CA1196888A - Coextruded multilayer cation exchange membranes - Google Patents

Abstract

TITLE
Coextruded Multilayer Cation Exchange Membranes ABSTRACT OF THE DISCLOSURE
A process for the preparation of a multilayer cationic ion exchange membrane is disclosed. At least two substantially incompatible melt-fabricable fluorinated polymers containing sulfonyl or carboxyl functional groups are heated to a temperature above the melting point of the polymers, brought into contact and coextruded into a composite film.
The resulting composite film is cooled to a temperature below the melting point of each of the films and the functional groups of the polymers are converted to ionizable functional groups. The resulting membrane is useful as an ion exchange membrane, especially in the production of chlorine and caustic.

Description

TITLE
Coextruded Multilayer Cation Exchange Membranes BACKGROUND OF THE INVENTION
Fluorinated polymers containing pendant side 10 chains are often used to prepare ion exchange membranes. Such membranes have outstanding properties as barrier membranes to separate the anode and cathode compartments of electrolytic cells used for the production of chlorine and caustic.
Fluorinated polymers containing carboxyl side chains provide excellent current efficiency in such electrolytic cells, but result in high operating voltages. By contrast, fluorinated polymers containing sulfonyl ~roups in the side chains permit 20 operation a~ low voltages, but result in poor current efficiency in the electrolytic cell It has previously been recognized that combinations of polymers having sulfonyl and carboxyl groups or combinations of polymers having different 25 equivalenk weights are desirable ~o provide an optimum balance of performance characteristics in an electrolytic cell using membranes prepared from such polymers. Under normal cell operation, the water permeation characteristics of the layers are sufficiently close that the layers remain in intimate contact with each other. However, abnormal cell conditions, such as 1055 of electrical power, failure of water feed ~o the cathode chamber and particularly interruption or loss of brine feed to the cell, can 35 produce a large difference in water transport. For , , ............. ... ................ ~ . .. .. . .. . . .,, . ~

example, iE the anolyte is depleted below 50 y/l NaCl, a large quanti-ty of water will be transported through a Eluorinated polymer having sulfonyl side chains. However, the water is substantially less able to permeate a polymer havi.ng carboxyl-containing side chalns. Thus, during an upset of cell operation, a composite of two such polymers may experience a buildup of water at the interface, resulting in delamination of the composite.
SUMMARY OF THE INVENTION
The instant invention provides composite cation exchange membranes exhibiting improved resistance to delamination in an electrolytic cell and a process for the production of such composite membranes by coextrusion.
Specifically, the instant invention provides a process for the preparation of a multilayer cation exchange membrane by heating at least two substantially incompatible melt-fabricable fluorinated polymers having pendant side chains containing functional groups selected from sulfonyl and carboxyl to a temperature above the melting point of the polymers, bringing the molten polymers into contact while each is at a temperature above the melting point of the polymer, coextruding the polymers into a composite film, cooling the resulting composite to a temperature below the melting points of each of the films, and subsequently converting the functional groups to ionizable functional groups.
DETAILED DESCRIPTION OF THE INVENTION

_ The melt-fabricable polymers used in the ins-tant invention are of the types generally used previously in the preparation of films or reinforced laminates for use in electrochemical cells, and especially chloralkali cells. These include ~.~,4~3~

fluorinated polymers with pendant side chains containing sulfonyl groups, carboxyl groups, or both.
The melt-fabricable polymer having sulfonyl functional groups has a fluorinated hydrocarbon bac]cbone chain to wh:ich are attached functional groups or pendant side ehains bearing the funetional groups. The pendant side ehains ean contain, for example, Rf groups wherein Rf is F, Cl, or a Cl to C10 perfluoralkyl radical. Fluorinated polymers of this type and their preparation are deseribed in detail in United States Patents 3,282,875, 3,560,568, 3,718,627, and 3,041,317. For ehlor-alkali cells, perfluorinated polymers are preferred.
The melt-fabricable polymer having carboxylie funetional groups has a fluorinated hydroearbon backbone ehain to which are attaehed the funetional groups or pendant side ehains whieh in turn carry the funetional groups. The pendant side chains can eontain, for example, ( CF ) W
Z t groups wherein Z is F or CF3/ t is 1 to 12 and preferably 1 to 3, and W is -COOR or -CN, wherein R
is lower alkyl. Preferably, the funetional group in the side ehains of the polymer will be present in terminal --O~ CF ) W
Z t groups. Sueh fluorinated polymers containing earboxylie functional groups and their preparation ~3~3~

are disclosed in British Patent 1,145,445 and United States Patents 3,506,635 and 4,116,888.
Preferred monomers for use in the preparation o such polymers are found in United States Patents 4,131,740 and 3,852,326. For chlor-alkali cells, perfluorinated polymers are preferred.

