WO2010135167A1

WO2010135167A1 - Copolyelectrolyte monomers bearing multiple acid groups

Info

Publication number: WO2010135167A1
Application number: PCT/US2010/034830
Authority: WO
Inventors: James T. Goldbach; Guillaume Breteche; Gregory J. P. Callet; Xiaobo Wan; David A. Mountz
Original assignee: Arkema Inc
Current assignee: Arkema Inc
Priority date: 2009-05-18
Filing date: 2010-05-14
Publication date: 2010-11-25
Anticipated expiration: 2011-11-18

Abstract

The invention relates to the polymerization and copolymerization of aryl-containing monomers containing two or more acid groups. These polymers and copolymers are useful as copolyelectrolytes, and can be effectively blended with other polymers to form membranes. These membranes are useful under hydrated conditions, and may find use as membranes in fuel cells, water purification, humidification and battery separators. The invention also relates to a novel means of synthesizing certain diacid aryl monomers, useful in the synthesis of the copolyelectrolytes.

Description

COPOLYELECTROLYTE MONOMERS BEARING MULTIPLE ACID GROUPS

Field of the Invention The invention relates to the polymerization and copolymerization of aryl- containing monomers containing two or more acid groups. These polymers and copolymers are useful as copolyelectrolytes, and can be effectively blended with other polymers and formed into membranes. These membranes are useful under hydrated or low-hydration conditions, and may find use as membranes in fuel cells, water purification, humidification, electrolyzers and battery separators. The invention also relates to a novel means of synthesizing certain diacid aryl monomers, useful in the formation of the copolyelectrolytes.

Background of the Invention Membranes, such as fuel cell membranes, battery membranes and water purification membranes may be exposed to very harsh acidic or basic media at temperatures that can reach 200⁰C, in an oxidizing and/or reducing environment due to the presence of metal ions and sometimes presence of solvents. This environment requires that the membrane be chemically and electrochemically resistant, as well as thermally stable.

The chemical nature of the polyelectrolyte component in a polymer blend membrane largely dictates the water swelling, hydrolytic (chemical) stability, and ion- conductive properties of the polymer blend material. Arkema scientists have found that poly electrolytes bearing a wide range of functionalities can be successfully incorporated into polyvinylidene fluoride (such as KYNAR resin) blends by carefully controlling the processing parameters utilized; providing that the polyelectrolytes bear a significant fraction of protogenic (acidic) units such as sulfonate, phosphonate, or carboxylate. The process for the polymer blending involves the conversion of the protogenic/acidic groups into a tetraalkylammonium (TAA)-neutralized form. This can be achieved through various processes; however, neutralization of the acid (protonated) form of the polyelectrolyte with an appropriate TAA hydroxide compound is commonly used. This technology is shown in US 7,396,880.

A critical limitation in the present polyelectrolyte blend materials is that the desirable proton conductivity performance declines rapidly as the local relative humidity decreases. This has implications for the use of these materials as fuel cell membranes. Constant externally applied humidification is required for the material to remain at peak performance. This constraint adds cost and complexity to the overall system and is seen as a drawback for commercial applications of these membranes into systems. The present invention solves the problem through the choice of monomeric units having two or more protogenic (acidic) functionalities for each monomer unit.

US 3,980,713 describes the dimerization of styrene disulfonic acids for use as fluorescent brighteners.

US 4,444,960 describes the reaction of aryl disulfonic acids with bisphenols to form a linear aromatic polysulfonate polymer, which is then blended with an aromatic polyester.

US 4,935,163 describes the grafting of aromatic multisulfom^'c acids to polyaniline through covalent bonds to produce conductive polymers.

US 2008/0182934 describes copolymers of aromatic diacid monomers with film forming monomers made as a latex particle for use as an ink-jet ink.

It has now been found that polyelectrolytes having more than one di-acid group per monomer unit can be used to improve the proton conductivity of polyelectrolyte membranes, even at low humidity conditions. Additionally, a novel synthesis method has been employed for the one-step synthesis of an aryl disulfonic acid, making use of this aryl disulfonic acid in polyelectrolyes commercially feasible.

Summary of the Inveniton

The invention relates to a copolymer composition useful as a copolyelectrolyte, comprising monomer units having the following general structures: A B

where: -Ar represents an aryl group, including but not limited to phenylene, naphthylene, or anthrylene, as well as substituted phenylene, naphthylene, or anthrylene;

- R₁ represents individually a proton, a fluorine atom, a substituent, or one or more sulfonate or phosphonate groups; wherein the sum of all R₁ units includes at least two sulfonate or phosphonate groups, or at least one phosphonate and at least one sulfonate group; each sulfonate or phosphonate group having associated therewith one or more positively-charged counterions, M⁺; the substituent being any C] to Cj₄ aryl group, C₁ to C_M aliphatic group, Ci to Cj₄ aliphatic ether group that is functionalized or non-functionalized; - M⁺ is a proton, alkali metal, alkali earth metal or positively charged C]_-3O organic cation;

- R₂ in both Figure A and B represents individually, a bond, a Ci to Ci₄ aryl group, Ci to C]₄ aliphatic group, Ci to C₁₄ aliphatic ether group; or the fluorinated or perfluorinated analogues thereof; - R₃ represents a functionality capable of cross-linking;

- n is the number of moles of one or more monomer units having two or more acid groups;

- m is the number of moles of one or more monomer units having at least one functional group capable of cross-linking; - p represents the number of substituents on the aryl group of monomer A, which my be the same or different;

- q represents the number of substituents on the aryl group of monomer B, which my be the same or different;

- monomer A is present in the copolymer at from 30 to 99 mole percent; - monomer B is present at from 1 to 50 mole percent; and

- n+m = 2 to 10,000.

The invention also relates to a polymer blend of this copolymer with another polymer, preferably a fluoropolymer and most preferably a polyvinylidene fluoride homopolymer or copolymer; and also to articles made from this blend. The invention further relates to a one-step process for the synthesis of disodium l-vinylphenyl-2,4-disulfonate (DSDS) in commercial quantities for use in making the copolymer of the invention. Detailed Description of the Invention

The invention relates to the polymers and copolymers of aryl-containing monomers containing two or more acid groups. These polymers and copolymers are useful as polyelectrolytes, and can be effectively blended with other polymers to form membranes. These membranes are useful under hydrated conditions, and may find use as membranes in fuel cells, water purification, humidification and battery separators. The invention also relates to a novel means of synthesizing certain diacid aryl monomers.

The copolymers of the invention contain one or more multi-acid aryl monomers (monomer A), in which each monomer unit contains two or more protogenic (acidic) functionalities. The aryl multi-acid monomers of the invention have the following general structure:

where:

-Ar represents an aryl group, including but not limited to phenylene, naphthylene, or anthrylene, as well as substituted phenylene, naphthylene, or anthrylene;

- R₁ represents individually a proton, a fluorine atom, a substituent, or one or more sulfonate or phosphonate groups; wherein the sum of all Ri units includes at least two sulfonate or phosphonate groups, or at least one phosphonate and at least one sulfonate group; each sulfonate or phosphonate group having associated therewith one or more positively-charged counterions, M⁺;

- M⁺ is a proton, alkali metal, alkali earth metal or positively charged Ci_-3O organic cation; - R₂ represents individually, a bond, a Ci to Cj₄ aryl group, Ci to Ci₄ aliphatic group, Ci to C₁₄ aliphatic ether group; or the fluorinated or perfhiorinated analogues thereof;

- n is the number of moles of one or more monomer units having two or more acid groups; - p represents the number of substituents on the aryl group of monomer A, which my be the same or different;

- monomer A is present in the copolymer at from 30 to 99 mole percent.

