Indian Patents. 227323:ION CONDUCTIVE RANDOM COPOLYMERS

Title of Invention	ION CONDUCTIVE RANDOM COPOLYMERS
Abstract	This invention relates to ion conduction random copolymers that are useful in forming polymer electrolyte membranes used in fuel cells.

Full Text	FORM 2 THE PATENT ACT 1970 (39 of 1970) & The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10 and rule 13) 1. ION CONDUCTIVE RANDOM COPOLYMERS 2. (A) POLYFUELINC. (B) UNITED STATES OF AMERICA. (C) 1245 Terra Bella Avenue, Mountain View, CA 94041 USA The following specification particularly describes the invention and the manner in which it is to be performed. 1 TECHNICAL FIELD This invention relates to ion conductive random copolymers that are useful in forming polymer electrolyte membranes used in fuel cells. BACKGROUND OF THE INVENTION Fuel cells have been projected as promising power sources for portable electronic devices, electric vehicles, and other applications due mainly to their non-polluting nature. Of various fuel cell systems, the polymer electrolyte membrane based fuel cell technology such as direct methanol fuel cells (DMFCs) has attracted much interest thanks to their high power density and high energy conversion efficiency. The "heart" of a polymer electrolyte membrane based fuel cell is the so called "membrane-electrode assembly" (MEA), which comprises a proton conducting polymer electrolyte membrane (PEM), catalyst disposed on the opposite surfaces of the PEM to form a catalyst coated member (CCM) and a pair of electrodes (i.e., an anode and a cathode) disposed to be in electrical contact with the catalyst layer. Proton-conducting membranes for DMFCs are known, such as Nation® from the E.I. Dupont De Nemours and Company or analogous products from Dow Chemicals. These perfluorinated hydrocarbon sulfonate ionomer products, however, have serious limitation when used in DMFCs. Nafion® loses conductivity when the operation temperature of the fuel cell is over 80°C. Moreover, Nafion® has a very high methanol crossover rate, which impedes its applications in DMFCs. U.S. Patent No. 5,773,480, assigned to Ballard Power System, describes a partially fluorinated proton conducting membrane from a, b, b -trifluorostyrene. One disadvantage of this membrane is its high cost of manufacturing due to the complex synthetic processes for monomer a, J3, P-trifluorostyrene and the poor sulfonation ability of poly (a, p, P-trifluorostyrene). Another disadvantage of this membrane is that it is very brittle, thus has to be incorporated into a supporting matrix. U.S. Patent Nos. 6,300,381 and 6,194,474 to Kerrres, et al. describe an acid-base binary polymer blend system for proton conducting membranes, wherein the sulfonated poly(ether sulfone) was made by post-sulfonation of the poly (ether sulfone). M. Ueda in the Journal of Polymer Science, 31(1993): 853, discloses the use of sulfonated monomers to prepare the sulfonated poly(ether sulfone polymers). U.S. Patent Application US 2002/0091225A1 to McGrath, et al. used this method to prepare sulfonated polysulfone polymers. The need for a good membrane for fuel cell operation requires balancing of various properties of the membrane. Such properties included proton conductivity, methanol-resistance, chemical stability and methanol crossover, fast start up of DMFCs, and durability to cell performance. In addition, it is important for the membrane to retain its dimensional stability over the fuel operational temperature range. In DMFCs methanol oxidation generates enough heat to raise the cell temperature. If the membrane swells significantly, it will increase methanol crossover. The membrane thus gradually loses its ability to block methanol crossover, resulting in degradation of cell performance. The dimension changes of the membrane also put a stress on the bonding of the membrane-electrode assembly (MEA). Often this results in delamination of the membrane from the electrode after excessive swelling of the membrane. Therefore, maintaining the dimensional stability over a wide temperature range and avoiding excessive membrane swelling are important for DMFC applications. 3 SUMMARY OF THE INVENTION In one aspect, the invention provides sulfonated random copolymer compositions which can be used to fabricate polymer electrolyte membranes (PEM's), catalyst coated membrane (CCM's) and membrane electrode assemblies (MEAs) which are useful in fuel cells. The invention includes three classes of random ion conductive copolymers. Such random polymers are of the following formulas: Formula I ## str( Q Jn CH3 wherein R is a single bond, a cycloaliphatic of the formula CnH2n-2; ## str( )## wherein a, b, c and d are mole fractions of the monomer present in the copolymer where each are independently, from 0.01 to 1; * Q is an ion conducting group comprising -SO3X, -COOX -PO3X or -S02-NH-S02Rf, where Rf is a prefluoronated hydrocarbon having 1-20 carbon atoms; and wherein X is a cation or a proton. ## str( Formula II ntO-v^O^O* Hy^h'^H. )## wherein Rl or R2 are independently a single bond, a cycloaliphatic of the formula CJHkn- CH3 CF3 —s— —O- CH3 CF3 W // —0- where R3 is aryl ketone, aryl sulfone, aryl nitrile, and substituted aryl mtrile; wherein a, b, c and d are mole fiactions of the monomer present in the copolymer where each are independently, from 0.01 to 1; Q is an ion conducting group comprising -SO3X, -COOX -PO3X or -SOj-NH-SChRf, and wherein X is a cation or a hydrogen atom. In another embodiment, four comonomers are used to make the ion conductive copolymer, where at least one comonomer is ion conducting. A specific embodiment is set forth in Formula III. Formula III -(AriXiAr2X2Ar3X3)a/-(Ar4-X4-Ar5-X5-Ar(S-X6)-b where Ar1, Ar2, Ar4, Ar5 are independently phenyl, substituted phenyl napthyl, terphenyl, aryl nitrile, substitute aryl nitrile, and A14 and/or Ar5 further comprise an ion conducting group, Xi and X4 are independently -C(0)- or -S(0)2, X2, X3, Xs and X6 are independently-O- or-S-. Ar3 and Ar6 are the same or different from each other and are: \ / CH, CH, \ // 6 CF, CF. \./ \ _/—\_J \ rrw CH, \ / \ / \ J-°-\_J \ y-°-Aj^°^_/ 7 ## str( O^^O )## wherein the ion conductive group comprises -S03H, -COOH, -HP03H or -S02NH-S02-RF where RF is a perfluorinated hydrocarbon having 1-20 carbon atoms and said ion conducting group are pendant to the copolymer backbone; wherein a is between 0.0land 0.99, b is between 0.01 and 0.99, a + b = 1.0. In some embodiments, at least one of X2, X3, X5 and/or X« is S. In some embodiments, X1 and/or X4 is -S(0)2-. In other embodiments, X1 and/or X4 is -C(0)-. m still other embodiments, X1 is -S(0)2- and X4 is -C(0)-. In other embodiments, A3 and A6 are different. A particularly preferred embodiment is Formula IV: fr Formula IV ## str( )## Where A = 0.60 and B= 0.40 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 demonstrates the performance of DMAc containing PEM's made of the copolymers of Example 20, Example 17 and Example 22 as compared between 50 and 100% relative humidity. DETAILED DESCRIPTION The invention provides random copolymers that are ion conductive. One use of such polymeric material is in the formation of polymer electrolyte membranes (PEMs), catalyst coated membrane (CCM) and membrane electrode assemblies (MCA's), which may be used in fuel DMFC's fuel cells. In one embodiment, random ion conductive copolymers can be made having the following formula: Formula V ## str( so,x CH3 CF3 CH3 CFg ## str( )## wherein R is a bond, a cycloaliphatic of the formula CnH2n-2, ## str( —O \ / —S-O )) —S— o .—CH5—O— )## Q is an ion conducting group comprising -SO3X, -COOX -PO3X or –SO2NH-SO2Rf where Rf is a perfluorinated hydrocarbon of 1 -20 carbon atoms and where X is a cation or probe. In this copolymer, a, b, c and d are mole fractions of each of the monomers present in the copolymer where each are independently, from 0.01 to about 1. In one particular embodiment, R is isopropylidene, cyclohexylidene, 11.4 diphenylene di-isopropylene. In general, the sulfonated copolymers include reaction products wherein (a+c)=(b+d), a is from about 0.05 to about 0.95, b is from about 0.01 to about 0.95, c is from about 0 to about 0.95 and d is from about 0 to about 0.99. Preferably, a is from about 0.10 to about 1.00, b is from about 0.05 to about 0.85, c is from about 0 to about 0.90 and d is from about 0.15 to about 0.95. Most preferably, a is from about 0.20 to about 0.9, b is from about 0.10 to about 0.45, c is from about 0 to about 0.80 and d is from about 0.55 to about 0.90. In another embodiment, the invention pertains to random ion conductive copolymers and proton exchange membranes having the formula: Formula VI wherein Ri or R2 is a single bond, a cycloaliphatic of the formula CnH-in-2, » > 9 9 where R3 is aryl ketone, aryl sulfone, aryl nitrile, and substituted aryl nitrile. 11 wherein a, b, c and d are mole fractions of the monomer present in the copolymer where each are independently, from 0.01 to 1; Q is an ion conducting group comprising –SO3X, -COOX -PO3X or –SO2NH-SO2Rf, where Rf is a prefluoronated hydrocarbon having 1-20 carbon atoms; and wherein X is a cation or a proton. In the sulfonated copolymer, a, b, c and d are mole fractions for each monomer present in the copolymer, each independently from 0.01 to about 1 and X is a cation or a hydrogen atom. In a preferred embodiment, Rl is cyclohexydyl, and R2 is fluorenyl. In general, the sulfonated copolymers include reaction products wherein (a+c)=l .00, (b+d)=1.00, a is from about 0.05 to about 1.00, b is from about 0.01 to about 1.00, c is from about 0 to about 0.95 and d is from about 0 to about 0.99. Preferably, a is from about 0.10 to about 1.00, b is from about 0.05 to about 0.85, c is from about 0 to about 0.90 and d is from about 0.15 to about 0.95. Most preferably, a is from about 0.20 to about 1.00, b is from about 0.10 to about 0.45, c is from about 0 to about 0.80 and d is from about 0.55 to about 0.90. A particularly preferred random copolymer is: SOsH O—1 )## where n and m are mole fractions and, n plus m equals 1, n is between 0.1 and 0.5, more preferably between 0.2 and 0.4 and most preferably between 0.25 and 0.35, m is 1 minus n, and k is between 40 and 200 more preferably between 50 and 100 In a particularly preferred polymer, n is 0.3 and m is 0.7 and has the formula: Vorff / \ too where k is between 40 and 200. Ion conductive polymers can also be represented by Formula HI: Formula III -(AriX1,Ar2X2Ar3X3)a/(Ar4-X4-Ar5-X5-Ar6-X6) b where Ar1, AR2, AX4, Ar5 are independently phenyl, substituted phenyl napthyl, terphenyl, aryl nitrile, substitute aryl nitrile, and Ar4 and/or Ar5 further comprise an ion conducting group, X1 and X4 are independently -C(0)- or -S(0)2, X2, X3, X5 and X6 are independently -O- or -S-. Ar3 and Ar6 are the same or different from each other and are v./ CHj V. / PS \ r-\_/ 12 O-0-^) KM- wherein the ion conductive groups comprise SO3', -COO", H2PO3" or sulfonimide. wherein a is between 0.0l and 0.99, b is between 0.01 and 0.99, a + b = 1.0. A particularly preferred embodiment is Formula IV: 3+0--0-,-Ot -ofo-o- Where A = 0.60 and B= 0.40 Polymer membranes may be fabricated by solution casting of the ion conductive copolymer. Alternatively, the polymer membrane may be fabricated by solution casting the ion conducting polymer the blend of the acid and basic polymer. When cast into a membrane for use in a fuel cell, it is preferred that the membrane thickness be between 1 to 10 mils, more preferably between 2 and 6 mils, most preferably between 3 and 4 mils. As used herein, a membrane is permeable to protons if the proton flux is greater than approximately 0.0O5 S/cm, more preferably greater than 0.01 S/cm, most preferably greater than 0.02 S/cm. As used herein, a membrane is substantially impermeable to methanol if the methanol transport across a membrane having a given thickness is less than die transfer of methanol across a Nafion membrane of the same thickness. In preferred embodiments the 15 permeability of methanol is preferably 50% less than that of a Nafion membrane, more preferably 75% less and most preferably greater than 80% less as compared to the Nafion membrane. After the sulfonated random copolymer has been formed into a membrane (PEM), it may be used to produce a catalyst coated membrane (CCM). As used herein, a CCM comprises a PEM where at least one side and preferably both of the opposing sides of the PEM are partially or completely coated with catalyst layers. The catalyst is preferable a layer made of catalyst and ionomer. Preferred catalysts are Pt and Pt-Ru. Preferred ionomers include Nafion and other ion conductive polymers. In general, anode and cathode catalysts are applied onto the membrane by well established standard techniques. For direct methanol fuel cells, platinum/ruthenium catalyst is typically used on the anode side while platinum catalyst is applied on the cathode side and platinum is applied on the cathode side. Catalysts may be optionally supported on carbon. The catalyst is initially dispersed in a small amount of water (about l00 g of catalyst in 1 g of water). To this dispersion a 5% Nafion solution in water/alcohol is added (0.25-0.75 g). The resulting dispersion may be directly painted onto the polymer membrane. Alternatively, isopropanol (1-3 g) is added and the dispersion is directly sprayed onto the membrane. The catalyst may also be applied onto the membrane by decal transfer, as described in the open literature (Electrochimica Acta, 40: 297 (1995)). The CCM is used to make MEA's. As used herein, an MEA refers to an ion conducting polymer membrane made from, a CCM according to the invention in combination with anode and cathode electrodes positioned to be in electrical contact with the catalyst layer of the CCM. The electrodes are in electrical contact with a membrane, either directly or indirectly, when they are capable of completing an electrical circuit which includes the polymer membrane and a load to which, a electric current is supplied. More particularly, a first catalyst is electrocatalytically associated with the anode side of the membrane so as to facilitate the oxidation of organic fuel. Such oxidation generally results in the formation 16 of protons, electrons, carbon