WO2010096027A1

WO2010096027A1 - Fluorochloro ionomers

Info

Publication number: WO2010096027A1
Application number: PCT/US2008/073505
Authority: WO
Inventors: Huey-Shen Wu
Original assignee: Huey-Shen Wu
Priority date: 2009-02-18
Filing date: 2009-02-18
Publication date: 2010-08-26

Abstract

This invention discloses novel fluorochloro ionomers and processes of making them. The first preferred body of invention is perfluorochloro ionomers having (1) equivalent weight between 600 and 1500, preferably between 800 and 1200, and most preferably between 900 and 1100; (2) chlorine content between 8 % and 30 % by weight. These ionomers are breathable and excellent barrier materials, capable of being processed into thin films or membranes and are well suited for low humidity or high temperature fuel cell applications and for chemical protective covering materials. The second preferred body of invention is partially fluorochloro ionomers having (1) moisture vapor permeability rate > 3000 gram H₂O/m2/day (about 1/2 mil thick film); (2) chlorine content of between 10 % and 39 % by weight. These ionomers are breathable and excellent barrier materials that can also be processed into thin films or membranes and are suited for some fuel cell applications and more preferably for breathable protective covering applications. The membranes can be monolithic films or multi-layers films, or composite films, or bipolar membranes. These novel fluorochloro ionomers are made by radical copolymerization of at least one fluorochloro monomer and at least one comonomer consisting of at least ionic group or at least one precursor that can be converted to ionic groups such as acid groups or amines or quaternary amine groups. The said fluorochloro monomer containing at least one fluorine and at least one chlorine atom is free radical polymerizable including chlorotrifluoroethylene (CFCl=CF₂) and dichlorodifluoroethylene (CFCl=CFCl).

Description

DESCRIPTION OF PCT/US2008/073505

FLUOROCHLORO I ONOM ERS

RELATED APPLICATION

This application claims the benefit of and priority to US Patent Application No. 1 1/894,061, filed August 20. 2007. the disclosure of which is incorporated herein by reference as if set forth in its entirty.

FIELD OFTHE INVENTION

This invention relates to fluorochloro ionomcrs, and specifically to fluorochloro iononicrs of high ionic conductivity, low methanol crossover rate, relatively low hydration and that can be processed into thin films. The fluorochloro ionomcrs arc preferably fluorochloro compounds suitable for applications where reasonably high ionic conductivity in low humidity environments and good barrier properties at high humidity is desirable. One major application is in solid polymer electrolyte fuel cells. Another major application is for protective covering against noxious liquids and gases.

BACKGROUND OF THE INVENTION

Tlic concept of using an ion-cxchangc membrane as an electrolyte separator for polymer electrolyte membrane (PEM) fuel cells was first introduced by General Electric in 1955. However, a real breakthrough in PEM fuel cell technology occurred in the mid- 1960s, after DuPont introduced Nafion membrane, a pcrfluorosulfonic acid (PFSA) membrane. Due to their inherent chemical, thermal, and oxidative stability, pcrfluorosulfonic acid membranes displaced unstable polystyrene sulfonic acid membranes. Even today, Nafion membranes and other related pcrfluorosulfonic acid membranes arc considered to be the state of the art for PEM fuel cell technology. Although perfluorosulfonic acid membrane structures are preferred, structural improvements are still needed to accommodate the increasing demands of fuel cell systems for specific applications. Higher performance, lower cost, greater durability, better water management, the capability to perform at higher temperatures, and flexibility in operating with a wide range of fuels arc some of the challenges that need to be overcome before widespread commercial adoption of the technology can be implemented.

Tlic membrane electrolyte in PEM fuel cells plays two critical roles: effectively separating both fuel and oxidant, preventing mixing: and transporting protons from the anode to the cathode to complete the redox reaction chemistry. This means that the membrane electrolyte should provide strong mechanical, chemical, and electrochemical stability and low gas permeability over a wide range of operating conditions. In addition, membranes arc required to have high proton conductivity at low to medium temperatures (sub-zero to 9O⁰C). Usually, an ionic conductivity of 90-100 mS/cm is an acceptable and useful range for several applications in the portable, stationary, and mobile classifications, with membrane thicknesses ranging from 20 micron to 200 micron. Thicker membranes arc currently preferred, due to the desire for less fuel crossover (in portable applications) and greater durability over 40,000 hours (in stationary applications). Transportation applications require thinner membranes to achieve higher power density with a durability of over 5000 hours. Today, PFSA membranes are the membranes of choice for PEM fuel cell systems, since their robustness, durability, and well-balanced physicochcmicaJ properties top general PEM requirements. Among the known PEM membranes (fluorinatcd and non-fiuorinated), Nafion membrane has been considered the benchmark material against which most results arc compared.

Tlic development of PFSA membranes has a long and rich history dating to the discovery of poly(tetrafluoroeth\ lene) (PTFE) in 1938. Nafion membrane was originally developed for chlor-alkali applications in early 1962, and later the functional group of the side chain was modified from a weaker acid to a stronger acid to suit fuel cell applications. As mentioned earlier, its first use in a fuel cell was in 1966 with its successful demonstration in NASA^'s space program. Φ

Nafion resin is a copolymer of TFE (tctrafluoroethylenc) and vinyl ether

[perfluoro (4-methyi-3,6-dioxa-7-octcne-l -sulfonyl fluoride)| (PSEPVE). Its chemical structure in non-ionic form is shown in Structure 1. Upon further chemical treatment with a base, followed by an acid, the polymer is converted from a non-conducting film (-SO2F form) to a highly conducting (-SO3H form) ionomer membrane.

TFE + PSEPVE -» -(CF2CF2)m-(CFCF2)-

O-CF2CF(CF3)-O-CF2CF2-SO2F (1) (m is about 3- 1 1, depending upon various grades.)