Useful multi-acid aryl monomers include, but are not limited to, vinylnaphthalene di sulfonic acid, vinylnaphthalene trisulfonic acid, vinylphthalocyanine tetrasulfonic acid, vinylpyrene disulfonic acid, and vinylpyrene trisulfonic acid, vinylanthracene disulfonic acid, vinylanthracene trisulfonic acid, styrene-2,4-di sulfonic acid, styrene-2, 5 -disulfonic acid, styrene-3,4-disulfonic acid, styrene-3,5-disulfonic acid, as well as the corresponding phosphonic acid, carbonic acid and boronic acid derivatives substituted for sulfonic acid.

In one preferred embodiment, the multi-acid aryl monomer contains two or more sulfonate groups. hi one embodiment, the multi-acid aryl monomer contains both sulfonate and phoshonate groups. hi the simplest form, the R₂ groups are each bonds. The styrene disulfonic acids are of this type and are a preferred embodiment, with the 2,4-diacid and 3,5- diacid being most preferred.

In another preferred embodiment, the acid-groups are separated from the aryl ring by a spacer (where R₂ is a C_M4 aryl group, C_1-H aliphatic group, Cj to Ci₄ aliphatic ether group; or the fluorinated or perfluorinated analogues thereof). This provides some steric advantages, and also provides a means for attaching more than five acid groups onto the same ring. When the spacer between the acid group and aryl is a fluorinated or perfluorinated analogue, this reduces the acidic proton pKa values causing the acid groups to take on a greater "acidic" character, making for a more effective polyelectrolyte.

In another useful embodiment a single spacer bears more than one acidic group.

Polvelectrolytc copolymers The multi-acid aryl monomers can be polymerized with other monomers to form a copolymer. The terms polymer and (copolymer, as used herein refer to polymers formed from one or more monomers. This includes homopolymers, copolymers, terpolymers and polymers formed from four or more monomers. Copolymer refers to both random and block copolymers, as well as graft copolymers. Copolymer is also used to describe a polymer resembling a copolymer which is formed by the partial reaction/substitution of some of the side groups of a homopolymer, resulting in a polymer backbone having two or more different moieties as side chains. The copolymer of the invention contains from 30 to 99 mole percent of the multi-acid aryl monomer units. The remainder of the copolymer is composed of one or more ethylenically unsaturated monomers polymerizable with the multi-acid aryl monomer(s).

In one preferred embodiment, at least one comonomer is a non-acid containing monomer having an aryl group (monomer B).

In order to facilitate cross-linking of the copolymer following formation into a final article of a polymer blend with a matrix polymer, at least one comonomer should contain a functionality making it capable of crosslinking. The copolymer will contain from 1-50 mole percent, preferably from 3 to 35 mole percent, and most preferably from 10 to 30 mole percent of monomers having a group capable of crosslinking. Preferably this is an aryl monomer. Crosslinking is desirable, since a fuel cell membrane relying on sulfonate or phosphonate functionalities for proton conduction will operate (at least part-time) in highly humidified or liquid water environments. Therefore, the hydrophilic portion(s) of the membrane material should be immobilized so as to be not lost to the environment by dissolution and/or leaching. The formation of a significant number of crosslinks serves to bind the polymer molecules together, immobilizing them, and reducing the amount of dimensional change in the overall material. The introduction of a second, typically non-sulfonated monomer into the polyelectrolyte structure can facilitate covalent cross-linking provided that it bears a functional group capable of reacting: 1) with an externally- added cross-linking agent, 2) by application of an external impetus (elevated temperature, radiation), or 3) application of both 1 and 2.

Useful functionalities providing the ability to crosslink inclide, but are not limited to alcohol, primary, secondary, and tertiary amines; N-methylol acrylamide; isobutoxy methacrylamide; N-methylenebisacrylamide; allyl groups, styryl groups; and glycidyl methacrylate. Examples of secondary cross-linkers include free and blocked isocyanates, melamines, epoxies, carboxylates, α,ω-dihaloalkanes, α,ω- dialdehydes, carboxylic acids, alkoxy silanes, silicones, aziridines, and carbodiimides. The crosslinking is typically achieved by any number of methods known to those skilled in the art. The method chosen will depend on the chemical nature and structure of the polyelectrolyte as well as the functional groups available to participate in the cross-linking reaction, hi general, it is desired that the cross-linking result in functional groups that fulfill the same requirement as were set for the rest of the copolyelectrolyte including, but are not limited to: hydrolytic, thermal, and free- radical-attack stability. In addition, it is of utmost importance that the cross-linking reaction not occur prematurely, ie. prior to film casting and formation. If this were to occur, film casting may not be possible and a non-homogeneous, non-uniform product may result. It is most preferred that the cross-linking reaction takes place by either the introduction (and activation) of an external agent, termed the 'cross-linking agent' or 'cross-linker', or by the application of an external stimulus such as heat, UV radiation, or electron beam. It is also possible that the cross-linking be afforded by a combination of these methods such as would occur for the addition of a UV-active sensitizer to the blend with subsequent UV irradiation of the film. The point at which the cross- linking occurs is of utmost importance. The reaction must be controllable such that a uniform film may be cast, with subsequent activation of the cross-linking. The application of the cross-linking may occur prior to or post drying of the wet film.

Blends

The invention relates to polymeric resin blends containing polyelectrolyte resins blended into a polymer or copolymer matrix. Specifically, the polyelectrolyte resins are (co)polymers without hydrolyzable groups. The matrix polymer is a tough, and highly chemical-resistant (co)polymer, preferably a fluoropolymer. The matrix polymer can be any of the polymers and copolymers described as the matrix in US2005077233, incorporated herein by reference. Preferably, the polymer matrix contains at least one fluoropolymer. The fluoropolymer can be a homopolymer or other type of polymer, and can be a mixture of fluoropolymers or a mixture of fluoropolymer with a non-fluoropolymer. Preferably, the fluoropolymer is a thermoplastic fluoropolymer and can form a polymer blend with the other components of a formulation, including other polymers present. Preferably, the fluoropolymer is a vinylidene fluoride polymer such as a poly(vinylidene fluoride) homopolymer. Other examples of fluoropolymers include, but are not limited to, a poly(alkylene) containing at least one fluorine atom, such as polyhexafluoropropylene, polytetrafluoroethylene, poly(vinyl fluoride), or combinations thereof. More preferably, the fluoropolymer is a polymeric composition containing from about 30% to about 100 weight % of vinylidene fluoride and from 0% to about 70 weight % of at least one poly(alkylene) containing at least one fluorine atom, such as, hexafluoropropylene, tetrafiuoroethylene, trifluoroethylene (VF3), chlorotrifrαoroethylene, and/or vinyl fluoride. Preferably, the molecular weight of the fluoropolymer which can include homopolymers, copolymers, terpolymers, oligomers, and other types of polymers is from about 80,000 MW to about 1,000,000 MW and, more preferably from about 100,000 MW to about 500,000 MW. The fluoropolymers can be prepared using the techniques described in U.S. Patent Nos. 3,051,677; 3,178,399; 3,475,396; 3,857,827; and 5,093,427, all incorporated herein in their entirety by reference.

The polymer blend of the present invention is an intimate blend of the polyelectrolyte and matrix polymer. The amount of matrix polymer can be from about 5 to about 95 weight % and the amount of the copolyelectrolyte can be from about 95 to about 5 weight %. Preferably, the matrix is a fluoropolymer at an amount of from about 20% to about 70 weight % and the amount of the copolyelectrolyte is from about 30 to about 80 weight %.