dioxide and water. Since the membrane is substantially impermeable to organic fuels such as methanol, as well as carbon dioxide, such components remain on the anodic side of the membrane. Electrons formed from the electrocatalytic reaction are transmitted from the cathode to the load and then to the anode. Balancing this direct electron current is the transfer of an equivalent number of protons across the membrane to the anodic compartment. There an electrocatalytic reduction of oxygen in the presence of the transmitted protons occurs to form water. In one embodiment, air is the source of oxygen. In another embodiment, oxygen-enriched air is used. The membrane electrode assembly is generally used to divide a fuel cell into anodic and cathodic compartments. In such fuel cell systems, an organic fuel such as methanol is added to the anodic compartment while an oxidant such as oxygen or ambient air is allowed to enter the cathodic compartment. Depending upon the particular use of a fuel cell, a number of cells can be combined to achieve appropriate voltage and power output. Such applications include electrical power sources for residential, industrial, commercial power systems and for use in locomotive power such as in automobiles. Other uses to which the invention finds particular use includes the use of fuel cells in portable electronic devices such as cell phones and other telecommunication devices, video and audio consumer electronics equipment, computer laptops, computer notebooks, personal digital assistants and other computing devices, GPS devices and the like. In addition, the fuel cells may be stacked to increase voltage and current capacity for use in high power applications such as industrial and residential services or used to provide locomotion to vehicles. Such fuel cell structures include those disclosed in U.S. Patent Nos. 6,416,895, 6,413,664, 6,106,964,5,840,438, 5,773,160, 5,750,281,5,547,776, 5,527,363, 5,521,018, 5,514,487,5,482,680,5,432,021, 5,382,478,5,300,370,5,252,410 and 5,230,966. Such CCM and MEM's are generally useful in fuel cells such as those disclosed in U.S. Patent Nos. 5,945,231, 5,773,162, 5,992,008, 5,723,229,6,057,051, 5,976,725, 5,789,093, 4,612,261,4,407,905,4,629,664,4,562,123,4,789,917,4,446,210,4,390,603,6,110,613, 6,020,083, 5,480,735,4,851,377,4,420,544, 5,759,712, 5,807,412, 5,670,266, 5,916,699, 5,693,434,5,688,613,5,688,614, each of which is expressly incorporated herein by reference. In another aspect, the invention relates to methods for the preparation of the ion conducting (e.g., sulfonate) random copolymers that are useful as polymer electrolyte membranes. In general, the methods to prepare the include combining a first monomer having at least one ion conducting group such as a sulfonate group with a second comonomer. The first monomer should have at least two leaving groups and the second comonomer should have at least two groups that can displace at least one leaving group of the first monomer. A third comonomer is included that has at least two leaving groups, such that at least one of the displacing groups of the second comonomer can displace at least one of the leaving groups of the third comonomer. In a particular embodiment for the preparation of such polymers, the process further includes the step of combining a fourth comonomer having at least two displacing groups that can react with the leaving groups of either the first comonomer or the third comonomer. The term "leaving group" is intended to include those functional moieties that can be displaced by a nucleophilic moiety found, typically, in another monomer. Leaving groups are well recognized in the art and include, for example, halides (chloride, fluoride, iodide, bromide), tosyl, mesyl, etc. In certain embodiments, the monomer has at least two leaving groups, which are "para" to each other with respect to the aromatic monomer to which they are attached. The term "displacing group" is intended to include those functional moieties that can act typically as nucleophiles, thereby displacing a leaving group from a suitable monomer. The result is that the monomer to which the displacing group is attached becomes attached, generally covalentlv, to the monomer to which the leaving group was associated with. An example of this is the displacement of fluoride groups from aromatic monomers by phenoxide or alkoxide ions associated with aromatic monomers. 14 EXAMPLES Table I. Monomers Used 1) Difluoro-end monomers Acronym Full name Molecular weight Chemical structure Bis K 4,4'-Difluorobenzophenone 218.20 #STR(~0C"0~F )## BisS02 4,4'-Difluorodiphenylsulfone 254.25 ## str(F~0~f"0~F )##6 S-Bis K 3,3'-disulfonated-4,4'-difluorobenzophone 422.28 ## str(SOsNaF"OC"0_F NaOsS )## 2) Dihydroxy-end monomers Bis AF (AF or6F) 2,2-Bis(4-hydroxyphenyl) hexafluoropropane or 4,4'-(hexafluoroisopropylidene) diphenol 336.24 ## str(^_,^ CF3 a=3 )## BP Biphenol ## str( )## Bis FL 9,9-Bis(4-hydroxyphenyl)fluorene 350.41 ## str(HO~^\XjTOH## str( Bis Z 4,4'-cyclohexyliden.ebisphenol 268.36 ## str(H0~O^O-°H.)## BisS 4,4'-thiodiphenol 218.27 ## str(H 3) Dithiol-end monomers Acronym Full name Molecular weight Chemical Structure 3S 4,4'-thiol bisbenzene thiol ## str(HS^_}^S—0~SH)## Example 1 Sulfonated PEEK with Bisphenol A composition In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, Bisphenol A (9.128g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g), anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175 tol80°C for 6h. The reaction mixture was precipitated with acetone or methanol to obtain the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1,5M H2SO4 for 16hr (overnight) and then rinsed in DI water for several times until no H2S04 residue was detected. The polymer membrane was swollen in water at room temperature and the polymer membrane conductivity was measured by AC impedance. The polymer membrane was swollen in an 8M methanol aqueous mixture at 80 °C for 24 hours to measure the dimensional stability. Methanol crossover was measured in 8M MeOH using H-Cell, and the permeation rate was obtained by gas chromatography analysis. The membrane conductivity: 0.021S/cm, Swelling at 80C, 8M: 620% by area 8M-MeOH Cross-over: 6.9 x 10"7 cm2/sec. 20 Example 2 Sulfonated PEEK with 50% Bisphenol A and 50% Hydroquinone composition In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, bisphenol A (4.564g), hydroquinone (2.202g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1.5M H2SO4 for 16hr (overnight) and then rinsed in DI water for several times until no H2S04 residue was detected. The membrane conductivity: 0.027 S/cm. Example 3 Sulfonated PEEK with 4,4'-Thiodiphenol composition In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-thiodiphenol (8.728g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The membrane conductivity: 0.021S/cm 21 Example 4 Sulfonated PEEK with 4,4'-(Hexafluoroisopropyldene)diphenol composition In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-(hexafluoroisopropyldene)diphenol (13.452g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1.5M H2SO4 for 16hr (overnight) and then rinsed in DI water for several times until no H2S04 residue was detected. The membrane conductivity: O.020S/cm. Example 5 Sulfonated PEEK with 50% 4,4'-(HexafluoroisoPropyldene) diphenol and 50% Hydroquinone composition In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-(hexafluoroisopropyldene)diphenol (6.726g), hydroquinone (2.202g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1.5M H2SO4for 16hr (overnight) and then rinsed in DI water for several times until no H2SO4 residue was detected. 22 The membrane conductivity: 0.021 S/cm. Example 6 Sulfonated PEEK with 4,4'-CyclohexyIidenebisphenoI -hydroqninone composition (95/5) In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-cyclohexylidenebisphenol (10.1977gg), hydroquinone (0.2202g), 4, 4'-difluorobenzophone (6.1096g), sulfonated 4,4'-difluorobenzophone (5.0664g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1.5M H2SO4 for 16hr (overnight) and then rinsed in DI water for several times until no H2SO4 residue was detected. The membrane conductivity: 0.017S/cm, Swelling at 80C, 8M: 120% by area 8M-MeOH Cross-over: 2.4 x 10'1 cm/sec. Example 7 This example discloses a random copolymer based on 4,4'- Cyclohexylidenebisphenol(BisZ)/Sulfonated Difluorobenzophenone(SBisk)/ with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-cyclohexylidenebisphenol (10.7344gl), 4,4'-difluorobenzophenone (6.546g), sulfonated 4,4'-difluorobenzophenone (4,222g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C 21 for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The conductivity and water up-take at room temperature are listed in table below. Example 8 This example discloses a random copolymer based on 4,4'- Cyclohexylidenebisphenol(BisZ)/Sulfonated Difluorobenzophenone(SBisk)/Difluorobenzophenone(Bisk). In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-cyclohexylidenebisphenol (10.7344), 4, 4'-difluorobenzophenone (6.3714g), sulfonated 4,4'-difluorobenzophenone (4.5598g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The conductivity and water up-take at room temperature are listed in table below. Example 9 This example discloses a random copolymer based on 4,4'- Cyclohexylidenebisphenol(Bis2ySulfonated Difluorobenzophenone(SBisk)/Difluorobenzophenone(Bisk). In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-cyclohexylidenebisphenol (10.7344g), 4, 4,-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the 24 crude product, then washed with hot water four times. The conductivity and water uptake at room temperature are listed in table below. Molar Composition % (BisZ/SBisk/Bisk) Conductivity S/cm Swelling % Example 7 0.005 25 Example 8 0.007 35 Example 9 0.017 120 Example 10 Sulfonated PEEK with 20% Hydroquinone/80% 4,4'-Cyclohexylidenebisphenol In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, hydroquinone (0.8808g), 4,4'-cyclohexylidenebisphenol (8.5875g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The membrane conductivity: 0.030 S/cm, Swelling at 80C, 8M: 92 % by area 8M-MeOH Cross-over : 5.4 x 10"7 cm2/sec. 25 Example 11 Sulfonated PEEK with 50% Hydroquinone/50% 4,4'-Cyclohexylidenebispheuol In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, hydroquinone (2.202g), 4,4'-cyclohexylidenebisphenol (5.3672g), 4, 4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g), anhydrous potassium carbonate (7.2g) were dissolved in a mixture DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The membrane conductivity: 0.033S/cm, 8M-MeOH Cross-over : 4.3 x 10"7 cm2/sec. Example 12 In a 500 mL three necked round flask, equipped with a mechanical stirrer, a thermometer probe connected with a nitrogen inlet, and a Dean-Stark trap/condenser, bis(4-fluorophenyl)sulfone (BisS, 24.79 g, 0.0975 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SbisK, 22.16 g, 0.0525 mol), BisZ (40.25 g, 0.15 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of Toluene. The reaction mixture was slowly stirred under a slow nitrogen stream. After heating at ~85 °C for l h and at ~120 °C for 1 h, the reaction temperature was raised to -135 °C for 3 h, and finally to -170 °C for 2 h. After cooling to -70 °C with continuing stirring, the viscous solution was dropped into 1L of cooled methanol with a vigorous stirring. The noodle-like precipitates were cut and washed with di-water four times and dried at 80 °C overnight. The sodium form polymer was exchanged to acid form by washing the polymer in hot sulfuric acid solution (0.5 M) twice (1 h each) and in cold di-water twice. The polymer was then dried at 80 °C overnight and at 80 °C under vacuum for 2 days. This polymer has an inherent viscosity of 0.60 dl/g in DMAc (0.25 g/dl). It's one-day swelling in 8M Methanol at 80°C was 142%, cross-over in 8 M methanol was 0.009 mg.mil/cc.min.cm2 (boiled), conductivity was 0.013 S/cm (non-boiled) and 0.041 S/cm (boiled). 26 Example 13 This polymer was synthesized in a similar way as described in example 1, using following compositions: bis(4-fluorophenyl)sulfone (BisS, 22.88 g, 0.090 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SbisK, 25.34 g, 0.060 mol), BisZ (40.25 g, 0.15 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of Toluene. This polymer has an inherent viscosity of 0.67 dl/g in DMAc (0.25 g/dl). Example 14 This polymer was synthesized in a similar way a described in example 1, using the following compositions: BisK (10.69 g, 0.049 mol), 2,6-difluorobenzonitrile (5.86 g, 0.042 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 20.69 g, 0.049 mol), BisZ (37.57 g, 0.14 mol), and anhydrous potassium carbonate (25.15 g, 0.18 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 0.86 dl/g in DMAc (0.25 g/dl). Example 15 This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difiuorobenzophone (BisK, 14.18 g, 0.065 mol), 3,3'-disuIfonated-4,4'-difluorobenzophone ((SBisK, 14.78 g, 0.035 mol), 9,9-bis(4-hydroxyphenyl)fluorene (35.04 g, 0.10 mol), anhydrous potassium carbonate (17,97 g, 0.13 mol), anhydrous DMSO (180 mL) and freshly distilled toluene (90 mL). This polymer has an inherent viscosity of 0.88 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 26%, cross-over in 8 M methanol was 0.013 mg.mil/cc. minxm2 (non-boiled) and 0.016 mgimil/ccjnin.cm2 (boiled), conductivity was 0.010 S/cm (non-boiled) and 0.019 S/cm (boiled). Example 16 This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 19.64 g, 0.09 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 25.34 g, 0.06 mol), 9,9-bis(4- 21 hydroxyphenyl)fluorene (52.56 g, 0.15 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mi of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 0.77 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M meflianol at 80°C was 35%, cross-over in 8 M methanol was 0.016 mg.mil/cc.min.cm2 (non-boiled) and 0.016 mg.mil/cc.mim.cm2 (boiled), conductivity was 0.015 S/cm (non-boiled) and 0.023 S/cm (boiled). Example 17 This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 18.33 g, 0.084 mol), 3,3'-disulfonated-4,4'-difiuorobenzophone (SBisK, 23.65 g, 0.056 mol), l,l-bis(4-hydroxyphenyl)cyclohexane (BisZ, 18.78 g, 0.070 mol), 9,9-bis(4-hydroxyphenyl)fluorene (FL, 24.53 g, 0.070 mol), and anhydrous potassium carbonate (25.15 g,0.18mol), 250 mL of DMSO and 125 mL of toluene. This polymer has an inherent viscosity of 0.97 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 54%, cross-over in 8 M methanol was 0.015 mg.mil/cc.min.cm2 (non-boiled) and 0.O25 mg.mil/cc.min.cm2 (boiled), conductivity was 0.018 S/cm (non-boiled) and 0.042 S/cm (boiled). Example 18 This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 21.27 g, 0.0975 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 22.17 g, 0.0525 mol), 9,9-bis(4-hydroxyphenyl)fiuorene (FL, 26.28 g, 0.075 mol), 4,4'-dihydroxydiphenyl ether (O, 15.16 g, 0.075 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 1.21 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 50%, cross-over in 8 M methanol was 0.023 mg.mil/cc.min.cm2 (non-boiled), conductivity was 0.030 S/cm (non-boiled) and 0.O39 S/cm (boiled). 