~ he particular polymers used in the present invention are substantially incompatible.
lO Substantially incompatible polymers are those which, -after blending above the melting point of each polymer, separate into distinct phases on cooling ~o ---room temperature~ Thus, the polymers used to form the component layers in the present invention can include one membrane having carboxylic functional groups and another membrane having sulfonyl functional groups. Alternatively, two polymers having similar ohemical composition, for example, both polymers being characterized by sulfonyl groups, ~0 but substantially incompatible due to variation in equivalent weight, can also be used in accordance - with the present invention.
In general, polymers used in the present invention having sulfonyl groups exhibit an 25 equivalent weight of about from 700 to 1600, and preferably about from lO00 to 1200. In the event that two fluorinated polymers having sulfonyl - functional groups are used~ the equivalent weight of .:-the polymers ~hould differ by at leas about 200 to ---30 realize the required degree of incompatibility. --In generalt the polymers having carboxylic functional groups exhibit an equivalent weight of -abo~t from 700 to 1200, and preferably about from l,050 to 1,150.

4 .

B~

Each of the melt fabricable resins used should be uniform or well-blended. The carboxylate resin should be protected from atmospheric moisture prior to coextrusion to prevent hydrolysis.
In accordance with the present invention, `the final product contains at least two layers, and preferably two or three layers. The total thickness of the final product of the present invention can be about from 25 to 250 microns. Particularly good 10 balance of cell voltage and durability in a chloralkali cell is realized with a total thickness of 75 ~o 150 microns~ and this composite thickness is accordingly preferred. Each component of a laminate of the present invention should comprise at least 15 about 5% of the total thickness of a composite. In general, in a two component laminate prepared from polymers having carboxylic and sulfonic functional groups, respectively, the carboxyl containing polymer preferably comprises about from 15 to 33~ of the 20 total thickness of the composite.
The present laminar structures are prepared by coextruding the polymers above the melting point of each polymer. A wide variety of mechanical variations can be used, including commercially 25 available coextrusion equipment such as that manufactured by Johnson Plastics Machinery Company of Chippewa Falls, Wisconsin. For example, the laminates can be prepared using multiple extruders feeding into separate zones of a common chamber, 30 following which the layered stream is fed to a single die. Another embodiment of the present invention involves the use of a single die known in the film processing industry as a "coat hanger'l die. In the use of such a die, multiple extruders feed separate 35 streams into the specialized die. The die expands 31~

the width of the streams and joins ~he two streams before they leave a sinyle exit orifice of the die.
Within the requirement that the polymers be above the melting point, the particular processing 5 tempera~ure will depend on known operational requirements for extrusion of films. The temperature will be adjusted to obtain continuous smooth films of uniform caliper without die drips or other defects.
Using the sulfonyl~containing and carboxyl-containing lO polymers of the present invention, an extrusion temperature range o about from 260 ~o 330C is preferred.
After coextrusion of the laminates, they are cooled to a temperature below the melting point of 15 each polymer and treated according to known techniques to convert the functional groups to forms more suitable for use in electrolytic cell applications. Such conversion also renders the polymers substantially less melt-fabricable.
A reinforcing layer is generally also added to the composite structure. A wide variety of support materials can be used, including woven fabric or nonwoven material~ In the case of woven fabric, weaves such as ordinary basket weave and leno weave 25 can be used. The reinforcement threads can be either monofilament or multistrandedO
Particularly preferred reinforcement materials are perhalocarbon polymer threads optionally in conjunction with sacrificial fibers 30 which are dissolved by caustic or destroyed by oxidizing agents. As used herein, the term "perhalocarbon polymer" means a polymer which has a carbon chain optionally containing ether linkages and which is totally substituted by fluorine or by 35 fluorine and chlorine atoms~ Varticularly preferred .~ 3~ 3 because of its inert: character is a perfluorocarbon polymer. Typical of such polymers are those made from tetrafluoroethylene and copolymers of tetrafluoroethylene with hexafluoropropylene and/or perfluorotalkyl vinyl ethers) wherein alkyl is from 1 to 10 carbon atoms.A preferred ether of this type is perfluoro~propyl vinyl ether).
The reinforcing material is conveniently applied to the sulfonyl-containing polymer in conjunction with another sulfonyl-containing polymer of the same equivalent weight. These two sulfonyl-con~aining polymers are then laminated, with the reinforcing material embedded in the composite layer of sulfonyl-containing polymer.
The laminar structures of the present invention are particularly useful as membranes for chloralkali electrolytic cells. Among the cells in which these laminar structures can be used are narrow-gap cells, in which the gap between anode and cathode is no greater than about 3 mm and the laminar structure is in contact with at least one of the anode and cathode. Such arrangements minimize the resistance con~ributed by the anolyte and catholyte, thus providing for operation at low voltage. The 25 membranes of this invention can also be used in a solid polymer electrolyte or composite electrode/membrane arran~ement, in which a thin porous anode and/or porous cathode are attached directly to the membrane surface, and rigid current 30 collectors can also be used in contact with these electrodes.
In any of the above arrangements, either or both of the electrodes can have a catalytically active surface layer of the type known in the art for 35 lowering the overvoltage of an electrode. Such electrocatalyst can be of a type known in the art, such as those described in U.S. Patents 4,224,121 and 3,134,697, and published UK Patent Application GB