The blending process of the matrix polymer and copolyelectrolyte preferably involves first exchanging the alkali metal counterion of the polyelectrolyte to a proton (acidification) while remaining in aqueous solution. This acidified polyelectrolyte solution is then neutralized using the proper type and amount of organic counterion hydroxide. This involves the conversion of the protogem^'c/acidic groups into a tetraalkylammonium (TAA)-neutralized form. This can be achieved through various processes known in the art. Preferably the ammonium salt has a molecular weight of at least 186. Examples of suitable ammonium salts include: tetramethylammmonium, tetraethylammoniurn, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, and asymmetric- type moieties such as trioctylmethylammonium. This aqueous solution is then converted to an organic solvent solution by addition of the appropriate organic solvent that may appropriately dissolve the matrix (co)polymer of choice, with concurrent evaporation of water.

Once an organic solvent solution of organic counterion-neutralized polyelectrolyte (with low water content) is obtained, it can be combined with a separate organic solvent solution of the matrix copolymer, resulting in a homogeneous solution of both polymers. This homogeneous solution can then be processed into useful articles by standard techniques such as film casting.

Membrane Formation

Casting of the blended solution can be carried out by many different procedures familiar to those skilled in the art, such as extrusion, molding, solvent casting, and latex casting. The formed film or membrane may be used as a single layer, or may be part of a multi-layer film or membrane. A preferred method is solution casting with heating. The thickness of the formed, wet film before drying is dependent on the end- use of the material, and can vary from 1.0 μm to 2.0mm. Preferrably, the formed film has a thickness of 10.0 μm to 500.0 μm and most preferrably from 20.0 μm to 500.0 μm. This 'wet' film is then dried in a air-circulating oven at elevated temperature. The time and temperature for drying the film can vary widely. The temperature used is from 20⁰C to 250⁰C, preferrably from 100 ⁰C to 220 ⁰C, and most preferrably from 120 ⁰C to 200 °C. The drying time for the wet film can also vary widely. The oven residence time should be commercially applicable and scalable in that it can be from 1.0 s to 24 h, preferrably from 1.0 min. to 2.0 h, and most preferrably from 1.0 min. to 45.0 min. The thickness of the final, dried film depends on the original thickness of the wet film before drying. This thickness will vary depending on the application intended for the final atricle. The thickness can be from l.Oμm to 2.0mm, preferrably from 5.0μm to 500.0μm, most preferrably from lO.Oμm to 300. Oμm. The dried film is removed from the substrate by typical methods familiar to those skilled in the art. The domain size of the polyelectrolyte in a cast film should be preferably less than l.Oμm, and more preferably between lnm to 500nm. The domain sizes discussed herein are with respect to maximum domain sizes and/or average domain sizes, hi a preferred embodiment, the domain sizes recited are the maximum domain sizes, but can be the average domain sizes. The proton conductivity of the polymer blend of the invention is >10 mS/cm, preferably >50 mS/cm, and most preferably >100 mS/cm. Additionally, the polymer blend has a high degree of mechanical strength, a low swelling when hydrated, hydrolytic (chemical) stability, and a low level of sulfur loss (if sulfonated) in hot water, hot acid, oxidizing and/or reducing environments.

An article, such as a membrane, produced from the polymer blend of the invention can be used as-is or further treated by an acidic washing step to remove the tetraalkyl groups, concurrently reprotonating the ionizable groups present on the starting (co)polymer component.

The copolymer blends of the invention are useful in many applications, including, but are not limited to, films, membranes, fuel cells, coatings, ion exchange resins, oil recovery, biological membranes, batteries, and the like. The resultant articles can be utilized as perm-selective membranes for battery, fuel cell, or electrolyzer applications. In addition, the resultant articles may be applied to electrodes for the construction of a membrane-electrode-assembly, may be imbibed with various liquids, or may be introduced onto or into a reinforcing matte or porous web to increase mechanical integrity. A polymeric ion membrane or polyelectrolyte membrane can be made from the polymer blend of the present invention. The formed film or membrane may be used as a single layer, or may be part of a multi-layer film or membrane. The polymeric ion membrane can be prepared from conventional film preparation methods, such as melt extrusion, solvent cast, latex cast, and the like. Membrane electrode assemblies can be made from the membranes of the present invention and fuel cells using this membrane electrode assembly can be prepared. In using the polymers of the present invention to form membranes, the polymer can have any equivalent weight (g of polymer per mol of acid groups) and preferably has an equivalent weight of from about 200 to about 8,000, and preferably from about 200 to about 1 ,500 and even more preferably from about 200 to about 1 ,400 g/mol.

In more detail, the compositions of the present invention are especially useful in fuel cells, batteries, and the like. The design and components used in the fuel cell and batteries would be the same as in conventional fuel cells and batteries except using the compositions of the present invention in the formation of the polymeric ionic exchange membrane. Accordingly, the designs and manners of making the fuel cells and batteries as described in U.S. Patent No. 5,795,668, EP 1 202 365 Al, PCT Publication No. WO 98/22989, WO 02/075835, and WO 98/20573, Lin et al., Journal of Applied Polymer Science, Vol. 70, 121-127 (1998) can be used in the present invention and are fully incorporated herein in their entireties by reference. The membrane can be used alone or with conventional fillers, such as silica and the like. The fuel cell may use a liquid or gaseous fuel such as a liquid hydrocarbon like methanol or gas like hydrogen. The fuel cell of the present invention is capable of operating at a wide range of operating conditions. The fuel cell of the present invention can have a porous support layer and an ion exchange resin wherein the ion exchange resin is supported on at least one side of the porous support layer. The present invention can be useful in hydrogen, direct methanol, or other fuel cells. Preferably, the fuel cells of the present invention have low fuel crossover, high protonic conductivity under humidified and low-humidity conditions, and/or high mechanical strength. The thickness of the membrane can be conventional but is preferably from about 0.5 to about 10 mils and more preferably from about 0.5 mil to about 5 mils. Further, the membrane preferably has an equivalent weight of from about 200 to about 2500, and more preferably about 200 to about 1400. The porous support layer can be made from any conventional material such as a fluoro-containnig polymer or other hydrocarbon containing polymers such as polyolefin. The porous support layer has conventional parameters with respect to pore diameter, porosity, and thickness. The fuel cells of the present invention preferably have excellent proton conductivity, chemical resistance and low gas cross-over, relatively high electrical resistance, and high protonic conductivity particularly under low-humidity conditions.

Examples

Analyses and Procedures

¹H NMR analysis was carried out using a Varian Mercury 300MHz spectrometer. Samples were dried and redissolved in deuterium oxide (D₂O) and analyzed at room temperature. Monomer conversion was calculated from the integration of peaks corresponding to vinylic and polymer aromatic protons. VBA incorporation values were calculated from the integration of peaks corresponding to VBA benzylic -CH₂-O- and polymer aromatic protons.

Gel Permeation Chromatography was carried out using a Waters Alliance system equipped with a model 2695 separations module, a three-column set of 8x3OOmm columns (10⁶A, 10⁵A, 100OA; lOμm) from Polymer Source, Inc. and differential refractive index (RI) (Waters 2414) and UV (254nm, Waters 2487) detectors. A solution of 0.1 OM sodium nitrite in deionized water was used as eluent and data was evaluated using Waters Millenium software relative to a calibration with sulfonated polystyrene narrow standards (10-point calibration encompassing a range of l.Okg/mol to 1,000 kg/mol).