After hydrolysis by a base and acidification by an acid, it becomes

-(CF2CF2)m-(CFCF2)-

O-CF2CF(CF3)-O-CF2CF2-SO3H

The pcrfluorinatcd backbone (PTFE like) imparts superior chemical and thermal stability to non-fluorinated polymers. The pendant sulfonic acid (-SO3H) group imparts super acidic characteristics for facile proton transport. The acid capacity or membrane equivalent weight (EW), of the membrane is determined by the composition of the vinyl ether and can be typically produced from 0.67-1.25 milli-equivalents per gram, corresponding to 1500-800 EW. The proton conductivity of the membrane is strongly dependent on the water content in the membrane structure. The acid capacity strongly affects the water uptake; therefore, the conductivity of the final membrane, as shown in Table 1 (published in WO 00/52060 PCT Patent application). An EW range from 800- 1 100 is preferred for all the practical fuel cell applications considered today because it produces the maximum ionic conductivity.

Table I: Water Uptake and Ionic Conductivity for Nafion® Membranes valent Weight(g/eq| ) Water Uptake(\vt %) Ionic Conductivity' at 23° C(S

1500 13.3 0.0123

1350 19.4 0.0253

1200 21.0 0.0636

1 100 25.0 0.0902

980 27.1 0.1 193

834 53.1 0.1 152 785 79.1 0.0791

The successful demonstration of PEM fuel cell operation with Nafion membranes has stimulated other fluoropolymcr producers to develop stable PFSA membrane structures. Asahi Kasci Corp. (formerly Asahi Chemical), Asahi Glass Co.. and Dow Chemical Co. introduced Aciplcx , Flemion , and Dow membranes, respectively. A chemically inert PTFE like backbone is common to all of these membranes_,: however, their side-chain structures are slightly different, as described in Table II. All of the membranes are currently available in the commercial market except the Dow membrane, which is no longer offered.

Table II: Typical Functional Monomers of Perfluorosulfonic Acid Membranes

Membrane Type Monomer Structure Nafion®, Flemion® CF2=CFO-CF2CF(CF3)-O-CF2CF2-SO2F Aciplex® CF2=CFO-CF2CF(CF3)-O-CF2CF2 CF2-SO2F Dow CF2=CFO-CF2CF2-SO2F

Membranes based on neat PFSA ionomcr have a tendency to swell undesirably when exposed to water, leading to poor handling and mechanical properties. This issue becomes more severe with thinner membrane structures, especially at elevated temperatures. In the early 1980s, reinforcement technologies were developed to improve the mechanical stability and durability of perfluorinated membranes, aiming at chlor- alkali electrolysis applications. PTFE-bascd woven fabrics and micro fibrils were widely used for reinforcement, for their chemical inertness and excellent compatibility w ith fluorinatcd ionomer structures. In 1995. W.L. Gore & Associates introduced the Gorc-

Sclcct membrane, which is a micro-reinforced composite structure of expanded PTFE and perfluorosulfonic acid ionomcr. A more robust and thinner membrane, as thin as 5 micron, was produced by this technique, allowing the fuel cell to achieve high power without sacrificing longevity and durability. Alternatively, Asahi Glass Co. introduced a thin, flat PTFE fibril-reinforced PFSA membrane with good mechanical strength and performance. A continuous-film production facility has been established that uses a newly developed process. In addition, a large number of research groups arc actively engaged in modifying existing PFSA membrane structures to further improve membrane functionality and durability while retaining the base membrane properties. Both physical and chemical modifications have been explored. These include impregnation of PFSA membranes with phosphoric and sulfuric acids: inorganic materials, namely, zirconium (hydrogen) phosphate and silica; and the development of blend composite membranes such as ionically cross-linked acid-base membranes, PFSA/polybcnzimidazolc, and perfluorinated composite membrane structures.

Tlic instant invention relates to fluorochloro ionomcrs made from copolymerization of fluorochloro monomers,, which form polymeric backbone, and comonomcrs consisting of ionic groups or precursors which can be converted to ionic groups such as acid groups or amines or quaternary amine groups. The said fluorochloro monomers are preferably perfluorochloroethyelene. Good examples include chlorotrifluorocthylcnc (CFC1=CF2) and dichlorodifluorocthylenc (CFCl=CFCl) and the like. Chlorotrifluorocthylenc is most preferred, because of its case and safe of handling far superior to tctrafluorocthylcne which is dangerously explosive. Furthermore, poly(chlorotrifluoroethylene) PCTFE has been demonstrated as the best barrier polymer against permeation of organics including methanol, far better than any known perfluorinated polymers. In fact, the barrier properties of PCTFE are 10 to 100 times better than those of PTFE or FEP for oxygen. CO2 and HCl. The most famous brand of such PCTFE barrier membrane has been Honeywell (now GE Plastics) AclonCΦ barrier membrane, wherein oxygen, moisture and organics all have the lowest crossover rate compared to any known plastic films. It is quite unexpected that a membrane electrolyte based on PCTFE backbone could exhibit superior barrier property against methanol crossover than PTFE backbone. Furthermore, PCTFE has also been demonstrated far stronger than PTFE in mechanical strength, which is also critical for control of undesirable membrane swollen with better water management. The combination of fluorine and chlorine in the polymeric backbone makes surprising improvement over PFSA ionomers and other ionomers. PCTFE maintains its useful service temperatures over a very broad temperature range (-100° C to 200° C). PCTFE has comparable mechanical strength and durability to Nylon and possesses excellent impact resistance at ambient and sub-ambient temperature. PCTFE also possesses low flame spread and low smoke generation characteristics.