28 Example 19 This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 21.27 g, 0.0975 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 22.17 g, 0.0525 mol), BisZ (20.12 g, 0.075 mol), 4,4'-dihydroxydiphenyl ether (0,15.16 g, 0.075 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 1.61 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 117%, cross-over in 8 M methanol was 0.019 mg.mil/cc.min.cm2 (non-boiled), conductivity was 0.026 S/cm (non-boiled) and 0.057 S/cm (boiled). Example 20 This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 19.64 g, 0.09 mol), 3,3'-disuIfonated-4,4'-difluorobenzophone (SBisK, 25.34 g, 0.06 mol), 9,9-bis(4-hydroxyphenyl)fiuorene (26.28 g, 0.075 mol), 4,4'-dihydroxydiphenyI ether (15.16 g, 0.075 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 1.50 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 72%, cross-over in 8 M methanol was 0.023 mg.mil/cc.min.cm2 (non-boiled), conductivity was 0.026 S/cm (non-boiled) and 0.056 S/cm (boiled). Example 21 This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 21.27 g, 0.0975 mol), 3,3'-ch^iilfonated-4,4'-difluorobenzpphone (SBisK, 22.17 g, 0.0525 mol), 4,4'-(Hexafluoroisopropylidene)-diphenol (25.21 g, 0.075 mol), 4,4'-hydroxyphenyl ether (15.16 g, 0.075 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 1.10 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 232%, cross-over in 8 M methanol was 0.020 mg.mil/cc.min.cm2 (non-boiled) and 0.079 29 mg.mil/cc.min.cm2 (boiled), conductivity was 0.024 S/cm (non-boiled) and 0.061 S/cm (boiled). Example 22 This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (17.02 g, 0.078 mol), 3,3'-disulfonated-4,4'-difluorobenzophone ((SBisK, 17.73 g, 0.042 mol),2,5-dihydroxy-4'-methylbiphenol (MB, 24.03 g, 0.12 mol), and anhydrous potassium carbonate (21.56 g, 0.156 mol), 216 mL of DMSO and 108 mL of toluene. This polymer has an inherent viscosity of 1.07 dl/g in DMAc (0.25 g/dl). Example 23 This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (9.93 g, 0.046 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 10.34 g, 0.024 mol), 4,4'-dihydroxytetraphenylmethane (24.67 g, 0.050 mol), and anhydrous potassium carbonate (12.57 g, 0.091 mol), 126 mL of DMSO and 63 mL of toluene. This polymer has an inherent viscosity of 1.01 dl/g in DMAc (0.25 g/dl). Example 24 This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (19.85 g), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 16.47), 9,9-bis(4-hydroxyphenyl)fluorene (22.77 g), Bis Z (17.44 g) and anhydrous potassium carbonate (23.36 g), 240 mL of DMSO and 120 mL of toluene. This polymer has an inherent viscosity of 0.74 dl/g in DMAc (0.25 g/dl). Example 25 This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (19.85 g), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 16.47), 9,9-bis(4-hydroxyphenyl)fluorene (11.39 g), Bis Z (26.16 g) and JO anhydrous potassium carbonate (23.36 g), 240 mL of DMSO and 120 mL of toluene. This polymer has an inherent viscosity of 0.63 dl/g in DMAc (0.25 g/dl). Example 26 This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (19.85 g), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 16.47), 9,9-bis(4-hydroxyphenyl)fiuorene (34.16 g), Bis Z (8.72 g) and anhydrous potassium carbonate (23.36 g), 240 mL of DMSO and 120 mL of toluene. This polymer has an inherent viscosity of 1.05 dl/g in DMAc (0.25 g/dl). Example 27 In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-(l ,4-phenyldiisopropyldiene)bisphenol (17.30g), Bis K(7.0915g), S-Bis K(7.3885g),, anhydrous potassium carbonate (9.0g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 6h, then increase temperature to 173-175°C for 6h. The reaction mixture precipitates from methanol to get the rude product. Conductivity: 0.0168S/cm (0.0436 S/cm, boiled), swelling by area in 8M methanol: 67%, 8M methanol cross-over: 0.013 mg/min.ml.mls. Example 28 In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-(l,4-phenyldiisopropyldiene)bisphenol (17.30g), Bis K(7.637g), S-Bis K(6.333g), anhydrous potassium carbonate (9.0g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 6h, then increase temperature to 173-175°C for 6h. The reaction mixture precipitates from methanol to get the rude product. 30 Conductivity: 0.00786S/cm (0.0315. S/cm, boiled), swelling by area in 8M methanol: 41%, 8M methanol cross-over: 0.011 mg/min.ml.mls. Example 29 This random copolymer was synthesized in a similar way as described in example 1: BisK (14.18 g), S-BisK (14.78 g), BisAF (33.62 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). This polymer has an inherent viscosity of 1.82 dl/g in DMAc (0.25 g/dl). EEC is 1.23 meq/g. Conductivity: 0.019 S/cm (0.049 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 27%, water-uptake after boiling the membrane in water 1 hr: 31% Example 30 This random copolymer was synthesized in a similar way as described in example 1: BisK (13.09 g), S-BisK (16.89 g), BisAF (33.62 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). This polymer has an inherent viscosity of 1.18 dl/g in DMAc (0.25 g/dl). IEC is 1.38 meq/g. Conductivity: 0.030 S/cm (0.071 S/cm, boiled in water lhr), swelling by area in boiled water 1 hr: 47%, water-uptake after boiling the membrane in water 1 hr: 53% Example 31 This random copolymer was synthesized in a similar way as described in example 1 : BisK (12.0 g), S-BisK (19.0 g), BisAF (33.62 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). 32 This polymer has an inherent viscosity of 1.18 dl/g in DMAc (0.25 g/dl). IEC is 1.38 meq/g. Conductivity: 0.045 S/cm (9.088 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 73%, water-uptake after boiling the membrane in water 1 hr: 85% Example 32 This random copolymer was synthesized in a similar way as described in example 1: BisK (13.09 g), S-BisK (16.89 g), biphenol (18.62 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). IEC is 1.87 meq/g. Conductivity: 0.045 S/cm (0.071 S/cm, boiled in water lhr), The membrane became mechanically weak (tears easily) after boiling in water, so swelling and water-uptake data were not obtained properly. Example 33 This random copolymer was synthesized in a similar way as described in example 1: BisK (12.87 g), S-BisK (17.31 g), biphenol (9.81 g), BisAF (16.81 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). This polymer has an inherent viscosity of 1.30 dl/g in DMAc (0.25 g/dl). IEC is 1.62 meq/g. Conductivity: 0.045 S/cm (0.090 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 47%, water-uptake after boiling the membrane in water 1 hr : 65% Example 34 This random copolymer was synthesized in a similar way as described in example 1: BisK (11.35 g), S-BisK (20.27 g)s biphenol (11.17 g), BisAF (13.45 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). 34 This polymer has an inherent viscosity of 1.29 dl/g in DMAc (0.25 g/dl). IEC is 1.92 meq/g. Conductivity: O.063 S/cm (0.103 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 77%, water-uptake after boiling the membrane in water 1 hr: 89% Example 35 This random copolymer, was synthesized in a similar way as described in example 1: BisK (12.87 g), S-BisK (17.31 g), BisFL (7.01 g), BisAF (26.90 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). This polymer has an inherent viscosity of 1.13 dl/g in DMAc (0.25 g/dl). DEC is 1.41 meq/g. Conductivity: O.027 S/cm (0.054 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 33%, water-uptake after boiling the membrane in water 1 hr : 40% Example 36 This random copolymer was synthesized in a similar way as described in example 1: BisS02 (15.51 g), S-BisK (16.47 g), BisFL (7.01 g), BisAF (26.90 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). This polymer has an inherent viscosity of 1.07 dl/g in DMAc (0.25 g/dl). EEC is 1.30 meq/g. Conductivity: 0.018 S/cm (0.048 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 27%, water-uptake after boiling the membrane in water 1 hr: 29% Example 37 This random copolymer was synthesized in a similar way as described in example 1 : BisK (13.09 g), S-BisK (16.89 g), 4,4'-cyclohexylidenebisphenol (BisZ, 26.84 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). 34 This polymer has an inherent viscosity of 1.01 dl/g in DMAc (0.25 g/dl). IEC is 1.57 meq/g. Conductivity: 0.038 S/cm (0.064 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 33%, water-uptake after boiling the membrane in water 1 hr: 45% Example 38 This random copolymer was synthesized in a similar way as described in example 1: BisK (13.09 g), S-BisK (16.89 g), BisZ (13.42 g), BisAF (16.81 g) and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). This polymer has an inherent viscosity of 1.14 dl/g in DMAc (0.25 g/dl). BBC is 1.47 meq/g. Conductivity: 0.027 S/cm (0.075 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 41%, water-uptake after boiling the membrane in water 1 hr: 50% Example 39 This random copolymer was synthesized in a similar way as described in example 1: BisK (13.09 g), S-BisK (16.89 g), BisZ (5.37 g), BisAF (26.90 g) and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration). This polymer has an inherent viscosity of 1.08 dl/g in DMAc (0.25 g/dl). DEC is 1.42 meq/g. Conductivity: 0.027 S/cm (0.077 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 44%, water-uptake after boiling the membrane in water 1 hr: 55% Example 40 In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-Thiolbisbenezenethiol (4.5074g), 4,4'-difluorophenyl sulfone(2.7459g), sulfonated 4,4'-difluorophenyl sulfone (3.2994g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, 35 keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times. The membrane conductivity: O.088S/cm, Swelling after boiled: 98% by area, water up-take:69%. This formula is that set forth for Formula EDA where a = 0.6 and c = 0.4 Example 41 In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-Thiolbisbenezenethiol (4.5074g), 4,4'-difluorophenyl sulfone(2.9747g), sulfonated 4,4'-difiuorophenyl sulfone (2.8874g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times. The membrane conductivity: O.056S/cm, Swelling after boiled: 46% by area, water up-take:29% Example 42 In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark: trap/condenser, 4,4'-Thiolbisbenezenethiol (4.5074g), 4,4'-difluorophenyl sulfone(3.3599g), sulfonated 4,4'-difluorophenyl sulfone (3.0933g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times. 36 Example 43 In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-Thiolbisbenezenethiol (4.5074g), 4,4'-difluorophenyl sulfone(2.9747g), sulfonated 4,4'-difluorophenyl sulfone (1.8306g), 2,5-Dichlorophenyl sulfone (1.1441g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times. The membrane conductivity: 0.054S/cm, Swelling after boiled: 154% by area, water up-take:209% Example 44 In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-Thiolbisbenezenethiol (3.3805g), 2,9-dihydroxyl-fluorene (1.53g), 4,4'-difluorophenyl sulfone (2.9747g), sulfonated 4,4'-difluorophenyl sulfone (2.8874g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times. The membrane conductivity: 0.065S/cm, Swelling after boiled: 60% by area, water up-take:84% All references cited throughout the specification, including those in the background, are specifically incorporated herein by reference in their entirety. 37 Although the present invention has been described with reference to preferred embodiments, persons skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. We Claim:- 1. An ion conductive copolymer having the formula: -Ar1XiAr2X2Ar3X3)a/(Ar4-X4-Ar5-X5-Ar6-X6) b where Ar1, Ar2, Ar4, Ar5 are independently phenyl, substituted phenyl napthyl, terphenyl, aryl nitrile, substitute aryl nitrite, and Ar4 and/or Ar5 further comprise an ion conducting group, X1 and X4 are independently -C(O)- or -S(0)2, X2, X3, X5 and X6 are independently -O- or -S- and wherein at least one of X2, X3, X5 and X6 is -S-; Ar3 and Ar6 are the same or different from each other and are: ## str( CH3 _ CHj ) ## 31 +0+ f ## str( )## wherein the ion conductive groups comprise SO3', -COO", H2PO3" or sulfonimide; wherein a is between 0.0 land 0.99, b is between 0.01 and 0.99, and a + b = 1.0. 2. An ion conductive copolymer having the formula: ## str( -0+0-s-G^-0~)r/--0-rd-s-0^-GH )## Q V_^ >^W W- ,B X> f Q Where A = 0.60 and B= 0.40 3. A sulfonated copolymer having the formula ## STR( ]I )## where n and m are mole fractions, n plus m equals 1, n is between 0.1 and 0.5, m is 1 minus n, and k is between 40 and 200. 4. A proton exchange membrane (PEM) comprising the ion conductive random copolymer of claim 1 through 3. 5. A catalyst coated membrane (CCM) comprising the PEM of claim 4 wherein all or part of at least one of the opposing surfaces of said membrane comprises a catalyst layer. 6. A membrane electrode assembly (MEA) comprising the CCM of claim 5. 7. A fuel cell comprising the MEA of claim 6. 8. An electronic device comprising the fuel cell of claim 7. 9. An electric motor comprising the fuel cell of claim 7. 10. Ion Conductive random copolymers as herein described with forgoing description and figures. Dated this 13th day of May 2006. Dr. Rajeshkumar H. Acharya Advocate & Patent Agent For and on Behalf of Applicant Abstract This invention relates to ion conducting random copolymers that are useful in forming polymer electrolyte membranes used in fuel cells.