All polymer solutions were cast into membrane using a Mathis LTE Labdryer. The casting substrate was 2 mil thick aluminum foil with approximate dimensions of 15x12 inches. Approximately 15g of polymer solution was spread on the foil and drawn down to a wet film thickness of 200-300 microns using a doctor blade. The dry membranes were then removed from the oven and cooled to room temperature. The thickness of the dried membranes was 20-50 microns. The conductivity on all membranes was measured using the following procedure. Membrane samples boiled in 18 MΩ deionized water for one hour. After cooling, the membranes were mounted in four point probe conductivity cells with 0.5 mm platinum wire. Impedance .data was collected at 70⁰C in 18 MΩ deionized water using a Gamry PC4/300 potentiostat connected to a 6 channel multiplexor. Conductivity was calculated using dimensions of the sample, inner electrode distance of the conductivity cell, and the sample impedance at 1000Hz (conductivity=inner electrode distance/(impedance*sample thickness* sample width).

Synthesis of diacid monomers Several methods for obtaining multi-acid aryl monomers are provided below.

Based on these examples, and synthesis methods known in the art, one of ordinary skill in the art can envision other synthesis schemes to produce the same or similar multi-acid aryl monomers.

Example 1: l.l-Diisopropyl-diphosphonato-2-f4-vinylphenyl) ethane

A 3 L 3 -neck flask equipped with addition funnel was purged with dry nitrogen, dried by heat gun and cooled under nitrogen. To the flask was added 300 mL toluene and sodium metal (16.89 g, 0.734 mol). Tetraisopropyl methylenediphosphonate (250.0 g, 0.726 mol, 0.99 eq) was added dropwise and the contents were stirred until all sodium was consumed (18h). Vinylbenzyl chloride (VBC) (91.4 mL/99.6 g, 0.653 mol, 0.9 eq) was added dropwise over 45 min and the mixture was stirred at 60° C for 18 h. After confirming complete consumption of VBC by ¹H NMR spectroscopy, the contents were cooled to room temperature and poured into water. After separation, the aqueous layer was extracted with two times each with 250 mL methylene chloride. The organic fractions were combined, washed with brine and dried with MgSO₄. After removal of solvent, a yellow oil was obtained (311.5 g). Structure was as expected by ¹H NMR, including -7% tetraisopropyl methyl enediphosphonate remaining as impurity.

Example 2: 2-(4-vmylphenyl) ethane- 1,1-dipho aphonic acid

A round-bottom flask was heat-gun dried under nitrogen purge and cooled under dry nitrogen. 0.664g of l,l-diisopropyl-diphosphonato-2-(4-vmylphenyl) ethane (13036-35) was dissolved in 5.OmL of dichloromethane and added to the flask. 1.14g (0.97mL, 5.0eq., 7.45mmol) of trimethylsilyl bromide (TMSBr) was added dropwise over two minutes and the contents were sealed and stirred for 18h. Dichloromethane and TMSBr were evaporated under vacuum, then 10.OmL of deionized water was added to the remaining viscous oil and shaken for 10 min. A white powder formed which was filtered and dried in vacuo. The powder was analyzed by ¹H NMR in DMSO-d6 solvent at 25⁰C and 80⁰C and was found to be the desired product with a small amount of unhydrolyzed TMS-phosphonate ester remaining.

Example 3 : (Mono-, di-, tri-, and terra-) Sodium 2-(4-vinyiρhenyl) ethane- 1.1- diphosphonate

2-(4-vinylphenyl) ethane-l,l-diphosphonic acid can be readily converted to the mono-

, di-, tri-, or tetra-neutralized salt form by reaction with an appropriate molar amount of base relative to the molar amount of phosphonate. A typical example is as follows: 1.Og (3.425mmol) of 2-(4-vinylphenyl) ethane- 1,1-diphosρhonic acid is dissolved in 2OmL of acetone. 0.137g (3.425mmol) of vacuum-dried sodium hydroxide is dissolved in 1.Og of deionized water. The sodium hydroxide solution is added dropwise to the acetone solution of 2-(4-vinylphenyl) ethane-l,l-diphosphonic acid and stirred at room temperature for 1 hour during which time a white precipitate forms. This precipitate is collected by filtration, and and additional quantity of white precipitate is recoved upon evaporation of the solvent. The precipitates were combined and dried at room temperature in vacuum. In total, 1.03g (95% of theoretical) of mono sodium 2-(4-vinylphenyl) ethane- 1,1-diphosphonate was isolated. The di-, tri-, and tetrasodium analogues of 2-(4-vinylphenyl) ethane- 1,1 -diphosphonic acid were produced following a similar procedure with the exception of increasing the amount of sodium hydroxide used to 6.850, 10.275, and 13.700mmol respectively.

Example 4: Dipotassium l-vinylphenyl-2,4-disulfonate (OPDS)

To a 2L 3 -necked round bottom flask equipped with a mechanical stirrer and an internal temperature container, were charged 100.0 g of 2,4-di sulfonic acid benzaldehyde disodium salt (0.322 mol), 345.5 g methyltriphenylphosphonium bromide (0.967 mol) and 134.1 g K₂CO₃ (0.967 mol). 700 mL anhydrous DMSO was then added with stirring to form a slurry. The mixture was heated at 110 ⁰C for 24 h with vigorous stirring. The mixture was then cooled to room temperature. The inorganic solid was carefully removed by filtration and around 800 mL clear DMSO solution was collected. This solution was gradually poured into 4L of acetone at room temperature to form a white precipitate, and the precipitate was filtered and washed four times with 300 mL of acetone each. The precipitate was then dried under reduced pressure to give 90.9 g of pure product (0.295 mol, 91% yield). The product was found to be greater than 90% in the potassium-ion form by elemental analysis.

This one-step process could be practiced on a commercial scale. The reaction generally using the following steps: a) admixing 2, 4-di sulfonic acid benzaldehyde di-metalic salt, (preferably di- sodium salt), methyltriarylphosphonium halide (preferably Br, Cl, I, F), a base and solvent to a reactor to form a slurry. The solvent could be an organic solvent or even water depending on the salt forms of the reactants. b) heating the admixture with vigorous stirring for an effective amount of time for the reaction to occur. Generally the heating is above 80 ⁰C and preferably above 9O⁰C. For good reaction yield, the stirring will take at least 30 minutes, and more likely several hours to several days. c) cooling the mixture, preferably to room temperature. d) separating the dipotassium l-vinylphenyl-2_?4-di sulfonate solid from the solvent. This can conveniently be done by filtration, or other separation techniques, e) optionally washing and/or purifying said dipotassium 1 -vinylphenyl-2,4- disulfonate, such as by precipitation, to remove impurities. f) then drying the dipotassium l-vinylphenyl-2,4-disulfonate solid under vacuum with heating or other appropriate drying method.

Example 5: Disodium l-vinylphenyl-2,4-disulfonate (DSDS)

To a 22L 3-necked round bottom flask equipped with a mechanical stirrer and an internal temperature container, were charged 2000.0 g of 2,4-disulfonic acid benzaldehyde disodium salt (6.452 mol), 3460.0 g methyltriphenylphosphonium bromide (9.692 mol) and 4230.0 g of trisodium phosphate (25.793 mol) that was previously dried in vacuo at 100^αC. 12.0 L of anhydrous dimethylsulfoxide (DMSO) was then added with stirring to form a slurry. The mixture was heated at 110 ⁰C for 20 h with vigorous stirring. A 2.OmL sample was removed, filtered and added to 5OmL of acetone to form a white precipitate. ¹H NMR analysis of this sample revealed that 3.0% of the aldehyde starting material remained unreacted. 21Og (0.588mol) of methyltriphenylphosphonium bromide was then added and the mixture was heated at 110 ⁰C for 5 hours. The mixture was then cooled to room temperature. The inorganic solid was carefully removed by filtration and 6000 mL of clarified DMSO solution was collected. The solid filter cake was then washed five times with 2.0L, 1.0L, 1.0L, LOL, and 2.0L each of anhydrous DMSO. A total of 18.6L of filtrate was collected. The entire procedure was then repeated, generating multiple batches of DMSO filtrates. Filtrates collected from the initial reaction filtration were combined and totaled 16.6L (Solution 'A'). Filtrates collected from the first and second filter cake washings were combined and totaled 12. IL (Solution 'B'). Filtrates from the third, fourth and fifth filter cake washings were combined and totaled 7.5L (Solution 'C) for a grand total of 36.2L of DMSO solution of product. A 200L glass reactor was then charged with 170L of acetone. With vigorous stirring, the 16.6L of Solution 'A' was added over a period of 1 hour during which time, a large amount of white precipitate formed. This solution was filtered, and a large amount of wet filter cake was recovered. The reactor was again charged with 170L of acetone, and Solution 'B' was added over a period of 1 hour, during which time a large amount of white precipitate formed. This solution was filtered, and a large amount of wet filter cake was recovered.