G as Permeability of PCTFE v. FEP (PTFE like) Films

Film Type (I mm) Moisture O2 Nj CO2

PCTFE 0.171 0.47 0.17 1.1

FEP 2.75-3.44 50-70 20-27 110-190

Moisture unit: kg/m².hr

O2, N2, CO2: m\mm/m² MPa

Direct methanol fuel cells (DMFC) offer high energy, compact power that is required to power numerous electronic devices for extended mission times. DMFC technology would benefit greatly with the advent of a PEM that maintains high proton conductivity under conditions of low humidity while also inhibiting methanol permeability. Swelling of the PEM due to high solvent uptake can compromise mechanical integrity and promote methanol diffusion through the membrane. A PEM that is a good proton conductor under conditions of low humidity would help to minimize these effects. Our PCTFE based polymer electrolytes unexpectedly have the advantage of improved internal water management and ion conductivity and reduced methanol crossover. Internal water balance within the PCTFE based polymer electrolyte membrane could enhance water management, and alleviate the need to recycle water formed at the cathode.

As used herein the acid form of an ionomcr means that substantially all the ion exchange groups, e.g., -SO3H sulfonic groups, -COOH carboxylic acid groups, and phosphonic acid groups are protonated. One important parameter used to characterize ionomcrs is the equivalent weight. Within this application, the equivalent weight (EW) is defined to be the weight of the polymer in acid form required to neutralize one equivalent of NaOH. Lower EW means that there are more active ionic species (e.g., protons) present. If it takes more NaOH to neutralize the ionomcrs, there must be more active ionic species within the polymer. Because the ionic conductivity is generally proportional to the number of active ionic species in the polymer, one would therefore like to lower the EW in order to increase conductivity.

Lowering the equivalent weight has previously not been a very succcssftil approach to making useful membranes, due to the physical weakness of tctrafluoroethylcnc backbone of current PSFA ionomcrs. As the equivalent weight goes down, the amount of water (or solvent) that the polymer absorbs goes up. The amount of water absorbed by the polymer is called the degree of hydration or hydration. It is expressed as the weight percent of water absorbed by the polymer after immersion in room temperature water for such as two hours. A higher degree of hydration is desirable up to a point because it tends to increase the ionic conductivity of the membrane. Correspondingly, lowering the degree of hydration has traditionally meant decreasing the conductivity. But there is a limit to the amount of water or solvent such that PFSA ionomer membranes can contain. If too much water is present, the film may lose much of its physical integrity, becoming gel-like with little rigidity and may completely disintegrate. In addition, depending un the polymer composition, low EW PFSA ionomers may even partially or completely dissolve in water Furthermore, even if the films were mechanically stable, too high a hydration would tend to dilute the number of ions present for conduction, thereby lowering the ionic conductivity. Thus, there is an optimal degree of hydration that is high enough to provide the highest conductivity, while not so high that the films become mechanically unstable when hydrated.

Various approaches have been used to improve this limitation. In U.S. Patent number: 5,654,109, 5,246,792, 5,981,097, 6,156,451, and 5,082,472, various forms of composite membranes were mentioned. Although each of these approaches may offer some improvement over a monolithic single layer PFSA ionomer membrane, they all involve the use of rather complex, composite, multilayer structures that are difficult and expensive to process. Our invented fluorochloro ionomers surprisingly improves the problem perhaps due to mechanically stronger fluorochloro polymeric backbone and low swelling when hydrated. Fluoropolymer ionically conducting membranes have been utilized in many different applications. One application that has been widely used is as chlor-alkali electrolytic cell membranes for the electrolysis of sodium chloride, for example, in U.S. Patent number: 4,358,545, 4,417,969, 4,478,695 and 6, 156.451. Additionally, this generic class of polymers, described as fluoropolymer ionomers, has been proposed for use as coatings as described in US. Pat. No. 4,661,41 1: as wire insulation such as in WO 90/15828; as replacements for acid catalysts, primarily in organic synthesis as described in "Pcrfluorinatcd Resin sulfonic Acid (Nafion-H©) Catalysis in Synthesis", by Olah, G. A.. Iyer P. S. and Surya P. G. K,. in Journal: Synthesis (Stuttgart), 1986 (7) 513 531, and in "Perfluorinated Resin sulfonic acid (Nafion-H) Catalysis in Organic Synthesis" by Yamato, T., in Yuki Gosci Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, volume 53. number 6, June 1995, p 487 499; as a membrane for water electrolysis as described in Yen, R. S., McBreen, J., Kissel, G., Kulesa, F. and Srinivasan, S. in the Journal of Applied Electrochemistry, volume 10, pg. 741, 1980, as a membrane for clcctrowinning as described, for example, in "The Use of Nation-415 Membrane in Copper Elcctrowinning from Chloride Solution" by Raudscpp, R., and Vreugdc. M., in CIM Bulletin. 1982, V75, N842. P 122; as a tube to continuously and very selectively dry wet gas streams (sec product literature from Pcrma Pure, Inc., Toms River, N. J.); in metal ion recover)' systems as described in product literature of Nafion® perfluorinated membrane case histories, DuPont Company, Polymer Products Department, Wilmington, Del. 19898; and as components in polymer electrolyte membrane (PEM) fuel cells. In the latter case, they can function both as the electrolyte or a component thereof, for example as described in by Bahar ct.al. in U.S. Patent number 5,547,551 and 5,599.614; and/or as a component in one or both of the electrodes of the MEA. DuPont Nafion® perfluoro ionomer films have also been demonstrated as a good barrier to chemical agents (US Patent No. 4,515,761 ); however, it has not been commercial for protective covering application due to its extremely high cost.