Full Text

FORM 2
THE PATENT ACT 1970
(39 of 1970)
&
The Patents Rules, 2003 COMPLETE SPECIFICATION (See section 10 and rule 13)
1. ION CONDUCTIVE RANDOM COPOLYMERS
2.
(A) POLYFUELINC.
(B) UNITED STATES OF AMERICA.
(C) 1245 Terra Bella Avenue, Mountain View,
CA 94041 USA
The following specification particularly describes the invention and the manner in which it is to be performed.
1

TECHNICAL FIELD
This invention relates to ion conductive random copolymers that are useful in forming polymer electrolyte membranes used in fuel cells.
BACKGROUND OF THE INVENTION
Fuel cells have been projected as promising power sources for portable electronic devices, electric vehicles, and other applications due mainly to their non-polluting nature. Of various fuel cell systems, the polymer electrolyte membrane based fuel cell technology such as direct methanol fuel cells (DMFCs) has attracted much interest thanks to their high power density and high energy conversion efficiency. The "heart" of a polymer electrolyte membrane based fuel cell is the so called "membrane-electrode assembly" (MEA), which comprises a proton conducting polymer electrolyte membrane (PEM), catalyst disposed on the opposite surfaces of the PEM to form a catalyst coated member (CCM) and a pair of electrodes (i.e., an anode and a cathode) disposed to be in electrical contact with the catalyst layer.
Proton-conducting membranes for DMFCs are known, such as Nation® from the E.I. Dupont De Nemours and Company or analogous products from Dow Chemicals. These perfluorinated hydrocarbon sulfonate ionomer products, however, have serious limitation when used in DMFCs. Nafion® loses conductivity when the operation temperature of the fuel cell is over 80°C. Moreover, Nafion® has a very high methanol crossover rate, which impedes its applications in DMFCs.