A 120L polypropylene batch can was then charged with 5OL of anhydrous ethanol. The filter cakes obtained from Solutions 'A' and 'B' were added to the ethanol with vigorous stirring to form a thick slurry. This slurry was stirred at room temperature for 24 hours. The slurry was filtered and then dried in vacuo at 35 ⁰C for 24 hours resulting in recovery of 3.25 kg of DSDS product (82.3% yield). The product was found to be 100% in the sodium-ion form by elemental analysis. IH NMR analysis revealed peaks characteristic of the desired DSDS monomer as well as <1.0 mol-% of residual starting materials as impurities.

This one-step process could be practiced on a commercial scale. The reaction generally using the following steps: g) admixing 2,4-disulfonic acid benzaldehyde di-metalic salt, (preferably di- sodium salt), methyltriarylphosphonium halide (preferably Br, Cl, I, F), a base and solvent to a reactor to form a slurry. The solvent could be an organic solvent or even water depending on the salt forms of the reactants. h) heating the admixture with vigorous stirring for an effective amount of time for the reaction to occur. Generally the heating is above 80 ⁰C and preferably above 9O⁰C. For good reaction yield, the stirring will take at least 30 minutes, and more likely several hours to several days, i) cooling the mixture, preferably to room temperature, j) separating the disodium l-vinylphenyl-2,4-disulfonate solid from the solvent. This can conveniently be done by filtration, or other separation techniques, k) optionally washing and/or purifying said disodium l-vinylphenyl-2,4- disulfonate, such as by precipitation, to remove impurities. 1) then drying the disodium l-vinylphenyl-2,4-disulfonate solid under vacuum with heating or other appropriate drying method.

Polymerization Examples

Example 6: Copolymerization of sodium vinylbenzyl sulfonate (NaVBS) and vinylbenzyl alcohoKVBA^

This copolymer example is included for reference for following Example 20 for the preparation of blends of two polyelectrolytes with matrix copolymers. To a 22L round bottomed flask equipped with a heating mantle, mechanical stirrer thermocouple and nitrogen inlet was added 2000.Og NaVBS, 304.2g VBA, 7715. Ig deionized water and 0.7714g VAZO 56. This mixture was vigorously sparged with nitrogen for 15 minutes with stirring. It was then heated to 80 ⁰C for 5.5 hours. 1.05g of VAZO 56 was then added and the mixture was heated at 80 ⁰C for an additional 6 hours. 7.8Og of VAZO 56 was added and the mixture was heated at 80 ⁰C for and additional 12 hours then cooled to room temperature. ¹H NMR analysis revealed that >99% of the monomer was reacted and peaks corresponding to the expected copolymer structure were observed. The poly(NaVB S -co- VB A) polyelectrolyte was ion-exchanged to proton counterion form, neutralized and solvent switched as described in the following-Examples 16-18. The neutralized poly(VBS-co-VBA) in NMP solution was then used for blending into polyelectrolyte/matrix (co)polymer blends and cast into films as described below.

Example 7: Homopolvmerization of 2-(4-vinylphenyl) ethane- 1,1-diphosphonic acid (VPEDPA)

To a 5OmL round bottomed flask was added 1.Og of VPEDPA, 10.Og of DMSO, and 0.1 Og of azobisisobutyronitrile (AIBN). This mixture was stirred and vigorously sparged with nitrogen for 10 minutes. It was then heated to 65 ⁰C for 6 hours. The reaction mixture was then added to 20OmL of a 1 :1 mixture of tetrahydrofuran and acetone, producing of a white precipitate (0.9Og after drying in vacuo). ¹H NMR analysis of the dried precipitate revealed no residual VPEDPA and contained peaks characteristic of the desired product, poly(VPEDPA).

Example 8: Homopolvmerization of DSDS

0.7Og of DSDS was added to 2.Og deionized water in a 1OmL round bottomed flask. 19.0mg of VAZO 56 was added and this mixture was sparged with nitrogen for

15 minutes with stirring. This mixture was heated to 65 ⁰C for 16 hours then cooled to room temperature. The reaction mixture was then added to 5OmL of acetone, producing 0.6Og of a white precipitate. This precipitate was filtered and dried in vacuo. Aqueous gel permeation chromatography analysis revealed that the poly(DSDS) product had a weight average molecular weight (Mw) of 450.8 kg/mol and polydispersity index of 2.4. ¹H NMR analysis revealed a monomer conversion of >99%.

Example 9: Copolymerization of DSDS with sodium styrenesulfonate (SSNaI

To a 25OmL, three-necked round-bottom flask equipped with heating mantle and mechanical stirrer, was added 100.Og of deionized water, 7.49g (24.2 mmol) of DSDS, 5.Og (24.2 mmol) of sodium styrene sulfonate (NaSS), and 0.152g VAZO 56. This mixture was vigorously sparged with nitrogen for 10 minutes. The reaction mixture was then heated to 65 ⁰C. After 70 minutes at this temperature, the polymerization mixture was cooled to room temperature. ¹H NMR analysis revealed that >75% of the monomers had been reacted and GPC analysis revealed a weight average molecular weight in excess of 1,000 kg/mol and polydispersity -2.4.

Example 10: Copolymerization of DSDS with 4-vinylbenzyl alcohol (VBA)

To a 12L, three-necked round-bottom flask equipped with heating mantle, mechanical stirrer, and feed inlets for VBA and initiator was added 6.60L of deionized water and 1500.Og of DSDS. This mixture was vigorously sparged with nitrogen for 60 minutes. 54.4Og of 4-vinylbenzyl alcohol (VBA) was added along with 0.2476g of VAZO 56. This mixture was vigorously sparged with nitrogen for an additional 30 minutes with stirring. The reaction mixture was then heated to 75 ⁰C. After one hour at 75 ⁰C (herein denoted as 'time T), 91.42g of VBA was fed into the reaction mixture over 25 minutes ('time 1 ' + 25min.) using a mechanical piston- type pump. Heating at 75 ⁰C was continued for an additional one hour ('time 1 ^* + Ih 25min) at which point VBA was fed into the reactor at a rate of 7.0 mL/hour for a total of four hours ('time 1 ' + 4h). Concurrently, starting at 'time V, VAZO 56 (6.0 wt.-% aqueous solution) was added to the reaction mixture at a rate of 2.86mL/h for two hours ('time 1 ' + 2h), then increased to 5.72mL/h for two hours (time T + 4h), then increased to 8.57mL/h for two hours (time ' 1 ' + 6h).

