysis, the equivalent weight is calculated to be 9 EXAMPLE 50 Polymerization of 3, 5-di (CQ2CH3) -Ph- OCF2CF2S03Li and bis (hydroxyethyl) terephthalate To a 500 ml round bottom flask with mechanical stirring and distillation head is charged with 28.5 g (0.0712 mol) of 3 , 5-di (C02CH3) -Ph-0CF2CF2S03Li and 20 g of ethylene glycol. The flask is immersed in a tin / bismuth alloy bath, preheated to 200 ° C, and the contents are stirred until a homogeneous solution is formed. The stirring is interrupted and 54.8 g (0.216 mol) of bis (hydroxyethyl) terephthalate and 0.02 g of titanium (IV) isopropoxide is added. The system is flushed with nitrogen and is alternatively evacuated and filled to an atmosphere several times. The rapid stirring is set at 50 rpm and the temperature bath is gradually increased to 240 ° C around 1 hour resulting in a slow distillation. The bath temperature is gradually increased to 250 ° C and the system pressure decreases to 160 millitorr at about 3.75 hr with the continuous collection of the distillate. Stirring torque increases from 24 to 180 during this period. The mixture is allowed to cool to room temperature and 82.lg of solid and 19.2 g of distillate are isolated. The solid is dissolved in? -butyrolactone and the solution is filtered and added to each excess to precipitate a gum. The rubber is dried at 135 ° C and 0.05 mm pressure. This is dissolved in about 1 L of acetone and the solution is concentrated to 500 ml and added in small portions to an excess ether. The precipitated polymer is dried at room temperature and 0.05 mm pressure to provide 63.8 g of product. The intrinsic viscosity (1: 1 CH2C12: CF3C00H) = 0.0334; Tg (DSC) = 84 ° C. The proton NHR (acetone-d6) shows a peak of d of 8.5 and 8.0 assigned to a proton of the substituted sulfonate aromatics, and two protons of the substituted sulfonate groups plus four protons of the terephthalate elements. By integration, the proportion of these groups is calculated to be 1: 3 according to the proportion of the starting material. Fluorine (acetone-d6) shows ridges of the same area at d of -81.2 and d of -116.7.

EXAMPLE 51 Polymerization of bis (hydroxyethyl i) terephthalate The procedure of Example 50 is still using 33.0 g (0.05 mol) of the lithium monomer sulfonate of Example 9 20.3 g (0.08 mol) of bis (hydroxyethyl) terephthalate, 30.0 g of ethylene glycol and 0.02 g of isopropoxide (IV ) from . »* _ * - yJSi ¡& ui, & -. i¡aa .. »-.» titanium. The final torque in the agitator motor is 150. 51.5 g of the polymer and 27.5 g of the distillate are isolated. The polymeron dissolves in acetone. This solution is filtered and the filtrate is slowly added to the excess ether. The resulting viscous polymer is collected and dried giving 31.8 g of a white matte foam. The NMR of the proton is similar to that described in Example 50 with the integration of the appropriate peaks indicating a ratio of 1.7: 1 of the terephthalate with the substituted sulfonate elements FNMR d, acetone-d6) -78.5 to -79.7 (m, 5 F , CF3 + CF2), -81.7 to -86.7 (m, 4F, 2CF2), -117.2 (s, 2F, 1CF2), -144.1 to 145.1 (m, 2F, CF + CFH).

EXAMPLE 52 The ionomer film of the solution form of Example 14 is dried in a nitrogen recirculation oven (Electric Hotpack Company, Inc., Model 633, Philadelphia, PA) at 110 ° C for 48 hours. The dried film is transferred to a sealed container while remaining lukewarm and is transported to a glove box and having a pressure. positive dry hydrogen applied to this, where the membrane is removed from the sealed container and allowed to stand at room temperature. The membrane is then cut into several sections of 1.0 cm X 1.5 cm in size. A 1: 1 by volume mixture of ethylene carbonate (EC, 98%, Aldrich Chemical Co., Inc., Milwaukee, Wl) and dimethyl carbonate (DMC, 99%, Alfa Aesar, Ward Hill, MA) are deposited by medium of a pipette on the top surface of a 1.0 cm X 1.5 cm film specimen cooled in an amount equal to 133% of the weight of the film sample. After waiting thirty minutes, the ionic conductivity is measured. The film of the treated solvent is dried and placed in the conductivity cell. The impedance of the cell is determined over the range of 10 Hz to 100,000 Hz, and the value with the zero phase angle in the higher frequency range is usually 500-5000 Hz) is attributed to the strength of the block sample Ohms The value of the raw strength is then converted to conductivity, in S / cm using the constant of the cell and the thickness of the inflated film of the liquid. The ionic conductivity is found to be 1.03 X 10"4 s / cm at 23 ° C.