When ionomers (ion conducting polymers) arc used as the electrolyte in PEM fuel cells, they conduct protons from one electrode to the other. A common problem associated with such fuel cells is that contaminants such as carbon monoxide tend to poison the catalysts used in the MEA. These contaminants can interfere with the flow of ions between the electrodes and thus degrade the performance of the fuel cell. One way to reduce the effect of carbon monoxide is to operate the fuel cell at an elevated temperature. This reduces the formation and/or increases the destruction rate of potential contaminants and thereby allows more efficient electrode performance. The problem with running at high temperatures, however, is that it vaporizes liquid water within the fuel cell, and in so doing, tends to reduce the degree of hydration in the membrane. As described above, decreasing the hydration lowers the ionic conductivity, thereby reducing the efficiency of ion transport through the membrane and adversely affecting fuel cell operation. In fact, at lower temperatures, in PEM fuel cells using conventional ionomers, the incoming gas streams are usually wcll-humidificd in order to maintain a relatively high degree of hydration Only by adding the additional water in the form of humidity in the gases can the hydration be kept high enough to allow efficient fuel cell operation for long period of time. However, as the temperature gets close to, or above, the boiling point of water this approach becomes difficult and ineffective. Thus, an ionomcr with relatively low hydration and acceptably high ionic conductivity would require less ambient water to function as the electrolyte in PEM fuel cells. It could function efficiently both in lower humidity environments at lower temperatures, as well as at temperatures closer to and even potentially above the boiling point of water.

Against this background of conventional wisdom, applicant has discovered fliiorochloro ionomers that have a combination of relatively high ionic conductivity and relatively low hydration, and excellent barrier against permeation of organics including methanol crossover. As a result, this invention makes possible the more effective use of solid polymer electrolyte membranes in existing applications such as those described above. Additionally, new applications heretofore not practical may become possible with this new. unique set of characteristics. The instant invention is particularly valuable as an electrolyte or component thereof, or as a component in the electrode of polymer electrolyte membrane fuel cells operating at high temperature or low humidity as well as breathable protective covering industry.

SUMMARY OF THE INVENTION This invention covers fluorochloro ionomcrs and processes of making them. The first embodiment of the invention is pcrfluorochloro ionomcrs having ( I) equivalent weight between 600 and 1500. preferably between 800 and 1200, and most preferably between 900 and 1100; (2) chlorine content between 8% and 30% by weight. The chlorine content can be determined by elemental analysis. These ionomers are capable of being processed into thin films or membranes (from 5 micrometer thick to 200 micrometer) and are extremely well suited for low humidity or high temperature fuel cell applications and for chemical protective covering materials. The second embodiment of the invention is partially fluorochloro ionomcrs having (1) moisture vapor permeability rate > 3000 gram H2θ/m²/day (about Vi mil thick film); (2) chlorine content of between 10% and 39% by weight. These ionomers can be processed into thin films or membranes (from 5 micrometer thick to 200 micrometer) and are suited for some fuel cell applications and more preferably for breathable protective covering materials. The third embodiment of the invention is process of producing these fluorochloro ionomcrs by radical copolymerization of at least one fluorochloro monomer and at least one comonomer consisting of ionic groups or precursors that can be converted to ionic groups such as acid groups or amines or quaternary amine groups. The said fluorochloro monomer containing at least one fluorine and at least one chlorine atom is free radical polymerizable. including but not limited to clilorotrifliioroethylene (CFCNCF₂) and dichlorodifluoroethylene (CFCl=CFCl).

DETAILED DESCRIPTION OF THE INVENTION

In this invention, novel fluorochloro ionomcrs and their applications are disclosed. Fluorochloro ionomers means polymers containing significant amount of fluorine and chlorine atoms on the polymer backbone and carrying ionic groups (anionic or cationic) on the polymer pendant side chain. These fluorochloro ionomers are made by copolymerization of at least one fluorochloro monomer and at least one comonomer that carrying ionic group or earn ing precursor group which can be converted to ionic groups.

The first preferred class of fluorochloro ionomers is perfluorochloro ionomers wherein the entire polymer backbone is substituted fully by fluorine and chlorine atoms and the polymer side chain carrying ionic groups. The perfluorochloro ionomers have ( 1) equivalent weight between 600 and 1500, preferably between 800 and 1200, and most preferably between 900 and 1 100; (2) chlorine content between 8% and 30% by weight. The chlorine content can be determined by elemental analysis. The perfluorochloro ionomers arc made by copolymerization of at least one perfluorochloro monomers and at least one functional monomers substantially fluorinated with at least one moiety that is ionic group or convertible to ionic groups. Example of perfluorochloro monomers includes, but not limited to, chlorotrifluorocthylcnc (CFCI=CF2) and dichlorodifluorocthylcnc (CFCl=CFCl). Example of the functional monomers includes, but not limited to, compounds of the following molecular structure:

CF2=CF -(O -CF2 -CF)n -O -(CF)-(CF)a -(CF2)h -Y CF2X Rf Ri wherein X is F, Cl or mixtures; n is an integer 0. 1 or 2; Rf is selected from F. Cl, pcrfluoroalkyl radical, and chloropcrfluoroalkyl radical; a is an integer of 0 or 1; b is an integer of 1, 2. or 3. Y is a functional group convertible to an ionic group. Example of Y include, but not limited to. sulfonyl halide (-SO2W); ester (-COOR); wherein W is F or Cl. and R is an alkyl group with carbon number from 1 to 12.

Functional group Y can be converted to certain ionic groups Z by chemical treatment. The resulting perfluorochloro ionomers have the following pendant side chain:

-(O -CF2 -CF)n -O -(CF)-(CF)a -(CF2)b -Z CF2X Ri Rf wherein X is F, Cl or mixtures; n is an integer 0. I or 2; Rf is selected from F, Cl. pcrfluoroalkyl radical, and chloropcrfluoroalkyl radical; a is an integer of 0 or 1; b is an integer of 1. 2, or 3. Z is a functional group with ionic character. Example of Z as an anionic group includes, but not limited to, sulfonic acid -SO3H, or its salt form -SO3M. sulfonamide -Sθ2N(R)-, sulfonimide -Sθ2N(Ri)-Sθ2R2, wherein Ri and R2 arc alkyl or perfluoroalkyl group, carboxylic acid -COOH, or its salt form, -COOM, phosphonic acid -PO(OH)2. and the like. Example of Z as an cationic group includes, but not limited to. sulfonamide amine -SO2N(-R-)2 NR, sulfonamide imidazole, sulfonamide quaternary amine, and the like.