At 'time 1 + 6h' 10.OmL of VBA was added to the reactor and the reaction mixture was stirred at 75 ⁰C for 4 additional hours ('time 1' + 1Oh) then cooled to room temperature for 12 hours ('time 1' + 22h). It was then heated to 75 ⁰C, and stirred for an additional 8 hours ('time 1' + 30h). ¹H NMR analysis of the product revealed greater than 95% of the DSDS and VBA had been reacted to form the desired product of poly(DSDS-coVBA) copolymer with a total incorporation of VBA units equal to 23.1 mol.-% of the total. Aqueous gel permeation chromatography analysis revealed that the poly(DSDS-co-VBA) had a weight average molecular weight (Mw) of 352.5 kg/mol and polydispersity index of 4.7.

Example 11: Copolymerization of DSDS with 4-vinylbenzyl alcohol (VBA)

To a 12L, three-necked round-bottom flask equipped with heating mantle, mechanical stirrer, and feed inlets for VBA and initiator was added 4.989L of deionized water and 1250.Og of DSDS. This mixture was vigorously sparged with nitrogen for 60 minutes. 45.58g of 4-vinylbenzyl alcohol (VBA) was added along with 0.52Og of VAZO 56. This mixture was vigorously sparged with nitrogen for an additional 30 minutes with stirring. The reaction mixture was then heated to 75 ⁰C. After one hour at 75 ⁰C (herein denoted as 'time 1 ')_> 60.42g of VBA was fed into the reaction mixture over 3 hours ('time 1 ' + 3h.), then 30.21g of VBA was fed into the reaction mixture over 3 hours ('time 1 ' + 6h) using a syringe pump. Concurrently, starting at 'time V, VAZO 56 (as a 7.5 wt.-% aqueous solution) was added to the reaction mixture at a rate of 0.2577g/h for two hours ('time 1^* + 2h), then increased to 0.5155g/h for two hours (time T + 4h), then increased to 0.6870g/h for two hours ('time 1' + 6h). The reaction mixture was then cooled to room temperature for 18 hours ('time V + 2Ah). It was then heated to 75 ⁰C, and an additional 6.8Og of VAZO 56 was added. Heating was continued for 5 hours then it was allowed to cool to room temperature again.

¹H NMR analysis of the product revealed greater than 97% of the DSDS and VBA had been reacted to form the desired product of poly(DSDS-co-VBA) copolymer with a total incorporation of VBA units equal to 19.3 mol.-% of the total. Aqueous gel permeation chromatography analysis revealed that the poly(DSDS-co- VBA) had a weight-average molecular weight (Mw) of 221.6 kg/mol and polydispersity index of 5.2.

Example 12: Terpolymerization of DSDS with SSNa and VBA

(3:1:1 mol:mol:mol) poMDSDS-co-NaSS-co-VBA)

To a 25OmL, three-necked round-bottom flask equipped with heating mantle, mechanical stirrer, and feed inlets for VBA 71.Og of deionized water and 15.Og of DSDS and 2.5 Ig of sodium styrene sulfonate (NaSS). This mixture was vigorously sparged with nitrogen for 10 minutes. 0.55g of 4-vinylbenzyl alcohol (VBA) was added along with 0.025Og of VAZO 56. This mixture was vigorously sparged with nitrogen for an additional 10 minutes with stirring. The reaction mixture was then heated to 75 ⁰C. After one hour at 75 ⁰C (herein denoted as 'time V), 1.08g of VBA was fed into the reaction mixture over 6 hours ('time 1 ' + 3h.), then 30.21g of VBA was fed into the reaction mixture over 3 hours ('time 1 ' + 6h) using a syringe pump. Concurrently, starting at ('time V + Ih), 0.03OgVAZO 56 was added to the reaction mixture, at ('time 1' + 3h) and additional 0.02Og VAZO 56 was added, at ('time I' + 5h) 0.03Og of VAZO 56 was added. The reaction mixture was then heated for 2 additional hours and cooled to room temperature for 18 hours ('time 1 ' + 24h). It was then heated to 75 ⁰C, and an additional O.0650g of VAZO 56 was added. Heating was continued for 5 hours then it was allowed to cool to room temperature again.

¹H NMR analysis of the product revealed greater than 98% of all monomers had been reacted to form the desired product of poly(DSDS-ct?-NaSS-cσ-VBA) copolymer with a total incorporation of VBA units equal to 20 mol.-% of the total. Aqueous gel permeation chromatography analysis revealed that the poly(DSDS-co- NaSS-co-VBA) had a weight- average molecular weight (Mw) of 329.4 kg/mol and polydispersity index of 5.8.

Example 13: Terpolvmerization of DSDS with SSNa and VBA f2:2:l mol:mol:mon polvfDSDS-co-NaSS-coVBA)

This copolymer was synthesized in a manner identical to that of the (3:1 :1) variant described above with the exception that the amounts of DSDS and NaSS were 10.54gDSDS and 7.051g NaSS, respectively.

¹H NMR analysis of the product revealed greater than 98% of all monomers had been reacted to form the desired product of poly(DSDS-coNaSS-co-VBA) copolymer with a total incorporation of VBA units equal to 20 mol.-% of the total. Aqueous gel permeation chromatography analysis revealed that the poly(DSDS-co- NaSS-co-VBA) had a weight-average molecular weight (Mw) of 376.3kg/mol and polydispersity index of 6.6.

Example 14: Terpolvmerization of DSDS with SSNa and VBA

(1:3:1 mol:mol:moD polvfDSDS-co-NaSS-co-VBA)

This copolymer was synthesized in a manner identical to that of the (3:1:1) variant described above with the exception that the amounts of DSDS and NaSS were

10.54g DSDS and 21.15Og NaSS, respectively, and 128.Og of deionized water was used in the initial reactor charge.

¹H NMR analysis of the product revealed greater than 98% of all monomers had been reacted to form the desired product of poly(DSDS-cσ-NaSS-co-VBA) copolymer with a total incorporation of VBA units equal to 20 mol.-% of the total.

Aqueous gel permeation chromatography analysis revealed that the poly(DSDS-co

NaSS-co-VBA) had a weight- average molecular weight (Mw) of 414.4 kg/mol and polydispersity index of 4.5.

Example 15: Copolymerization of DSDS with Sodium 2-(4-vinylphenyl) ethane-1,1- diphosphonate

To a 10OmL, three-necked round-bottom flask equipped with heating mantle and mechanical stirrer, was added 25.Og of deionized water, 1.Og of DSDS, 1.Og of sodium styrene sulfonate (NaSS), and 0.055g VAZO 56, This mixture was vigorously sparged with nitrogen for 10 minutes. The reaction mixture was then heated to 75 ⁰C. After 180 minutes at this temperature, the polymerization mixture was cooled to room temperature. ¹H NMR analysis revealed that >90% of the monomers had been reacted and GPC analysis revealed a weight average molecular weight of 135.0 kg/mol and polydispersity of 3.1.

Example 16: Ion-Exchange of Polyelectrolytes to Acid Form

Ion-exchange of any of the polyelectrolytes described in this document is possible in order to exchange the acid counterions to protons (ie. acidify, or 'protonate') using an acidic ion-exchange resin such as DOWEX Marathon C (Dow Chemicals, Inc.) or other strongly acidic ion-exchange resin as known in the art. An example is provided here for poly(DSDS-cσ-VBA) synthesized in Example 11 above, but the procedure can be scaled up or down and applied to other water-soluble polyelectrolytes as necessary and as described in US 7396880B2 (Goldbach, etaL). A glass column with flow-controlling stopcock at the bottom of 6 inch inside diameter and 48 inches in length was charged with 9.5kg of DOWEX Marathon C ion-exchange resin. This resin was washed with deionized water until the pH of the eluent was measured to be greater that 5.5 as determined by pH paper (EM Sciences, pH range 0-14). 6.20kg of the poly(DSDS-co-VBA) solution as described above was added to the column and allowed to drain through the ion-exchange resin bed over a period of three hours. After three hours, an overpressure of lOpsi of nitrogen was applied to force the remainder of the solution through the column. The viscous, acidic solution was collected. 4.0L of deionized water was then added and again an overpressure of lOpsi of nitrogen was applied to force the remainder of the solution through the column. The viscous, acidic solution was collected and combined with the previously-collected solution. A total of 11.50kg of viscous, acidic, aqueous solution was collected.