EXAMPLE 53 Several grams of the dry lithium salt of Example 3 are placed in a glove box having a positive pressure of dry nitrogen applied thereto. The salt is combined with the EC / DMC mixture of example 52 to form a 0.5 M solution. This liquid conductivity of this solution is measured and is 1.72 X 10 ~ 3 s / cm at 23 ° C. EXAMPLE 54 Several grams of the dry lithium salt of Example 7 are placed in a glove box having a positive pressure of dry nitrogen applied thereto. The salt is combined with the EC / DMC mixture of Example 52 to form an IOM solution. This solution is diluted to 50% to produce a 0.5 M solution, the ividated conductivity of the liquid is measured and is 4.30 X 10"3 s / cm at 23 ° C.

EXAMPLE 55 The ionomer film of Example 16 is dried in a nitrogen re-circulation bath (Electric Hotpack Comany, Inc., Model 633, Philadelphia, PA) at 100 ° C for 48 hours. A sample of the cooled 1.0 cm by 15 cm membrane is immersed in deionized water for a period of several hours. The ionic conductivity is determined as in Example 52, except that the specimen is tested outside the glove box, and is found to be 1588 X 10"3 s / cm at 23 ° C.

EXAMPLE 56 The ionomer film of Example 49 (E93722-105-5 *) is dried in a nitrogen recirculation oven (Electric Hotpack Company Inc., Model 633, Philadelphia, PA) at 75 ° C under vacuum for 48 hours and then transferred to a dry box of purged nitrogen vacuum atmospheres. A sample of the cooled 1.0 cm by 1.5 cm membrane is immersed in an excess of propylene carbonate (Selectipur, EM Industries) for a period of 5 minutes. After this period, the membrane sample is dried on its surface with a paper towel and its absorbed weight and ionic conductivity are measured. The absorbed weight of the propylene carbonate is equal to 554% by weight of the dry sample. The inflated solvent film is free-standing and easy to handle. The ionic conductivity is determined with Example 52 and found to be 2.59 X 10 ~ 4 s / cm at 23 ° C.

EXAMPLE 57 The ionomer film of Example 30 (EP2207-78) is obtained as described therein and transferred directly to a dry box of purged nitrogen vacuum atmospheres. A sample of the cooled 1.0 cm by 1.5 cm membrane is immersed in an excess of propylene carbonate (Selectipur, EM Industries) for a period of ten minutes. After this period, the membrane sample is dried on its surface with a paper towel and the absorbed weight and ionic conductivity are measured. The absorbed weight of the propylene carbonate is equal to 366% by weight of the dry sample. The inflated solvent film is free-standing and easy to handle. The ionic conductivity is determined as in Example 52 and found to be 4.12 X 10"4 s / cm at 23 ° C.

EXAMPLE 58 AND 59 A slurry is prepared by mixing 65 g of graphite MCMB 25-28 (Osaka Gas Co., Ltd., Osaka, Japan), 10 g of the fluoride-hexa fluoruropropyl polyvinylidene 2801 Kinar Flex® copolymer (Elf Atochem, Philadelphia , PA), 3.5 g of Super P carbon black (MMM SA Coal, Brussels, Belgium), 21.5 g of dibutyl phthalate titrant and 150 g of acetone as the foundry solvent. The slurry is then formed into a graphite electrode film of 0.111 to 0.126 mm thick, using a scraper blade with an ac gate height. 0.500 mm. A stratified structure is formed by placing a piece of the electrode film between the brass sheets of about 0.127 mm thick, using 0.095 mm thick diaphragms between the thin sheets of metal to prevent excessive pressure on the electrode. In order to better consolidate the electrode film, the stratified structure is passed through a 120 X RL Western Magnum laminator set at a temperature of 115 ° C, and at a pressure of 20 psig. After consolidation, the electrode is removed from the brass sheets and the thickness is determined with a value of 0.108 mm. The dibutyl phthalate is then extracted from the consolidation electrode film using diethyl ether after which two circular pieces of about 15.9 mm in diameter are cut from the electrode film, extracted the circular pieces are dried in an antechamber and introduced in a glove box under an argon atmosphere. to * ,,' .