The pcrfluorochloro ionomers arc most suited for fuel cell applications, including hydrogen or methanol fuel cell applications. These ionomers arc capable of being processed into thin films or membranes (from 5 micrometer thick to 200 micrometer) and arc extremely well suited for low humidity or high temperature fuel cell applications and for breathable chemical protective covering materials. Here "'breathable" means the protective covering allows sufficient moisture vapor permeability, which is important for the comfort of human body.

The second preferred class of fluorochloro ionomers is partially fluorochloro ionomers wherein polymer backbone is partially substituted by fluorine and chlorine atoms and the polymer side chain earn ing ionic groups. The partially fluorochloro ionomers have (1) moisture vapor permeability rate > 3000 gram H2θ/m²/day (about Vi mil thick film); (2) chlorine content of between 10% and 39% by weight. The chlorine content can be determined by elemental analysis. These ionomers arc suited for certain fuel cell applications but more suited for breathable protective covering materials. The partially fluorochloro ionomers are made by copolymerization of at least one fluorochloro monomer and at least one functional monomer carrying at least one moiety that is ionic group or convertible to ionic groups. Example of fluorochloro monomer includes. but not limited to. chlorotrifluorocthylcnc (CFC1=CF2) and dichlorodifluorocthylcnc (CFCl=CFCl). Example of the functional monomer includes, but not limited to, acrylic acid, tcrt-butyl acrylatc, mcthacrylic acid, malcic anhydride, malcic acid, itaconic acid, itaconic anhydride, styrcne, methylstyrenc, 2-acrylamido-2- mcthyl-1-propancsulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, allyl chloride, allyl bromide, vinyl imidazole, vinylpyridine, O-acrylamidopropyOtrimethylammonium chloride, and the like. Other comonomers that can be used to enhance physical property of the partially fluorochloro ionomers arc alkcncs, including but not limited to ethylene, propylene, butylcncs, and vinyl acetate and the like. When tcrt-butyl acrylate monomer is used, the tert-butyl group can be hydrolyzed by a base or thermally hydrolyzed into carboxylic acid group. When styrcne or methylstyrenc is used, the aromatic ring can be acidified by sulfur trioxide or concentrated sulfuric acid to create pendant sulfonic acid group onto aromatic ring. When ally chloride or ally bromide is used, the halidc group can be converted to quaternary amine group by reacting with a tertiary amine. This is simply to demonstrate that some precursors which have no ionic character can be converted to ionic group by chemical treatment. These partially fluorochloro ionomcrs are capable of being processed into thin films or membranes (from 5 micrometer thick to 200 micrometer) and are extremely well suited for fuel cell applications and for breathable chemical protective covering applications.

To initiate copolymcrization, the reaction can occur in an aqueous system or in a solvent system. When the functional comonomcrs are less water soluble, the copolymerization reaction is preferred to be in aqueous emulsions, mini-emulsions, or micro-emulsions. On the other hand, when the functional comonomers are more water soluble, it is preferred to use solvent system for copolymcrization. wherein all monomers arc soluble in the selected solvent system before polymerization. The temperature of copolymcrization in cither case is ranged from 0 to 150° C, preferably 40 to 100° C. Initiators for polymerization include free-radical initiators, such as pcrsulfatcs, azo initiators, peroxides, or photo initiators, of which free radicals can be generated by heat, chemical, ultraviolet or gamma rays. Amount of initiators present can range between 0.01 and 3 percent by weight based on the final polymer content. The fluoiochloro monomers are introduced to the reactor mostly from vapor phase. Sufficient mixing between liquid and vapor phases is important to encourage adequate mass transfer.

Tlic product made from the copolymcrization may be precursors of ion conducting polymers. Further chemical treatment is required to convert precursors to ionomcrs. Since most applications arc for coating or extrusion, film fomiation quality is critical. It is possible to do the coating or extrusion application using precursor polymers or ionomcrs directly. Either coating or extrusion application would allow the ionomers to be processed into thin films, either alone or in composite forms with other porous substrates to form a composite membrane. The said other porous substrates can be a support of woven or non-woven porous material preferably microporous membranes, including but not limited to. microporous Nylon (polyamidc). microporous polyvinylidcne fluoride (PVDF), or microporous polytetrafluoroethylene (PTFE). The term "porous" means having a plurality of interconnected passages and pathways. Solutions of the ionomcr can be impregnated into the porous support by methods known in the art. such as examples described in U.S. Patent number 5,547,551, 5,599,614, and 6,156,451.

In another aspect of this invention is the use of bipolar membrane, ie. a double layers of membrane wherein each layer of ionomcr has opposite charge to the other layer. This can be done by double coating or co-extrusion of two fluorochloro ionomers of opposite charged ionomers. For chlor-alkali industry application, this invented fluorochloro ionomers can be applied as double layers structure wherein one layer is fluorochloro sulfonic acid ionomer and the other layer is fluorochloro carboxylic acid ionomer. Such double layer membrane can be made by double coating or co-extrusion. Another aspect of this invention is to make one monolithic layer of fluorochloro sulfonyl fluoride membrane first, following by chemical treatment to convert one side of fluorochloro sulfonyl fluoride membrane into carboxylic acid membrane and the other side to become fluorochloro sulfonic acid membrane. This would avoid the traditional challenging need for laminating sulfonic acid and carboxylic acid membrane together for chlor-alkali industry application.