Example 17: Neutralization of Acidic Polvelectrolyte Solutions

Acidic aqueous solutions of the polyelectrolytes described herein are produced by the ion-exchange process described above. It can be advantageous to neutralize these solutions with a base to exchange the proton counterions for metal or organic counterions. The particular nature and amount of the base chosen will determine the nature and amount of the counterion, and can vary widely, particularly as described in US7396880B2, US7629426 and will be obvious to those skilled in the art.

A general example is as follows. This procedure can be scaled-up or down, or alternate bases or aqueous solutions of bases can be used as required:

9176.6g of aqueous, acidic poly(DSDS-co-VBA) solution was added to a 22L round bottom flask equipped with a thermocouple, addition funnel, and electronic pH probe. 2659.8g of tetrapropylammonium hydroxide (55.0 wt.-% solution, Sachem,

Inc.), equivalent to 90.05% of the total acid in solution was added slowly maintaining the temperature of the solution below 31 ⁰C. The final pH of the solution was 2.54.

Example 18: Solvent Exchange of Neutralized Polvelectrolyte Solutions

It can be advantageous to exchange neutralized, aqueous solutions to an organic solvent for further processing or blending with additional materials. The particular nature of the solvent chosen will be determined by the nature of the further processing or blending required, but will typically be a polar aprotic solvent such as dimethylsulfoxide (DMSO), N,N'-dimethylacetamide (DMAc), N₅N'- dimethylformamide (DMF) or N-methylpyrrolidone (NMP) as known in the art and particularly as described in US7396880B2, US7629426.

A general example is as follows and can be scaled-up or down as required: 18.OL of poly(DSDS-cσ-VBA) having previously subjected to ion-exchange to proton form, then neutralized with an aqueous tetraalkylammonium hydroxide solution as described above was charged into a 22L round bottom flask equipped with heating mantle, mechanical stirrer, temperature probe and nitrogen inlet. To this solution was added 1.0L of N-methylpyrrolidone (NMP). This mixture was heated to 80 ⁰C and exposed to rapid flow of dry nitrogen. As the level of solution decreased, NMP was added to return the solution to its original level. This process was continued until the solution contained less than 1 OOOppm of water as determined by Karl-Fischer titration at which point the solution was cooled to room temperature for further application in formulation, blending with other (co)polymers, and film casting.

Blending / Formulation / Film Casting Examples

Example 19: Membranes Comprised of Styrene Disulfonic Acid Polvelectrolyte and KYNAR Polv(vinylidene fluoride) Resin

Two membrane compositions were made in this example from the polyelectrolyte described in Example 11 containing 81 mole % sulfonated monomer and 19 mole % VBA. The polyelectrolyte was ion- exchanged, reneutralized and solvent switched as described in Examples 16-18. The solids content of the polyelectrolyte/l-methyl-2-pyrrolidone (NMP) solution was determined to be

16.0wt.-% as was determined by measuring the mass loss from 5.Og of solution heated to 185⁰C for 60 minutes.

For the first composition, 3Og of the polyelectrolyte solution in NMP was combined with 19.8g of a 21.0wt.-% solution of KYNAR poly(vinylidene fluoride)

(PVDF - Arkema Inc.) 2801 in NMP. 1.19g of a 50.0wt.-% solution of TRIXENE Bl

7982 in NMP and 0.47g of a 10.0wt.-% solution of FASCAT 4202 in NMP was also added to the solution. The components were mixed together for 20 hours using ajar rolling mill. The solution was cast into a membrane using the film preparation procedure and dryer apparatus as described above. The solution was dried at 185°C for 10 minutes using a blower speed of 2000 rpm.

The membrane was released from the aluminum foil substrate by immersing it in deionized water. The membrane was then exchanged to the proton form by immersing it in 3 liters of 5M aqueous sulfuric acid. The acid was heated to 80-85⁰C at a rate of 40°C/hr and held in this temperature range for 1 hour. The membrane was then removed from the acid and the was washed with deionized water until the pH of the water was >4.0. This membrane was determined to have a proton conductivity of 210mS/cm.

The second composition was made by combining 30. Ig of the polyelectrolyte solution with 14.2g of a 21wt.-% solution of KYNAR PVDF 2801 in NMP. 1.21g of a 50wt.-% solution of TRIXENE Bl 7982 in NMP and 0.47g of a 10.0 wt.-% solution of FASCAT 4202 in NMP was also added to the solution. The components were mixed together, cast into membrane, released from the substrate, and exchanged to the proton form as described for the first composition. The membrane was found to have a proton conductivity of 250mS/cm.

Example 20: Membrane Blends Comprised of Polyelectrolytes and KYNAR Polyfvinylidene fluoride) Resin

Three membrane compositions were made using the polyelectrolyte from Example 11 containing 81 mole % sulfonated monomer and 19 mole % VBA and a polyelectrolyte of sodium vinylbenzyl sulfonate and VBA (poly(VBS-cø-VBA)) which was synthesized as described in Example 6 and in US 7,396,880. Both polyelectrolytes were ion-exchanged, reneutralized and solvent switched as described in Examples 16-18. The solids content of the neutralized poly(VBS-co-VBA)/NMP solution was 29.5wt.-% and was determined by measuring the mass loss from 5.Og of solution heated to 185°C for 60 minutes. The three membrane compositions were prepared from solutions mixed in proportions described in the Table below. After all of the components were combined, each solution was stirred for several hours using mechanical agitation.

Solution is identical to the one described m Example 19

Each solution composition was cast into membrane, released from the substrate, and exchanged to the proton form using the same procedures described in Example 19. The proton conductivities for compositions 1, 2, and 3 were determined to be 163, 162, and 203 mS/cm, respectively.

Example 21 : Membrane Comprised of a Polyelectrolyte Terpolymer and KYNAR Polyfvinylidene fluoride) Resin

The polyelectrolyte described in Example 12 containing a mole ratio of 3:1 :1 DSDS:NaSS:VBA was used in this example as a 8.0 wt% aqueous solution after ion- exchange to the protonated form. The acid content of the solution was determined by combining approximately 1 gram of the polyelectrolyte solution with 49g of deiomzed water and titrating it to a phenolphthalein endpoint with 0.1 ON aqueous potassium hydroxide solution (KOH). Approximately 90.0 mole % of the acid groups were neutralized in 71.Og of the polyelectrolyte solution using 16.Og of 41.1 wt% aqueous tetrapropylammomum hydroxide solution. 47.2g of NMP was added to the neutralized solution. The water in the solution was removed using a rotary evaporator to produce a polyelectrolyte/NMP with a mass of 55.Og.

21.2g of the polyelectrolyte/NMP was combined with 19.5g of a 21wt.-% solution of KYNAR PVDF 2801 in NMP containing 0.644g of TRIXENE Bl 7982 and 0.0455g of FASCAT 4202. The components were blended together for several hours using a mechanical stirrer. The membrane was cast, released from the substrate, and exchanged to the acid form using the same procedures described in Example 19. The membrane was determined to have a proton conductivity of 171mS/cm. Example 22: Membranes Comprised of a Polyelectrolyte Terpolymer and KYNAR Pol yfvinylidene fluoride) Resin

The polyelectrolyte described in Example 13 containing a mole ratio of 2:2:1 DSDS:NaSS:VBA was used in this example after ion-exchange to the protonated form as a 6.8 wt% aqueous solution. The acid content of the solution was determined by combining 1.Og of the polyelectrolyte solution with 49g of deionized water and titrating it to a phenolphthalein endpoint with 0.10N aqueous KOH. About 95 mole % of the acid groups were neutralized in 28.9g of the polyelectrolyte solution using 5.39g of 41.1 wt. -% aqueous tetrapropylammoniurn hydroxide solution. 16.Og of NMP was added to the neutralized solution. The water in the solution was removed using a rotary evaporator to produce a polyelectrolyte/NMP with a mass of 18.5g.