In a glove box under an argon atmosphere, 0.725 g of C2H3C6H4OCF2CF2S03Li is prepared in the same manner as in Example 3 is placed in a 10 ml volumetric flask to which a 1: 1 by weight mixture of sodium carbonate is added. ethylene and dimethyl carbonate, adding EC / DMC 1: 1 (by weight) and the mixture thus formed is stirred at room temperature for 20 minutes to form an electrolytic solution, and the stirring time is 10 minutes. The conductivity of the electrolyte solution is determined and is 1131 s / cm at room temperature, using the method described above. The two 15.9mm diameter specimens of the dry graphite electrode film and two 15.9mm diameter pieces of 24 micrometer thick Celgard® 3501 microporous propylene are soaked in the electrolyte solution in separate small closed vials in the box of handling with gloves for 20 minutes. Two miniature electrochemical coils of size 2325 are formed by using the soaked graphite electrode as the positive electrode, the Celgard® film soaked as the separator, and a 0.333 mm thick circle as the negative electrode. Each coined cell is sealed and discharged with the current constant of 0.5 mA at a voltage of 0.01 V, which is below 0.05 mA. Each cell is then discharged to a present constant of 0.5 mA at 1.1 V, and then the voltage is kept constant at 1.1 V the present load drops below 0.05 mA. The capacities of the positive electrode in the loading and unloading for the two coined cells are shown in Table 1.

Table 1: positive electrode capacities . * ki * ¡* ssaj? tL * »Mat ~? A t ~ Í ^ Ü.

EXAMPLES 60 and 61 The procedures of Examples 58 and 59 are repeated with the exceptions mentioned herein. The film specimens of the electrode and the separator have a diameter of 12.7 mm, the films of the positive electrode are 0.095 mm thick. The electrode solution is formed as in Examples 58 and 59 except that 0.660 g of C2H3C6H4OCF2CF2S03Li is used. The conductivity of the electrolyte solution is determined and is 1249 ms / cm at room temperature under Argon, using the method described above. The capacities of the positive electrode in the loading and unloading for the two coined cells are shown in Table 2. . , tet & Table 2: positive electrode capacities It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present invention. Having described the invention as above, property is claimed as contained in the following

Claims (26)

1. - A polymer comprising pendant groups comprising the radical described by formulas I (a) and I (b): O-CF 2-Rf CF2S02Y (SO 2 Rf ') n 0-CF 2 -Rf-CF 2 SO 2 Y (SO 2 Rf characterized in that Rf is a bond or is a fluoroalkylene group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, and is N, O, or C, Rf 'is a group f luoroa Iqui from 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, n = 0, 1 or 2 with the proviso that n = 0 when Y = 0, n = l when Y = N, and n = 2 when Y = C, and Z is hydrogen or a univalent metal.

2. A compound described by the formula (II) 0-CF2-RrCF2S02Y (SO 2Rf characterized in that m = 0, 1 or 2 and when m = l R is a polymerizable group or bromine or iodine, and when m = 2, R represents polymerizable groups, or bromine groups, or iodo groups, which are optionally the same, Rf is a bond or is a group f luoroalquileno of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, Y is N, O, C, Rf 'is a group f luoroalkyl from 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, n = 0, 1 or 2 n = 0, or 2, with the proviso that n = 0 when Y = 0, n = l when Y = N and n = 2 when Y = C, and Z is hydrogen or a univalent metal.

3. A process characterized in that it comprises: reacting the alkali metal salts of substituted phenols described by the formula (III), with 1,2-dibromotetraf luoroethylene to produce compounds described by the formula (IV) jBr wherein m is 0, 1 or 2 and (R) is bromo, iodo, C02R 'or N02, R' is an alkyl group of 1 to 1C carbon atoms and M is an alkali metal. reacting the compound described by the formula (IV) with a sul fi cation reagent to form an alkali metal sulfinate described by the structure (V) 2S02M (V) the reaction of an alkali metal sulphinate of structure (V) with an elemental chlorine or bromine to provide the corresponding sulfonyl chloride or bromide described by structure (VI) wherein X = Cl or Br; ^ O ^ (V) (VI)

4. A conductive composition ionically characterized in that it comprises the ionomer of claim 1 and a liquid imbibed therefrom.