The following methods were used to characterize the fluorochloro ionomers prepared. Degree of Hydration

A sample of 1 cm x 1.5 cm in size was cut from a membrane and placed in a vacuum oven at 120" C for 24 hours at about 60 mm Hg using a nitrogen bleed to maintain the pressure. Then, the sample was removed, and weighed when cool in I minute to obtain the dry weight. The sample was then placed in de-ionized water for 2 hours at 21~25" C. The sample was then removed from water, patted dry with a paper cloth, and immediately weighed to obtain the hydratcd weight. The degree of hydration in percent is calculated as

100% x IWt(wct) - Wt(dry) | / Wt (dry) Three samples for each membrane were tested, and the reported hydration is the arithmetic mean of the three measurements.

Equivalent Weight

Equivalent weight determination is based on the method of WO 00/52060 PCT patent application.

Room Temperature Ionic Conductivity

The conductivity determination is based on the method of Doyle ct al, WO 98/20573 PCT patent application.

Moisture Vapor Permeability Rate

Moisture vapor permeability rate determination is based on ASTM-E96-66BW test method. BW test is an inverted cup test, wherein water is in direct contact with each sample.

Chemical Agent Permeation Test

Chemical agent permeation rate determination is based on method described in US Patent No. 6,395,383.

EXAMPLES

The following examples illustrate specific embodiments of the present invention. It should be understood that the scope of the invention is not limited to these particular embodiments. The examples are briefly described as follows:

Example I : the synthesis of copolymer of chlorotrifluoroethylene (CFCl=CF₂) and PSEPVE (CF2=CFO-CF2CF(CF3)-O-CF2CF2-SO2F). The resulting copolymer (IA) is further converted to sulfonic acid of pcrfluorochloro ionomcrs (IB), carboxylic acid of pcrfluorochloro ionomcrs (1C), sulfonamide amine of fluorochloro ionomers (ID), bi- layer of (1 B)/( 1C), composite membrane of (I B)/(1C), composite bipolar membrane of ( 1B)/(1D). Example 2: the synthesis of copolymer of chlorotrifluorocthylcnc (CFCNCF2) and tcrt- butyl acrylatc. The resulting copolymer is further converted to carboxylic acid sodium salt partially fluorochloro ionomcrs.

Example 3: the synthesis of copolymer of chlorotrifluoroethylcne (CFC1=CF2) and maleic anhydride. The resulting copolymer is further converted to amide carboxylic acid ammonium salt partially fluorochloro ionomers.

Example 4: the synthesis of tcrpolymcr of chlorotrifluorocthylcnc (CFC1=CF2) and ethylene, and maleic anhydride. The resulting terpolymcr is further converted to carboxylic acid potassium salt of partially fluorochloro ionomcrs.

Example 5: the synthesis of copolymer of chlorotrifluoroethylene (CFCl=CF₂) and acrylic acid. The resulting copolymer is converted to carboxylic acid sodium salt of partially fluorochloro ionomcrs.

Example 6: die synthesis of tcrpolymcr of chlorotrifluorocthylcnc (CFC1=CF2) and ethylene and acrylic acid. The resulting tcrpolymer is converted to carboxylic acid lithium salt of partially fluorochloro ionomcrs.

Example 7: the synthesis of copolymer of chlorotrifluoroethylene (CFC1=CF2) and styrenc. The resulting copolymer is further converted to sulfonic acid of partially fluorochloro ionomcrs.

EXAMPLE 1

The Example 13 of US Patent number 6,743,549 is repeated, except that vinylidcnc fluoride is replaced by chlorotrifluorocthylcnc (CFC1=CF2). Additionally, trichloroacctvl peroxide is used as a free radical initiator. The resulting copolymer has the following structure:

-(CFCICF2)m-(CF2CF)- (IA)

O-CF2CF(CF3)-O-CF2CF2-SO2F (m=3~ 10) Following the same example, some copolymer of (IA) is then converted to sulfonic acid lithium salt, which is suitable for electrolyte lithium batteries application. Using the acidification method taught in Example I of US Patent number 6,156,451, the lithium salt of perfluorochloro ionomer is further acidified to sulfonic acid of perfluorochloro ionomers as follows:

-(CFClCF2)m-(CF2CF)- ( 1 B)

0-CF2CF(CF3)-0-CF2CF2-SO3H (m=3~10)

The sulfonic acid of perfluorochloro ionomers ( IB) can form uniform thin film (after drying from 5 micrometer thick up to 200 micrometer) by removing volatile solvent in an hot air circulated oven at 160° C for 3 minutes. Degree of hydration and chemical agent permeation rate of our invented perfluorochloro sulfonic acid ionomer membrane arc all better than Nafion® perfluoro ionomer membrane when compared with that of similar equivalent weight, while ionic conductivity remains the same for the ionomers with similar equivalent weight. It shows that our perfluorochloro ionomers containing PCTFE polymer backbone surprisingly have superior barrier properties against organic permeation and better water management capability and stronger mechanical strength especially at wet environment than Nafion® type PTFE based perfluoro ionomers. The coated membrane with thickness of about 20 micrometer has moisture vapor permeability rate > 3,000 gram/m²/day. These unusual physical properties of our invented perfluorochloro ionomers are extremely suitable for various fuel cell applications and breathable protective covering.