14.5g of the polyelectrolyte/NMP solution was combined with 13.7g of a 21wt.-% solution of KYNAR PVDF 2801 in NMP containing 0.487g of TRIXENE Bl 7982 and 0.0333g of FASCAT 4202. The components were blended together for several hours using a mechanical stirrer. The membrane was cast, released from the substrate, and exchanged to the acid form using the same procedures described in Example 19. The membrane was found to have a proton conductivity of 171mS/cm.

Example 23: Membranes Comprised of a Polyelectrolyte Terpolymer and KYNAR Polyfvmylidene fluoride) Resin

The polyelectrolyte described in Example 14 containing a mole ratio of 1 :3:1 DSDS:SS:VBA was used in this example after ion-exchange as a 10.3wt.-% aqueous solution. The acid content of the solution was determined by combining 1.0 gram of the polyelectrolyte solution with 49g of deionized water and titrating it to a phenolphthalein endpoint with 0.1 ON KOH. About 95 mole % of the acid groups were neutralized in 60.12g of the polyelectrolyte solution using 15.4g of 41.1 wt-% aqueous tetrapropylammonium hydroxide solution. 47.9g of NMP was added to the neutralized solution. The water in the solution was removed using a rotary evaporator to produce a polyelectrolyte/NMP with a mass of 56.7g.

17.6g of the polyelectrolyte/NMP solution was combined with 17.2g of a 21.0wt.-% solution of KYNAR PVDF 2801 in NMP containing 0.662g of TRTXENE Bl 7982 and 0.0391g of FASCAT 4202. The components were blended together for several hours using a mechanical stirrer. The membrane was cast, released from the substrate, and exchanged to the acid form using the same procedures described in Example 19. The membrane was determined to have a proton conductivity of 158mS/cm.

Example 24: Membranes Comprised of Styrene Disulfonic Acid Polyelectrolvte and KYNAR Polv(vinylidene fluoride) Resin

The polyelectrolvte described in Example 10 containing 77 mole % DSDS and 23 mole% VBA was used in this example after ion-exchange treatment to the proton counterion form as a 10.7wt.-% aqueous solution. The acid content of the solution was determined by combining approximately 1 gram of the polyelectrolvte solution with 49g of deionized water and titrating it to a phenolphthalein endpoint with 0.1 ON KOH. About 90 mole % of the acid groups were neutralized in 40.Og of the polyelectrolvte solution using 12.4g of 41.1 wt% aqueous tetrapropylammonium hydroxide solution. 35.9g of NMP was added to the neutralized solution. The water in the solution was removed using a rotary evaporator to produce a polyelectrolyte/NMP with a mass of 43.6g.

41.9g of the polyelectrolyte/NMP solution was combined with 36.5g of a 21.0wt.-% solution of KYNAR PVDF 2801 in NMP containing 1.16g of TRIXENE Bl 7982 and 0.0856g of FASCAT 4202. The components were blended together for several hours using a mechanical stirrer. The membrane was cast, released from the substrate, and exchanged to the acid form using the same procedures described in Example 19. The membrane was determined to have a proton conductivity of 208mS/cm.

Claims

What is claimed is:

1. A copolymer composition comprising monomer units having the following general structures: A B

where:

-'Ar' represents an aryl group, including but not limited to phenylene, naphthylene, or anthrylene, as well as substituted phenylene, naphthylene, or anthrylene; - R₁ represents individually a proton, a fluorine atom, a substituent, or one or more sulfonate or phosphonate groups; wherein the sum of all Ri units comprises at least two sulfonate or phosphonate groups, or at least one phosphonate and at least one sulfonate group; each sulfonate or phosphonate group having associated therewith one or more positively-charged counterions, M⁺; - M⁺ is a proton, alkali metal, alkaline earth metal or positively charged Ci_-3O organic cation;

- R₂ in both Figure A and B represents individually, a bond, a Ci to Cj₄ aryl group, Ci to Ci₄ aliphatic group, Ci to Ci₄ aliphatic ether group; or the fluorinated or perfluorinated analogues thereof; - R₃ represents a functionality capable of cross-linking

- n+m - 2 to 10,000.

2. The copolymer composition of claim 1, wherein said M⁺ is ammonium, alkyl ammonium, phosphonium, sulfonium, imidazolium, triazolinium, tetraazolinium, pyridinium, pyrimidinium, piperidinium or morpholinium.

3. The copolymer composition of claim 1 wherein said R₃ functionality capable of cross-linking is an alcohol, amine, unsaturated aliphatic, isocyanate, epoxide, or alkyl halide.

4. The copolymer composition of claim 1 wherein R₂ represents only bonds.

5. The copolymer composition of claim 1, wherein Ri comprises at least two sulfonate groups.

6. The copolymer composition of claim 1, wherein at least any one Ri itself comprises two sulfonate groups, or two phosphonate groups.

7. The copolymer composition of claim 4, wherein said monomer A is either disodium l-vinylphenyl-2,4 disulfonate or disodium l-vinylρhenyl-3,5-disulfonate.

8. The copolymer composition of claim 1, wherein at least two of the groups R₂ are selected from the group consisting of alkyl, fluoroalkyl or perfluoroalkyl.

9. The copolymer composition of claim 5, wherein said at least two sulfonate groups are bound to at least two alkyl, fluoroalkyl, or perfluoroalkyl groups from Rg through

Rl2.

10. The copolymer composition of claim 1, wherein on monomer B, group R₂ is a C₁. ₁₆ alkyl and R₃ is alcohol.

11. The copolymer composition of claim 1, wherein said copolymer further comprises one or more additional ethylenically unsaturated monomers copolymerizable with monomers A and B.

12. A polymer blend comprising from 5 to 95 weight percent of said polymer composition of Claim 1 with from 5 to 95 weight percent of a matrix polymer.

13. The polymer blend of claim 12, wherein said polymer composition of claim 1 comprises a blend of at least two different sulfonated polyelectrolytes, each comprising from 5 to 95 weight percent of said blend.

14. The polymer blend of Claim 12, wherein said matrix polymer is fluorinated.

15. The polymer blend of Claim 14, wherein said matrix polymer comprises a poly(vinylidene fluoride) homopolymer or copolymer.

16. The polymer blend of Claims 14 within said matrix copolymer is poly(vinylidene fluoride-cohexafruoropropylene).

17. An article comprising the polymer blend of claiml2.

18. The article of Claim 16 comprising a membrane, fuel cell, humidification device, electrolyzer, water purification device, battery, ion exchange resin or dental adhesive.

19. A process for forming disodium l-vinylphenyl-2,4-disulfonate (DSDS) comprising the steps of: a) admixing 2,4-disulfonic acid benzaldehyde di-metalic salt, methyltriarylphosphonium halide, a base and solvent to a reactor to form a slurry; b) heating the admixture with vigourous stirring for an effective amount of time for the reaction to occur; c) cooling the mixture; d) separating the disodiuml-vinylphenyl-2,4-disulfonate solid from the solvent; e) optionally washing and/or purifying said disodium l-vinylρhenyl-2,4- disulfonate; f) drying the disodium l-vinylphenyl-2,4-disulfonate.