U.S. Patent No. 5,773,480, assigned to Ballard Power System, describes a partially fluorinated proton conducting membrane from a, b, b -trifluorostyrene. One disadvantage of this membrane is its high cost of manufacturing due to the complex synthetic processes for monomer a, J3, P-trifluorostyrene and the poor sulfonation ability of poly (a, p, P-trifluorostyrene). Another disadvantage of this membrane is that it is very brittle, thus has to be incorporated into a supporting matrix.
U.S. Patent Nos. 6,300,381 and 6,194,474 to Kerrres, et al. describe an acid-base binary polymer blend system for proton conducting membranes, wherein the sulfonated poly(ether sulfone) was made by post-sulfonation of the poly (ether sulfone).
M. Ueda in the Journal of Polymer Science, 31(1993): 853, discloses the use of sulfonated monomers to prepare the sulfonated poly(ether sulfone polymers).
U.S. Patent Application US 2002/0091225A1 to McGrath, et al. used this method to prepare sulfonated polysulfone polymers.
The need for a good membrane for fuel cell operation requires balancing of various properties of the membrane. Such properties included proton conductivity, methanol-resistance, chemical stability and methanol crossover, fast start up of DMFCs, and durability to cell performance. In addition, it is important for the membrane to retain its dimensional stability over the fuel operational temperature range. In DMFCs methanol oxidation generates enough heat to raise the cell temperature. If the membrane swells significantly, it will increase methanol crossover. The membrane thus gradually loses its ability to block methanol crossover, resulting in degradation of cell performance. The dimension changes of the membrane also put a stress on the bonding of the membrane-electrode assembly (MEA). Often this results in delamination of the membrane from the electrode after excessive swelling of the membrane. Therefore, maintaining the dimensional stability over a wide temperature range and avoiding excessive membrane swelling are important for DMFC applications.
3

SUMMARY OF THE INVENTION
In one aspect, the invention provides sulfonated random copolymer compositions which can be used to fabricate polymer electrolyte membranes (PEM's), catalyst coated membrane (CCM's) and membrane electrode assemblies (MEAs) which are useful in fuel cells.
The invention includes three classes of random ion conductive copolymers. Such random polymers are of the following formulas:
Formula I
## str(
Q
Jn
CH3
wherein R is a single bond, a cycloaliphatic of the formula CnH2n-2;
## str(

)##

wherein a, b, c and d are mole fractions of the monomer present in the copolymer where
each are independently, from 0.01 to 1;
*
Q is an ion conducting group comprising -SO3X, -COOX -PO3X or -S02-NH-S02Rf, where Rf is a prefluoronated hydrocarbon having 1-20 carbon atoms; and wherein X is a cation or a proton.
## str( Formula II

ntO-v^O^O*
Hy^h'^H.

)##
wherein Rl or R2 are independently a single bond, a cycloaliphatic of the formula CJHkn-

CH3 CF3 —s—
—O-
CH3 CF3
W //

—0-

where R3 is aryl ketone, aryl sulfone, aryl nitrile, and substituted aryl mtrile;
wherein a, b, c and d are mole fiactions of the monomer present in the copolymer where each are independently, from 0.01 to 1;
Q is an ion conducting group comprising -SO3X, -COOX -PO3X or -SOj-NH-SChRf, and wherein X is a cation or a hydrogen atom.
In another embodiment, four comonomers are used to make the ion conductive copolymer, where at least one comonomer is ion conducting. A specific embodiment is set forth in Formula III.
Formula III
-(AriXiAr2X2Ar3X3)a/-(Ar4-X4-Ar5-X5-Ar(S-X6)-b
where Ar1, Ar2, Ar4, Ar5 are independently phenyl, substituted phenyl napthyl, terphenyl, aryl nitrile, substitute aryl nitrile, and A14 and/or Ar5 further comprise an ion conducting group, Xi and X4 are independently -C(0)- or -S(0)2, X2, X3, Xs and X6 are independently-O- or-S-.
Ar3 and Ar6 are the same or different from each other and are:

\ /

CH,
CH,

\ //

6

CF,
CF.

\./

\ _/—\_J

\ rrw

CH,
\ /
\ /

\ J-°-\_J

\ y-°-Aj^°^_/

7

## str( O^^O
)##
wherein the ion conductive group comprises -S03H, -COOH, -HP03H or -S02NH-S02-RF where RF is a perfluorinated hydrocarbon having 1-20 carbon atoms and said ion conducting group are pendant to the copolymer backbone;
wherein a is between 0.0land 0.99, b is between 0.01 and 0.99, a + b = 1.0.
In some embodiments, at least one of X2, X3, X5 and/or X« is S. In some embodiments, X1 and/or X4 is -S(0)2-. In other embodiments, X1 and/or X4 is -C(0)-. m still other embodiments, X1 is -S(0)2- and X4 is -C(0)-. In other embodiments, A3 and A6 are different.
A particularly preferred embodiment is Formula IV:
fr

Formula IV
## str(

)##
Where A = 0.60 and B= 0.40
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 demonstrates the performance of DMAc containing PEM's made of the copolymers of Example 20, Example 17 and Example 22 as compared between 50 and 100% relative humidity.
DETAILED DESCRIPTION
The invention provides random copolymers that are ion conductive. One use of such polymeric material is in the formation of polymer electrolyte membranes (PEMs), catalyst coated membrane (CCM) and membrane electrode assemblies (MCA's), which may be used in fuel DMFC's fuel cells.
In one embodiment, random ion conductive copolymers can be made having the following formula:
Formula V
## str(

so,x

CH3 CF3

CH3 CFg
## str(

)##
wherein R is a bond, a cycloaliphatic of the formula CnH2n-2,
## str(

—O
\ /
—S-O
))
—S—
o .—CH5—O—
)##
Q is an ion conducting group comprising -SO3X, -COOX -PO3X or –SO2NH-SO2Rf where Rf is a perfluorinated hydrocarbon of 1 -20 carbon atoms and where X is a cation or probe.
In this copolymer, a, b, c and d are mole fractions of each of the monomers present in the copolymer where each are independently, from 0.01 to about 1. In one particular embodiment, R is isopropylidene, cyclohexylidene, 11.4 diphenylene di-isopropylene.
In general, the sulfonated copolymers include reaction products wherein (a+c)=(b+d), a is from about 0.05 to about 0.95, b is from about 0.01 to about 0.95, c is from about 0 to about 0.95 and d is from about 0 to about 0.99. Preferably, a is from about 0.10 to about 1.00, b is from about 0.05 to about 0.85, c is from about 0 to about 0.90 and d is from about 0.15 to about 0.95. Most preferably, a is from about 0.20 to about 0.9, b is from

about 0.10 to about 0.45, c is from about 0 to about 0.80 and d is from about 0.55 to about 0.90.
In another embodiment, the invention pertains to random ion conductive copolymers and proton exchange membranes having the formula:
Formula VI
wherein Ri or R2 is a single bond, a cycloaliphatic of the formula CnH-in-2,

» >
9 9
where R3 is aryl ketone, aryl sulfone, aryl nitrile, and substituted aryl nitrile.
11

wherein a, b, c and d are mole fractions of the monomer present in the copolymer where each are independently, from 0.01 to 1;
Q is an ion conducting group comprising –SO3X, -COOX -PO3X or –SO2NH-SO2Rf, where Rf is a prefluoronated hydrocarbon having 1-20 carbon atoms; and wherein X is a cation or a proton.
In the sulfonated copolymer, a, b, c and d are mole fractions for each monomer present in the copolymer, each independently from 0.01 to about 1 and X is a cation or a hydrogen atom. In a preferred embodiment, Rl is cyclohexydyl, and R2 is fluorenyl.
In general, the sulfonated copolymers include reaction products wherein (a+c)=l .00, (b+d)=1.00, a is from about 0.05 to about 1.00, b is from about 0.01 to about 1.00, c is from about 0 to about 0.95 and d is from about 0 to about 0.99. Preferably, a is from about 0.10 to about 1.00, b is from about 0.05 to about 0.85, c is from about 0 to about 0.90 and d is from about 0.15 to about 0.95. Most preferably, a is from about 0.20 to about 1.00, b is from about 0.10 to about 0.45, c is from about 0 to about 0.80 and d is from about 0.55 to about 0.90.
A particularly preferred random copolymer is:

SOsH
O—1
)##
where n and m are mole fractions and, n plus m equals 1,
n is between 0.1 and 0.5, more preferably between 0.2 and 0.4 and most preferably between 0.25 and 0.35, m is 1 minus n, and k is between 40 and 200 more preferably between 50 and 100
In a particularly preferred polymer, n is 0.3 and m is 0.7 and has the formula:

Vorff / \ too
where k is between 40 and 200.
Ion conductive polymers can also be represented by Formula HI:
Formula III
-(AriX1,Ar2X2Ar3X3)a/(Ar4-X4-Ar5-X5-Ar6-X6) b
where Ar1, AR2, AX4, Ar5 are independently phenyl, substituted phenyl napthyl, terphenyl, aryl nitrile, substitute aryl nitrile, and Ar4 and/or Ar5 further comprise an ion conducting group, X1 and X4 are independently -C(0)- or -S(0)2, X2, X3, X5 and X6 are independently -O- or -S-.
Ar3 and Ar6 are the same or different from each other and are

v./
CHj

V. /
PS

\ r-\_/

12

O-0*-^)

KM-

wherein the ion conductive groups comprise SO3', -COO", H2PO3" or sulfonimide. wherein a is between 0.0l and 0.99, b is between 0.01 and 0.99, a + b = 1.0.
A particularly preferred embodiment is Formula IV:

3+0-*-0-,-Ot
-ofo-o-

Where A = 0.60 and B= 0.40
Polymer membranes may be fabricated by solution casting of the ion conductive copolymer. Alternatively, the polymer membrane may be fabricated by solution casting the ion conducting polymer the blend of the acid and basic polymer.
When cast into a membrane for use in a fuel cell, it is preferred that the membrane thickness be between 1 to 10 mils, more preferably between 2 and 6 mils, most preferably between 3 and 4 mils.
As used herein, a membrane is permeable to protons if the proton flux is greater than approximately 0.0O5 S/cm, more preferably greater than 0.01 S/cm, most preferably greater than 0.02 S/cm.
As used herein, a membrane is substantially impermeable to methanol if the methanol transport across a membrane having a given thickness is less than die transfer of methanol across a Nafion membrane of the same thickness. In preferred embodiments the
15

permeability of methanol is preferably 50% less than that of a Nafion membrane, more preferably 75% less and most preferably greater than 80% less as compared to the Nafion membrane.
After the sulfonated random copolymer has been formed into a membrane (PEM), it may be used to produce a catalyst coated membrane (CCM). As used herein, a CCM comprises a PEM where at least one side and preferably both of the opposing sides of the PEM are partially or completely coated with catalyst layers. The catalyst is preferable a layer made of catalyst and ionomer. Preferred catalysts are Pt and Pt-Ru. Preferred ionomers include Nafion and other ion conductive polymers.
In general, anode and cathode catalysts are applied onto the membrane by well established standard techniques. For direct methanol fuel cells, platinum/ruthenium catalyst is typically used on the anode side while platinum catalyst is applied on the cathode side and platinum is applied on the cathode side. Catalysts may be optionally supported on carbon. The catalyst is initially dispersed in a small amount of water (about l00 g of catalyst in 1 g of water). To this dispersion a 5% Nafion solution in water/alcohol is added (0.25-0.75 g). The resulting dispersion may be directly painted onto the polymer membrane. Alternatively, isopropanol (1-3 g) is added and the dispersion is directly sprayed onto the membrane. The catalyst may also be applied onto the membrane by decal transfer, as described in the open literature (Electrochimica Acta, 40: 297 (1995)).
The CCM is used to make MEA's. As used herein, an MEA refers to an ion conducting polymer membrane made from, a CCM according to the invention in combination with anode and cathode electrodes positioned to be in electrical contact with the catalyst layer of the CCM.
The electrodes are in electrical contact with a membrane, either directly or indirectly, when they are capable of completing an electrical circuit which includes the polymer membrane and a load to which, a electric current is supplied. More particularly, a first catalyst is electrocatalytically associated with the anode side of the membrane so as to facilitate the oxidation of organic fuel. Such oxidation generally results in the formation
16

of protons, electrons, carbon dioxide and water. Since the membrane is substantially impermeable to organic fuels such as methanol, as well as carbon dioxide, such components remain on the anodic side of the membrane. Electrons formed from the electrocatalytic reaction are transmitted from the cathode to the load and then to the anode. Balancing this direct electron current is the transfer of an equivalent number of protons across the membrane to the anodic compartment. There an electrocatalytic reduction of oxygen in the presence of the transmitted protons occurs to form water. In one embodiment, air is the source of oxygen. In another embodiment, oxygen-enriched air is used.
The membrane electrode assembly is generally used to divide a fuel cell into anodic and cathodic compartments. In such fuel cell systems, an organic fuel such as methanol is added to the anodic compartment while an oxidant such as oxygen or ambient air is allowed to enter the cathodic compartment. Depending upon the particular use of a fuel cell, a number of cells can be combined to achieve appropriate voltage and power output. Such applications include electrical power sources for residential, industrial, commercial power systems and for use in locomotive power such as in automobiles. Other uses to which the invention finds particular use includes the use of fuel cells in portable electronic devices such as cell phones and other telecommunication devices, video and audio consumer electronics equipment, computer laptops, computer notebooks, personal digital assistants and other computing devices, GPS devices and the like. In addition, the fuel cells may be stacked to increase voltage and current capacity for use in high power applications such as industrial and residential services or used to provide locomotion to vehicles. Such fuel cell structures include those disclosed in U.S. Patent Nos. 6,416,895, 6,413,664, 6,106,964,5,840,438, 5,773,160, 5,750,281,5,547,776, 5,527,363, 5,521,018, 5,514,487,5,482,680,5,432,021, 5,382,478,5,300,370,5,252,410 and 5,230,966.
Such CCM and MEM's are generally useful in fuel cells such as those disclosed in U.S. Patent Nos. 5,945,231, 5,773,162, 5,992,008, 5,723,229,6,057,051, 5,976,725, 5,789,093, 4,612,261,4,407,905,4,629,664,4,562,123,4,789,917,4,446,210,4,390,603,6,110,613, 6,020,083, 5,480,735,4,851,377,4,420,544, 5,759,712, 5,807,412, 5,670,266, 5,916,699, 5,693,434,5,688,613,5,688,614, each of which is expressly incorporated herein by reference.

In another aspect, the invention relates to methods for the preparation of the ion conducting (e.g., sulfonate) random copolymers that are useful as polymer electrolyte membranes. In general, the methods to prepare the include combining a first monomer having at least one ion conducting group such as a sulfonate group with a second comonomer. The first monomer should have at least two leaving groups and the second comonomer should have at least two groups that can displace at least one leaving group of the first monomer. A third comonomer is included that has at least two leaving groups, such that at least one of the displacing groups of the second comonomer can displace at least one of the leaving groups of the third comonomer.
In a particular embodiment for the preparation of such polymers, the process further includes the step of combining a fourth comonomer having at least two displacing groups that can react with the leaving groups of either the first comonomer or the third comonomer.
The term "leaving group" is intended to include those functional moieties that can be displaced by a nucleophilic moiety found, typically, in another monomer. Leaving groups are well recognized in the art and include, for example, halides (chloride, fluoride, iodide, bromide), tosyl, mesyl, etc. In certain embodiments, the monomer has at least two leaving groups, which are "para" to each other with respect to the aromatic monomer to which they are attached.
The term "displacing group" is intended to include those functional moieties that can act typically as nucleophiles, thereby displacing a leaving group from a suitable monomer. The result is that the monomer to which the displacing group is attached becomes attached, generally covalentlv, to the monomer to which the leaving group was associated with. An example of this is the displacement of fluoride groups from aromatic monomers by phenoxide or alkoxide ions associated with aromatic monomers.
14

EXAMPLES
Table I. Monomers Used
1) Difluoro-end monomers

Acronym Full name Molecular weight Chemical structure
Bis K 4,4'-Difluorobenzophenone 218.20 #STR(~0*C"0~F )##
BisS02 4,4'-Difluorodiphenylsulfone 254.25 ## str(F~0~f"0~F )##6
S-Bis K 3,3'-disulfonated-4,4'-difluorobenzophone 422.28 ## str(SOsNaF"OC"0_F NaOsS )##
2) Dihydroxy-end monomers

Bis AF (AF or6F) 2,2-Bis(4-hydroxyphenyl) hexafluoropropane or 4,4'-(hexafluoroisopropylidene) diphenol 336.24 ## str(^_,^ CF3 a=3 )##
BP Biphenol ## str( )##
Bis FL 9,9-Bis(4-hydroxyphenyl)fluorene 350.41 ## str(HO~^\XjTOH## str(
Bis Z 4,4'-cyclohexyliden.ebisphenol 268.36 ## str(H0~O^O-°H.)##
BisS 4,4'-thiodiphenol 218.27 ## str(H 3) Dithiol-end monomers
Acronym Full name Molecular weight Chemical Structure
3S 4,4'-thiol bisbenzene thiol ## str(HS^_}^S—0~SH)##

Example 1
Sulfonated PEEK with Bisphenol A composition
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, Bisphenol A (9.128g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g), anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175 tol80°C for 6h. The reaction mixture was precipitated with acetone or methanol to obtain the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1,5M H2SO4 for 16hr (overnight) and then rinsed in DI water for several times until no H2S04 residue was detected.
The polymer membrane was swollen in water at room temperature and the polymer membrane conductivity was measured by AC impedance. The polymer membrane was swollen in an 8M methanol aqueous mixture at 80 °C for 24 hours to measure the dimensional stability.
Methanol crossover was measured in 8M MeOH using H-Cell, and the permeation rate was obtained by gas chromatography analysis.
The membrane conductivity: 0.021S/cm, Swelling at 80C, 8M: 620% by area
8M-MeOH Cross-over: 6.9 x 10"7 cm2/sec.
20

Example 2
Sulfonated PEEK with 50% Bisphenol A and 50% Hydroquinone composition
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, bisphenol A (4.564g), hydroquinone (2.202g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1.5M H2SO4 for 16hr (overnight) and then rinsed in DI water for several times until no H2S04 residue was detected.
The membrane conductivity: 0.027 S/cm.
Example 3
Sulfonated PEEK with 4,4'-Thiodiphenol composition
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-thiodiphenol (8.728g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times.
The membrane conductivity: 0.021S/cm
21
Example 4
Sulfonated PEEK with 4,4'-(Hexafluoroisopropyldene)diphenol composition
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-(hexafluoroisopropyldene)diphenol (13.452g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1.5M H2SO4 for 16hr (overnight) and then rinsed in DI water for several times until no H2S04 residue was detected.
The membrane conductivity: O.020S/cm.
Example 5
Sulfonated PEEK with 50% 4,4'-(HexafluoroisoPropyldene) diphenol and 50%
Hydroquinone composition
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-(hexafluoroisopropyldene)diphenol (6.726g), hydroquinone (2.202g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1.5M H2SO4for 16hr (overnight) and then rinsed in DI water for several times until no H2SO4 residue was detected.
22

The membrane conductivity: 0.021 S/cm.
Example 6
Sulfonated PEEK with 4,4'-CyclohexyIidenebisphenoI -hydroqninone composition (95/5)
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-cyclohexylidenebisphenol (10.1977gg), hydroquinone (0.2202g), 4, 4'-difluorobenzophone (6.1096g), sulfonated 4,4'-difluorobenzophone (5.0664g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The dry polymer was dissolved in DMAC for 20% coating solution. The obtained 2mil thick membrane was soaked in 1.5M H2SO4 for 16hr (overnight) and then rinsed in DI water for several times until no H2SO4 residue was detected.
The membrane conductivity: 0.017S/cm, Swelling at 80C, 8M: 120% by area
8M-MeOH Cross-over: 2.4 x 10'1 cm/sec.
Example 7
This example discloses a random copolymer based on 4,4'-
Cyclohexylidenebisphenol(BisZ)/Sulfonated
Difluorobenzophenone(SBisk)/ with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-cyclohexylidenebisphenol (10.7344gl), 4,4'-difluorobenzophenone (6.546g), sulfonated 4,4'-difluorobenzophenone (4,222g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C
21

for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The conductivity and water up-take at room temperature are listed in table below.
Example 8
This example discloses a random copolymer based on 4,4'-
Cyclohexylidenebisphenol(BisZ)/Sulfonated
Difluorobenzophenone(SBisk)/Difluorobenzophenone(Bisk).
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-cyclohexylidenebisphenol (10.7344), 4, 4'-difluorobenzophenone (6.3714g), sulfonated 4,4'-difluorobenzophenone (4.5598g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times. The conductivity and water up-take at room temperature are listed in table below.
Example 9
This example discloses a random copolymer based on 4,4'-
Cyclohexylidenebisphenol(Bis2ySulfonated
Difluorobenzophenone(SBisk)/Difluorobenzophenone(Bisk).
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-cyclohexylidenebisphenol (10.7344g), 4, 4,-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the
24

crude product, then washed with hot water four times. The conductivity and water uptake at room temperature are listed in table below.