5. A conductive composition ionically characterized in that it comprises the compound described by the formula (II) and a liquid.

6. An ion exchange membrane characterized in that it comprises an ionomer comprising pendant groups comprising the radical described by the formula: O-CF 2-Rf CF2S02Y (SO 2 Rf ') n 0-CF2.RÍ-CF? SO 2Y (SO 2 Rf wherein Rf is a bond or is a f-alkoalkylene group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, Y is N, O, or C, Rf 'is a fluorine group of from 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more; hydrogen atoms, n = 0, 1 or 2 with the proviso that n = 0 when Y = 0, n = l when Y = N, and n = 2 when Y = C, and Z is hydrogen or a univalent metal.

7. An electrochemical cell characterized in that it comprises a cathode, an anode and a separa at least one of which comprises an ionomer comprising pendant groups comprising the radical described by the formula: O-CF 2-Rf CF2S02Y ($ 02Rf *) n O-CF ^ Rf-CF? SO 2 Y (SO 2 Rf where R f is a bond or is a f-alkoalkylene group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more atoms of hydrogen, Y is N, O, or C, Rf 'is a fluoroalkyl group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, n = 0, 1 or 2 with the proviso that n = 0 when Y = 0, n = l when Y = N, and n = 2 when Y = C, and Z is hydrogen or a univalent metal.

8. An electrochemical cell characterized in that it comprises an anode, a cathode, a separator, and a conductive composition comprising the compound described by the formula (II) and a liquid.

9. An electrode characterized in that it comprises a reactive material and an ionomer comprising pendant groups comprising the radical described by the formula: O-CF 2-Rf-CF2S02Y (SO 2 Rf ') n 0-CF2.Rf.CF 02Y (SO 2Rf wherein Rf is a bond or is a fluoroalkylene group of 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, and is N, O, or C, Rf 'is a luoroalkyl group from 1 to about 10 carbon atoms, optionally substituted by one or more ether oxygens and one or more hydrogen atoms, n = 0, 1 or 2 with the proviso that n = 0 when Y = 0 , n = l when Y = N, and n = 2 when Y = C, and Z is hydrogen or a uni metal lens.

10. The ionically conductive composition according to claim 4 or 5 in a form selected from the group consisting of a film, sheet and gel.

11. The ionically conductive composition according to claim 10 characterized in that it further comprises an electrically insulated microporous polymer sheet or film on the micropores of which the gel is embedded.

12. The compound according to claim 2 characterized in that R is in the position for

13. The polymer according to claim 1 characterized in that Rf is CF2 and Rf 'is CF3 or C2F5.

14. The polymer according to claim 1 characterized in that the main chain is degradable.

15. The polymer according to claim 1 characterized in that Z is Li +.

16. The polymer according to claim 1 characterized in that Y is N.

17. The polymer according to claim 1 characterized in that Y is 0.

18. The composition according to claim 2 characterized in that Rf is CF2 and Rf 'is CF3 or C2F5.

19. The composition according to claim 2 characterized in that Z is Li +.

20. The composition according to claim 2 characterized in that 16 Y is N.

21. The composition according to claim 2 characterized in that Y is 0.

22. The composition according to claim 2 characterized in that R is -CH = CH2 and m = 1.

23. The composition according to claim 2 characterized in that R is -C02R 'and m = 2, wherein R' is an alkyl radical having 1-10 carbon atoms.

24. The ionically conductive composition according to claim 4 or claim 5 characterized in that the liquid is selected from the group consisting of organic carbonates, diesters, and esters, and mixtures thereof.

25. The ionically conductive composition according to claim 24, characterized in that the liquid is a mixture of a cyclic organic carbonate and a diester.

26. The ionically conductive composition according to claim 25, characterized in that the liquid is a mixture of ethylene carbonate and dimethyl succinate. S ^ tó ^^^^^^^^^^^^^^ g ^^^^