Some copolymer ( IA) is also converted to carboxylic acid perfluorochloro ionomers with the same chemical reaction methods taught by M. Seko. H. Miyauchi, J. Ohmura, and K. Kimoto, in '" Modem Chlor-Alkali Technology (C. Jackson, ed.). Vol. 3, p. 76, Ellis Horwood, Chichcstcr (1983). The resulting carboxylic acid perfluoro ionomers have the following structure:

-(CFClCF2)m-(CF2CF)- ( 1C)

O-CF2CF(CF3)-O-CF2-COOH (m=3~ i 0) Some copolymer (IA) is also converted to cationic charge sulfonamide amine group by chemical reaction of (IA) with 1- mcthylpipcrazinc in dimthylformamide at 100" C for 6 hours to form the following tertian' amine structure:

-(CFCICF2)m-(CF2CF)- (ID)

O-CF2CF(CF3)-O-CF2CF2-SO2N(CH2CH2)2NCH3

Additionally, copolymer ( IA) is processed into thin film of about 2-mil thick. One side of ( IA) is treated with the chemical method of (IB) and the other side is treated with the chemical method of ( 1C). The resulting membrane has one side of sulfonic acid pcrfluorochloro ionomcr and the other side of carboxylic acid pcrfluorochloro ionomcr. Such film with two layers of ionomcrs without lamination is very suitable for chlor-alkali industrial applications.

Furthermore, perfluorochloro ionomcrs with sulfonic acid group (I B) is coated onto one side of microporous 0.2 micron PVDF membrane (1 Vi mil thick) and the other side of the PVDF membrane is coated with pcrfluorochloro ionomcrs with carboxylic acid group ( 1C). The resulting composite membrane (1B)/(1C) is useful for chlor-alkali industrial application.

Finally, perfluorochloro ionomers with sulfonic acid group ( IB) is coated onto one side of microporous 0.2 micron PVDF membrane ( 1 Yi mil thick) and the other side of the PVDF membrane is coated with pcrfluorochloro ionomcrs with sulfonamide amine group ( I D). The resulting bipolar membrane ( 1 B)/( 1 D) has moisture vapor permeability rate > 3,000 gram/nr/day. The bipolar membrane has unusually low chemical agent permeability rate easily satisfying specifications and low methanol crossover rate, which shows the membrane is very useful for many industrial applications as well as breathable protective covering applications.

EXAMPLES 2 Example 1 of this invention is repeated, except that PSEPVE is replaced by tert- butyl acrylatc. The copolymer is then treated with sodium hydroxide NaOH(aq) at 95° C for 6 hours to obtain carboxylic acid sodium salt ionomcrs as follows:

-(CFClCF2)m-(CH2CH)-

COO Na

The partially fluorochloro ionomcrs are coated onto one side of microporous 0.2 micron Nylon membrane (about 2-mil thick) and dried at 130° C for 2 minutes. The add-on weight to the microporous Nylon membrane is about 20 gram/m². This partially fluorochloro ionomer coating thickness is about '/^■> mil. The coated membrane has moisture vapor permeability rate > 3.000 gram/nr/day. The coated membrane has low chemical agent permeability rate satisfying specifications, which means the invented fluorochloro ionomers have unusually good barrier properties for breathable protective covering applications.

EXAMPLE 3

Example 6 of US Patent number 6.228.963 is repeated, except that PPVE is not used and TFE is replaced by CTFE (Chlorotrifluoroethylene). The copolymer made is shown below:

-(CFClCF2)m-(CHCH)- (m=3~10)

O=C C=O

O Tlic copolymer is further ionized by ammonia NH4θH(aq) at 95° C for 6 hours to become

-(CFClCF2)m-(CHCH)- (m=3~10)

O=C C=O NH4 0 NH2

EXAMPLE 4 Example 6 of US Patent number 6,228,963 is repeated, except that PPVE is replaced by ethylene and TFE is replaced by CTFE (Chlorotrifluorocthylcne). The copolymer made is shown below:

-(CFClCF2)m-(CH2CH2)n-(CHCH)- O=C C=O

O The copolymer is further ionized, with the method taught in Example 1 of US Patent number 6, 156,451, by potassium hydroxide KOH(aq) to become

-(CFClCF2)m-(CH2CH2)n-(CHCH)-

O=C C=O

OK OK

EXAMPLE 5

Example 3 of this invention is repeated except that malcic anhydride is replaced by acrylic acid. The copolymer made is shown below:

-(CFClCF2)m-(CH2CH)- COOH

The copolymer is further ionized by NaOH(aq) at 95° C for 6 hours to become sodium salt of carboxylic acid of fluorochloro ioiiomcrs.

-(CFClCF2)m-(CH2CH)-

COONa

Tlic partially fluorochloro ionomcrs arc coated onto one side of microporous 0.2 micron Nylon membrane (about 2-mil thick) and dried at 130 C for 2 minutes. The add-on weight to the microporous Nylon membrane is about 16 gram/m². This partially fluorochloro ionomer coating thickness is about 'Λ mil. The coated membrane has moisture vapor permeability rate > 3,000 gram/m²/day. The coated membrane has low chemical agent permeability rate satisfying specifications, which means the invented fluorochloro ionomers have unusually good barrier properties for breathable protective covering applications. EXAMPLE 6

Example 4 of this invention is repeated, except that malcic anhydride is replaced by acrylic acid. The copolymer is shown below:

-(CFCICF2)m-(CH2CH2)n-(CH2CH)-

COOH

The copolymer is further ionized by LiOH(aq) at 100° C for 6 hours to become

-(CFCICF2)m-(CH2CH2)n-(CH2CH)-

COO Li

EXAMPLE 7

Example 1 of US Patent number 6, 153,697 is repeated except that 785 grams CHHPM is replaced by 236 grams styrene and isobutylene is not used. The copolymer made is shown below:

-(CFClCF2)m-(CH2CH)- (m=3~10)

C6H5

The copolymer is further ionized by sulfur trioxidc SOs at 1 10° C for 6 hours to become sulfonic acid of fluorochloro ionomers.