Molar Composition % (BisZ/SBisk/Bisk) Conductivity S/cm Swelling %
Example 7 0.005 25
Example 8 0.007 35
Example 9 0.017 120
Example 10
Sulfonated PEEK with 20% Hydroquinone/80% 4,4'-Cyclohexylidenebisphenol
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, hydroquinone (0.8808g), 4,4'-cyclohexylidenebisphenol (8.5875g), 4,4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g) and anhydrous potassium carbonate (7.2g) were dissolved in a mixture of DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times.
The membrane conductivity: 0.030 S/cm, Swelling at 80C, 8M: 92 % by area
8M-MeOH Cross-over : 5.4 x 10"7 cm2/sec.
25
Example 11
Sulfonated PEEK with 50% Hydroquinone/50% 4,4'-Cyclohexylidenebispheuol
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, hydroquinone (2.202g), 4,4'-cyclohexylidenebisphenol (5.3672g), 4, 4'-difluorobenzophenone (5.6732g), sulfonated 4,4'-difluorobenzophenone (5.9108g), anhydrous potassium carbonate (7.2g) were dissolved in a mixture DMSO and toluene (about 20% solid concentration). The mixture was heated to toluene reflux with stirring, keeping the temperature at 150°C for 4h, then increasing the temperature to 175-180°C for 6h. The reaction mixture was precipitated with acetone or methanol to get the crude product, then washed with hot water four times.
The membrane conductivity: 0.033S/cm, 8M-MeOH Cross-over : 4.3 x 10"7 cm2/sec.
Example 12
In a 500 mL three necked round flask, equipped with a mechanical stirrer, a thermometer probe connected with a nitrogen inlet, and a Dean-Stark trap/condenser, bis(4-fluorophenyl)sulfone (BisS, 24.79 g, 0.0975 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SbisK, 22.16 g, 0.0525 mol), BisZ (40.25 g, 0.15 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of Toluene. The reaction mixture was slowly stirred under a slow nitrogen stream. After heating at ~85 °C for l h and at ~120 °C for 1 h, the reaction temperature was raised to -135 °C for 3 h, and finally to -170 °C for 2 h. After cooling to -70 °C with continuing stirring, the viscous solution was dropped into 1L of cooled methanol with a vigorous stirring. The noodle-like precipitates were cut and washed with di-water four times and dried at 80 °C overnight. The sodium form polymer was exchanged to acid form by washing the polymer in hot sulfuric acid solution (0.5 M) twice (1 h each) and in cold di-water twice. The polymer was then dried at 80 °C overnight and at 80 °C under vacuum for 2 days. This polymer has an inherent viscosity of 0.60 dl/g in DMAc (0.25 g/dl). It's one-day swelling in 8M Methanol at 80°C was 142%, cross-over in 8 M methanol was 0.009 mg.mil/cc.min.cm2 (boiled), conductivity was 0.013 S/cm (non-boiled) and 0.041 S/cm (boiled).
26

Example 13
This polymer was synthesized in a similar way as described in example 1, using following compositions: bis(4-fluorophenyl)sulfone (BisS, 22.88 g, 0.090 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SbisK, 25.34 g, 0.060 mol), BisZ (40.25 g, 0.15 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of Toluene. This polymer has an inherent viscosity of 0.67 dl/g in DMAc (0.25 g/dl).
Example 14
This polymer was synthesized in a similar way a described in example 1, using the following compositions: BisK (10.69 g, 0.049 mol), 2,6-difluorobenzonitrile (5.86 g, 0.042 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 20.69 g, 0.049 mol), BisZ (37.57 g, 0.14 mol), and anhydrous potassium carbonate (25.15 g, 0.18 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 0.86 dl/g in DMAc (0.25 g/dl).
Example 15
This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difiuorobenzophone (BisK, 14.18 g, 0.065 mol), 3,3'-disuIfonated-4,4'-difluorobenzophone ((SBisK, 14.78 g, 0.035 mol), 9,9-bis(4-hydroxyphenyl)fluorene (35.04 g, 0.10 mol), anhydrous potassium carbonate (17,97 g, 0.13 mol), anhydrous DMSO (180 mL) and freshly distilled toluene (90 mL). This polymer has an inherent viscosity of 0.88 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 26%, cross-over in 8 M methanol was 0.013 mg.mil/cc. minxm2 (non-boiled) and 0.016 mgimil/ccjnin.cm2 (boiled), conductivity was 0.010 S/cm (non-boiled) and 0.019 S/cm (boiled).
Example 16
This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 19.64 g, 0.09 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 25.34 g, 0.06 mol), 9,9-bis(4-
21

hydroxyphenyl)fluorene (52.56 g, 0.15 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mi of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 0.77 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M meflianol at 80°C was 35%, cross-over in 8 M methanol was 0.016 mg.mil/cc.min.cm2 (non-boiled) and 0.016 mg.mil/cc.mim.cm2 (boiled), conductivity was 0.015 S/cm (non-boiled) and 0.023 S/cm (boiled).
Example 17
This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 18.33 g, 0.084 mol), 3,3'-disulfonated-4,4'-difiuorobenzophone (SBisK, 23.65 g, 0.056 mol), l,l-bis(4-hydroxyphenyl)cyclohexane (BisZ, 18.78 g, 0.070 mol), 9,9-bis(4-hydroxyphenyl)fluorene (FL, 24.53 g, 0.070 mol), and anhydrous potassium carbonate (25.15 g,0.18mol), 250 mL of DMSO and 125 mL of toluene. This polymer has an inherent viscosity of 0.97 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 54%, cross-over in 8 M methanol was 0.015 mg.mil/cc.min.cm2 (non-boiled) and 0.O25 mg.mil/cc.min.cm2 (boiled), conductivity was 0.018 S/cm (non-boiled) and 0.042 S/cm (boiled).
Example 18
This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 21.27 g, 0.0975 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 22.17 g, 0.0525 mol), 9,9-bis(4-hydroxyphenyl)fiuorene (FL, 26.28 g, 0.075 mol), 4,4'-dihydroxydiphenyl ether (O, 15.16 g, 0.075 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 1.21 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 50%, cross-over in 8 M methanol was 0.023 mg.mil/cc.min.cm2 (non-boiled), conductivity was 0.030 S/cm (non-boiled) and 0.O39 S/cm (boiled).
28

Example 19
This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 21.27 g, 0.0975 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 22.17 g, 0.0525 mol), BisZ (20.12 g, 0.075 mol), 4,4'-dihydroxydiphenyl ether (0,15.16 g, 0.075 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 1.61 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 117%, cross-over in 8 M methanol was 0.019 mg.mil/cc.min.cm2 (non-boiled), conductivity was 0.026 S/cm (non-boiled) and 0.057 S/cm (boiled).
Example 20
This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 19.64 g, 0.09 mol), 3,3'-disuIfonated-4,4'-difluorobenzophone (SBisK, 25.34 g, 0.06 mol), 9,9-bis(4-hydroxyphenyl)fiuorene (26.28 g, 0.075 mol), 4,4'-dihydroxydiphenyI ether (15.16 g, 0.075 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 1.50 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 72%, cross-over in 8 M methanol was 0.023 mg.mil/cc.min.cm2 (non-boiled), conductivity was 0.026 S/cm (non-boiled) and 0.056 S/cm (boiled).
Example 21
This polymer was synthesized in a similar way as described in example 1, using following compositions: 4,4'-difluorobenzophone (BisK, 21.27 g, 0.0975 mol), 3,3'-ch^iilfonated-4,4'-difluorobenzpphone (SBisK, 22.17 g, 0.0525 mol), 4,4'-(Hexafluoroisopropylidene)-diphenol (25.21 g, 0.075 mol), 4,4'-hydroxyphenyl ether (15.16 g, 0.075 mol), and anhydrous potassium carbonate (26.95 g, 0.19 mol), 270 mL of DMSO and 135 mL of toluene. This polymer has an inherent viscosity of 1.10 dl/g in DMAc (0.25 g/dl). Its one-day swelling in 8 M methanol at 80°C was 232%, cross-over in 8 M methanol was 0.020 mg.mil/cc.min.cm2 (non-boiled) and 0.079
29

mg.mil/cc.min.cm2 (boiled), conductivity was 0.024 S/cm (non-boiled) and 0.061 S/cm (boiled).
Example 22
This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (17.02 g, 0.078 mol), 3,3'-disulfonated-4,4'-difluorobenzophone ((SBisK, 17.73 g, 0.042 mol),2,5-dihydroxy-4'-methylbiphenol (MB, 24.03 g, 0.12 mol), and anhydrous potassium carbonate (21.56 g, 0.156 mol), 216 mL of DMSO and 108 mL of toluene. This polymer has an inherent viscosity of 1.07 dl/g in DMAc (0.25 g/dl).
Example 23
This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (9.93 g, 0.046 mol), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 10.34 g, 0.024 mol), 4,4'-dihydroxytetraphenylmethane (24.67 g, 0.050 mol), and anhydrous potassium carbonate (12.57 g, 0.091 mol), 126 mL of DMSO and 63 mL of toluene. This polymer has an inherent viscosity of 1.01 dl/g in DMAc (0.25 g/dl).
Example 24
This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (19.85 g), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 16.47), 9,9-bis(4-hydroxyphenyl)fluorene (22.77 g), Bis Z (17.44 g) and anhydrous potassium carbonate (23.36 g), 240 mL of DMSO and 120 mL of toluene. This polymer has an inherent viscosity of 0.74 dl/g in DMAc (0.25 g/dl).
Example 25
This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (19.85 g), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 16.47), 9,9-bis(4-hydroxyphenyl)fluorene (11.39 g), Bis Z (26.16 g) and
JO

anhydrous potassium carbonate (23.36 g), 240 mL of DMSO and 120 mL of toluene. This polymer has an inherent viscosity of 0.63 dl/g in DMAc (0.25 g/dl).
Example 26
This polymer was synthesized in a similar way as described in example 1, using following compositions: BisK (19.85 g), 3,3'-disulfonated-4,4'-difluorobenzophone (SBisK, 16.47), 9,9-bis(4-hydroxyphenyl)fiuorene (34.16 g), Bis Z (8.72 g) and anhydrous potassium carbonate (23.36 g), 240 mL of DMSO and 120 mL of toluene. This polymer has an inherent viscosity of 1.05 dl/g in DMAc (0.25 g/dl).
Example 27
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-(l ,4-phenyldiisopropyldiene)bisphenol (17.30g), Bis K(7.0915g), S-Bis K(7.3885g),, anhydrous potassium carbonate (9.0g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 6h, then increase temperature to 173-175°C for 6h. The reaction mixture precipitates from methanol to get the rude product.
Conductivity: 0.0168S/cm (0.0436 S/cm, boiled), swelling by area in 8M methanol: 67%, 8M methanol cross-over: 0.013 mg/min.ml.mls.
Example 28
In a 500ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-(l,4-phenyldiisopropyldiene)bisphenol (17.30g), Bis K(7.637g), S-Bis K(6.333g), anhydrous potassium carbonate (9.0g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 6h, then increase temperature to 173-175°C for 6h. The reaction mixture precipitates from methanol to get the rude product.
30

Conductivity: 0.00786S/cm (0.0315. S/cm, boiled), swelling by area in 8M methanol: 41%, 8M methanol cross-over: 0.011 mg/min.ml.mls.
Example 29
This random copolymer was synthesized in a similar way as described in example 1: BisK (14.18 g), S-BisK (14.78 g), BisAF (33.62 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
This polymer has an inherent viscosity of 1.82 dl/g in DMAc (0.25 g/dl). EEC is 1.23 meq/g. Conductivity: 0.019 S/cm (0.049 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 27%, water-uptake after boiling the membrane in water 1 hr: 31%
Example 30
This random copolymer was synthesized in a similar way as described in example 1: BisK (13.09 g), S-BisK (16.89 g), BisAF (33.62 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
This polymer has an inherent viscosity of 1.18 dl/g in DMAc (0.25 g/dl). IEC is 1.38 meq/g. Conductivity: 0.030 S/cm (0.071 S/cm, boiled in water lhr), swelling by area in boiled water 1 hr: 47%, water-uptake after boiling the membrane in water 1 hr: 53%
Example 31
This random copolymer was synthesized in a similar way as described in example 1 : BisK (12.0 g), S-BisK (19.0 g), BisAF (33.62 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
32

This polymer has an inherent viscosity of 1.18 dl/g in DMAc (0.25 g/dl). IEC is 1.38 meq/g. Conductivity: 0.045 S/cm (9.088 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 73%, water-uptake after boiling the membrane in water 1 hr: 85%
Example 32
This random copolymer was synthesized in a similar way as described in example 1: BisK (13.09 g), S-BisK (16.89 g), biphenol (18.62 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
IEC is 1.87 meq/g. Conductivity: 0.045 S/cm (0.071 S/cm, boiled in water lhr), The membrane became mechanically weak (tears easily) after boiling in water, so swelling and water-uptake data were not obtained properly.
Example 33
This random copolymer was synthesized in a similar way as described in example 1: BisK (12.87 g), S-BisK (17.31 g), biphenol (9.81 g), BisAF (16.81 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
This polymer has an inherent viscosity of 1.30 dl/g in DMAc (0.25 g/dl). IEC is 1.62 meq/g. Conductivity: 0.045 S/cm (0.090 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 47%, water-uptake after boiling the membrane in water 1 hr : 65%
Example 34
This random copolymer was synthesized in a similar way as described in example 1: BisK (11.35 g), S-BisK (20.27 g)s biphenol (11.17 g), BisAF (13.45 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
34

This polymer has an inherent viscosity of 1.29 dl/g in DMAc (0.25 g/dl). IEC is 1.92 meq/g. Conductivity: O.063 S/cm (0.103 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 77%, water-uptake after boiling the membrane in water 1 hr: 89%
Example 35
This random copolymer, was synthesized in a similar way as described in example 1: BisK (12.87 g), S-BisK (17.31 g), BisFL (7.01 g), BisAF (26.90 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
This polymer has an inherent viscosity of 1.13 dl/g in DMAc (0.25 g/dl). DEC is 1.41 meq/g. Conductivity: O.027 S/cm (0.054 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 33%, water-uptake after boiling the membrane in water 1 hr : 40%
Example 36
This random copolymer was synthesized in a similar way as described in example 1: BisS02 (15.51 g), S-BisK (16.47 g), BisFL (7.01 g), BisAF (26.90 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
This polymer has an inherent viscosity of 1.07 dl/g in DMAc (0.25 g/dl). EEC is 1.30 meq/g. Conductivity: 0.018 S/cm (0.048 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 27%, water-uptake after boiling the membrane in water 1 hr: 29%
Example 37
This random copolymer was synthesized in a similar way as described in example 1 : BisK (13.09 g), S-BisK (16.89 g), 4,4'-cyclohexylidenebisphenol (BisZ, 26.84 g), and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
34

This polymer has an inherent viscosity of 1.01 dl/g in DMAc (0.25 g/dl). IEC is 1.57 meq/g. Conductivity: 0.038 S/cm (0.064 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 33%, water-uptake after boiling the membrane in water 1 hr: 45%
Example 38
This random copolymer was synthesized in a similar way as described in example 1: BisK (13.09 g), S-BisK (16.89 g), BisZ (13.42 g), BisAF (16.81 g) and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
This polymer has an inherent viscosity of 1.14 dl/g in DMAc (0.25 g/dl). BBC is 1.47 meq/g. Conductivity: 0.027 S/cm (0.075 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 41%, water-uptake after boiling the membrane in water 1 hr: 50%
Example 39
This random copolymer was synthesized in a similar way as described in example 1: BisK (13.09 g), S-BisK (16.89 g), BisZ (5.37 g), BisAF (26.90 g) and anhydrous potassium carbonate (16.59 g) were dissolved in a mixture of DMSO and Toluene (about 20% solid concentration).
This polymer has an inherent viscosity of 1.08 dl/g in DMAc (0.25 g/dl). DEC is 1.42 meq/g. Conductivity: 0.027 S/cm (0.077 S/cm, boiled in water l hr), swelling by area in boiled water 1 hr: 44%, water-uptake after boiling the membrane in water 1 hr: 55%
Example 40
In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-Thiolbisbenezenethiol (4.5074g), 4,4'-difluorophenyl sulfone(2.7459g), sulfonated 4,4'-difluorophenyl sulfone (3.2994g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring,
35

keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times.
The membrane conductivity: O.088S/cm, Swelling after boiled: 98% by area, water up-take:69%. This formula is that set forth for Formula EDA where a = 0.6 and c = 0.4
Example 41
In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-Thiolbisbenezenethiol (4.5074g), 4,4'-difluorophenyl sulfone(2.9747g), sulfonated 4,4'-difiuorophenyl sulfone (2.8874g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times.
The membrane conductivity: O.056S/cm, Swelling after boiled: 46% by area, water up-take:29%
Example 42
In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark: trap/condenser, 4,4'-Thiolbisbenezenethiol (4.5074g), 4,4'-difluorophenyl sulfone(3.3599g), sulfonated 4,4'-difluorophenyl sulfone (3.0933g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times.
36

Example 43
In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-Thiolbisbenezenethiol (4.5074g), 4,4'-difluorophenyl sulfone(2.9747g), sulfonated 4,4'-difluorophenyl sulfone (1.8306g), 2,5-Dichlorophenyl sulfone (1.1441g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times.
The membrane conductivity: 0.054S/cm, Swelling after boiled: 154% by area, water up-take:209%
Example 44
In a 100ml three necked round flask, equipped with a mechanical stirrer, thermometer, nitrogen inlet and Dean-Stark trap/condenser, 4,4'-Thiolbisbenezenethiol (3.3805g), 2,9-dihydroxyl-fluorene (1.53g), 4,4'-difluorophenyl sulfone (2.9747g), sulfonated 4,4'-difluorophenyl sulfone (2.8874g), anhydrous potassium carbonate (3.3g) were dissolved in a mixture DMSO and Toluene (about 20% solid concentration). The mixture was heated to toluene flux with stirring, keeping the temperature at 140°C for 4h, then increase temperature to 175°C for 6h. The reaction mixture was filtered and precipitates from methanol to get the rude product, then washed by hot water four times.
The membrane conductivity: 0.065S/cm, Swelling after boiled: 60% by area, water up-take:84%
All references cited throughout the specification, including those in the background, are specifically incorporated herein by reference in their entirety.
37

Although the present invention has been described with reference to preferred embodiments, persons skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.

We Claim:-
1. An ion conductive copolymer having the formula:
-Ar1XiAr2X2Ar3X3)a/(Ar4-X4-Ar5-X5-Ar6-X6) b
where Ar1, Ar2, Ar4, Ar5 are independently phenyl, substituted phenyl napthyl, terphenyl, aryl nitrile, substitute aryl nitrite, and Ar4 and/or Ar5 further comprise an ion conducting group, X1 and X4 are independently -C(O)- or -S(0)2, X2, X3, X5 and X6 are independently -O- or -S- and wherein at least one of X2, X3, X5 and X6 is -S-;
Ar3 and Ar6 are the same or different from each other and are:
## str( CH3 _
CHj
) ##
31

+0+
f

## str(
)##
wherein the ion conductive groups comprise SO3', -COO", H2PO3" or sulfonimide;
wherein a is between 0.0 land 0.99, b is between 0.01 and 0.99, and a + b = 1.0.
2. An ion conductive copolymer having the formula:
## str(
-0+0-s-G^-0~)r/--0-rd-s-0^-GH
)##
Q V_^ >^W W-* ,B X> f Q
Where A = 0.60 and B= 0.40
3. A sulfonated copolymer having the formula
## STR(
]I )##
where n and m are mole fractions, n plus m equals 1, n is between 0.1 and 0.5, m is 1 minus n, and k is between 40 and 200.
4. A proton exchange membrane (PEM) comprising the ion conductive random copolymer of claim 1 through 3.

5. A catalyst coated membrane (CCM) comprising the PEM of claim 4 wherein all or part of at least one of the opposing surfaces of said membrane comprises a catalyst layer.
6. A membrane electrode assembly (MEA) comprising the CCM of claim 5.
7. A fuel cell comprising the MEA of claim 6.
8. An electronic device comprising the fuel cell of claim 7.
9. An electric motor comprising the fuel cell of claim 7.
10. Ion Conductive random copolymers as herein described with forgoing
description and figures.
Dated this 13th day of May 2006.

Dr. Rajeshkumar H. Acharya Advocate & Patent Agent For and on Behalf of Applicant

Abstract
This invention relates to ion conducting random copolymers that are useful in forming polymer electrolyte membranes used in fuel cells.

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Patent Number

227323

Indian Patent Application Number

566/MUMNP/2006

PG Journal Number

10/2009

Publication Date

06-Mar-2009

Grant Date

06-Jan-2009

Date of Filing

15-May-2006

Name of Patentee

POLYFUEL INC.

Applicant Address

1245 TErra Bella Avenue, Mountain View, CA 94041 USA

Inventors:

#	Inventor's Name	Inventor's Address
1	CAO, Shuguang	# 9, 303 Chiquita Avenue Mountian View CA 94041 USA
2	NAM, Kie Hyun	#208, 1091 Tanland Drive, Palo Alto CA 94303 USA

PCT International Classification Number

H01B 1/00 ; H01M 8/00 ; H01M 8/10

PCT International Application Number

PCT/US2004/037815

PCT International Filing date

2004-11-12

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/520,266	2003-11-13	U.S.A.
2	60/545,293	2004-02-17	U.S.A.