-(CFClCF2)m-(CH2CH)- (m=3~10)

C6H5SO3H

The partially fluorochloro ionomers arc coated onto one side of microporous 0.2 micron PVDF membrane (about 1 Vi mil thick) and dried at 130 ° C for 2 minutes. The add-on weight to the microporous PVDF membrane is about 18 gram/m². This partially fluorochloro ionomer coating thickness is about Vi mil. The coated membrane has moisture vapor permeability rate > 3,000 gram/m²/day. The coated membrane has unusually low chemical agent permeability rate satisfying specifications, which means the invented fluorochloro ionomers have unusually good barrier properties for breathable protective covering applications.

Claims

CLAIMS OF PCT/US2008/073505 THAT WHICH IS CLAIMED IS:

1. Perfluorochloro ionomers having ( 1) equivalent weight between 600 and 1500, preferably between 800 and 1200. and most preferably between 900 and 1 100; (2) chlorine content between 8% and 30% by weight.

2. The perfluorochloro ionomers of Claim 1 made by copolymcrization of at least one perfluorochloro monomer and at least one functional monomer substantially fluorinatcd with at least one moiety that is ionic group or convertible to ionic group.

3. The perfluorochloro monomer of Claim 2 including chlorotrifluorocthylene (CFCl=CF₂) and dichlorodifluoroethylene (CFCl=CFCl).

4. The functional monomers of Claim 2 including compounds of the following molecular structure:

CF2=CF -(O -CF2 -CF)n -O -(CF)-(CF)a -(CF2)b -Y CF2X Rr Rf wherein X is F, Cl or mixtures; n is an integer 0, 1 or 2; Rf is selected from F, Cl, perfluoroalkyl radical, and chloroperfluoroalkyl radical; a is an integer of 0 or 1 ; b is an integer of 1. 2. or 3. Y is a functional group convertible to an ionic group, including sulfonyl halidc (-SO2W); ester (-COOR); wherein W is F or Cl, and R is an alkyl group with carbon number from 1 to 12.

5. Perfluorochloro ionomers of Claim I having the following pendant side chain:

-(O -CF2 -CF)n -O -(CFHCF)a -(CF2)b-Z CF2X Rf Rr wherein X is F, Cl or mixtures; n is an integer 0. I or 2: Rf is selected from F, Cl. perfluoroalkyl radical, and chloroperfluoroalkyl radical; a is an integer of 0 or 1 ; b is an integer of 1, 2, or 3. Z is a functional group with ionic character. As an anionic group, Z is sulfonic acid -SO3H, or its salt form -SO3M, sulfonamide - Sθ2N(R)-, sulfonimide -Sθ2N(Rι)-Sθ2R2, wherein Ri and R2 are alkyl or perfluoroalkyl group, carboxylic acid -COOH, or its salt form. -COOM, phosphonic acid -P0(0H)2, and the like. As a cationic group, Z is sulfonamide amine -Sθ2lM(-R-)2 NR, sulfonamide imidazole, sulfonamide quaternary amine, and the like.

6. Perfluorochloro ionomers of Claim 1 in a physical form of membrane or film, 5 micrometer to 200 micrometer in thickness, suitable for fuel cell applications and/or breathable protective covering.

7. The membrane or film of Claim 6 a composite membrane wherein at least one type of perfluorochloro ionomers of Claim 1 is partially or fully impregnated onto porous substrates

8. The porous substrates of Claim 7 including microporous membranes of Nylon, poly(vinylidcnc fluoride), or poly(tctrafluoroethylcnc).

9. The membrane or film of Claim 6 a multi-layers membrane consisting of at least two different types of perfluorochloro ionomers of Claim 1 to form each layer.

10. The multi-layers membrane of Claim 9 including (one layer of perfluorochloro ionomers with sulfonic acid group and another layer of perfluorochloro ionomers with cartκm lic acid group) and/or (one layer of perfluorochloro ionomers with anionic charge group and one layer of perfluorochloro ionomers with cationic charge group).

1 1. Partially fluorochloro ionomers having (I) moisture vapor permeability rate > 3000 gram H2θ/m²/day (about Vz mil thick film); (2) chlorine content of between 10% and 39% by weight.

12. The partially fluorochloro ionomers of Claim 1 1 made by copolymcrization of at least one fluorochloro monomer and at least one functional monomer earn ing at least one moiety that is ionic group or convertible to ionic group

13. The fluorochloro monomer of Claim 12 including chlorotrifluorocthylcnc (CFC1=CF2) and dichlorodifluorocthyicne (CFCI=CFCI).

14. The functional monomer of Claim 12 including acrylic acid, tert-butyl aery late, methacrylic acid, maleic anhydride, maleic acid, itaconic acid, itaconic anhydride, styrene, methylsryrene, 2-acrylamido-2-methyl-I-propanesulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, allyl chloride, allyl bromide, vinyl imidazole, vinylpyridinc, (S-acrylamidopropyOtrimethylammonium chloride, and the like.

15. The partially fluorochloro ionomers of Claim 1 1 made by terpolymerization of at least one fluorochloro monomer and at least one functional monomer earn ing at least one moiety that is ionic group or convertible to ionic group, and at least another monomer selected from alkenes, including ethylene, propylene, butylenes, and/or vinyl acetate.

16. Partially fluorochloro ionomers of Claim 1 1 in a physical form of membrane or film, 5 micrometer to 200 micrometer in thickness, suitable for fuel cell applications and/or breathable protective covering.

17. The membrane or film of Claim 16 a composite membrane wherein at least one type of partially fluorochloro ionomers of Claim 1 1 is partially or fully impregnated onto porous substrates.

18. The porous substrates of Claim 17 including microporous membranes of Nylon, poly(vinylidcnc fluoride), or poly(tctrafluorocthylcnc).

19. The membrane or film of Claim 16 a multi-layers membrane consisting of at least two different types of partially fluorochloro ionomers of Claim 1 1 to form each layer.

20. Tlic multi-layers membrane of Claim 19 including at least one layer of partially fluorochloro ionomers with anionic charge group and at least one layer of partially fluorochloro ionomers with cationic charge group.