2,009,788A. Preferred cathodic electrocatalysts include platinum black, Raney nickel and ruthenium black. Preferred anodic electrocatalysts include platinum black and mixed ruthenium and iridium oxides.
The membranes described herein can also be modified on either surface or both surfaces thereof so as to have enhanced gas release properties, for example by providing optimum surface roughness or smoothness, or, preferably, by providing thereon a gas- and liquid~permeable porous non-electrode layer~ Such non-electrode layer can be in the form of a thin hydrophilic coa~ing or spacer and is ordinarily of an inert electroinactive or non-electrocatalytic substance. Such non-electrode layer should have a porosity of 10 to 99~, preferably 30 to 70%, and an average pore diameter of 0~01 to 2000 ~icrons, preferably 0.1 to 1000 microns, and a thickness generally in the range of 0.1 to 500 microns, preferably 1 to 300 microns. A
non-electrode layer ordinarily comprises an inorganic component and a binder; the inorganic component can 25 be of a type as set forth in published UK Patent Application G~ 2~064,586A, preferably tin oxide, titanium oxide, zirconium oxide, or an iron oxide such as Fe2O3 or Fe3O4. Other information regarding non-electrode layers on ion-exchange 30 membranes is found in published European Patent Application 0,031,660, and in Japanese Published Patent Applications 56-108888 and 56-112487.
The binder component in a non-electrode layer, and in an electrocatalyst composition layer, 35 can be, for example, polytetrafluoroethylene, a

3~

fluorocarbon polymer at least the surface of which is hydrophilic by virtue of treatment with ionizing radiation in air or a modifying agent to introduce functional groups such as -COOH or -SO3H (as described in published UK Patent Application G~
2,0~0,703A) or treatment with an agent such as sodium in liquid ammonia, a functionally substituted fluorocarbon polymer or copolymer which has carboxylate or sulfonate functional groups, or polytetrafluoroethylene particles modified on their surfaces with fluorinated copolymer having acid type functional groups (GB 2,064,586A~. Such binder can be used in an amount of about from 10 to 50~ by wt.
of the non-electrode layer or of ~he electrocatalyst composition layer.
Composite structures having non-electrode layers and/or electrocatalyst composition layers thereon can be made by various techniques known in the art, which include preparation of a decal which is then pressed onto the membrane surface, application of a slurry in a liquid composition (e.g., dispersion or solution) of the binder follo~ed by drying, screen or gravure printing of compositions in paste form, hot pressing of powders distributed on the membrane surface, and other methods as set forth in GB 2,064,586A. Such structures can be made by applying the indicated layers onto membranes in melt-fabricable form, and by some of the methods onto membranes in ion-exchange Eorm; the polymeric component of the resulting structures when in melt-fabricable form can be hydrolyzed in known manner to the ion-exchange form.
Non-electrode layers and electrocatalyst composition layers can be used in combination in various ways on a membrane. For example, a surface of a membrane can be modified with a non-electrode layer, and an electrocatalyst composition layer disposed over the latter. It is also possible to place on a membrane a layer containing both an electrocatalyst and a conductive non-electrode material, e.g. a metal powder which has a higher overvoltage than the electrocatalyst, ~ombined into a single layer with a binder. One preferred type of membrane is that which carries a cathodic electrocatalyst composition on one surface ~hereof, and a non-electrode layer on the opposite surface thereof.
Membranes which carry thereon one or more electrocatalyst layersr or one or more non-electrode layers, or combinations thereof, can be employed in an electrochemical cell in a narrow-gap or zero-gap configuration as described above.

In chloralkali electrolytic cells, the present membranes show outstanding resistance to damage or delamina4ion, particularly in non-standard cell operating conditions. Moreover, the laminates show particular resistance to delamination or separation of the layers when the salt in the anolyte is depleted below 50 gpl. The present laminar structures also show increased storage life and permit the efficient preparation of laminates with a low frequency of defects.
The present invention is further illustrated 0 in the following specific examples.

A two-component laminar structure was prepared using an apparatus consisting of three single barrel screw extruders, two of which were used in this preparation, coupled with heated transfer lines to a common chamber where the polymer streams met. The combined polymer stream was transferred from the cor~on chamber through another heated transfer line to a six-inch slit die.
One extruder o~ this apparatus, having a one inch diameter barrel, was charged with cubes of a copolymer of tetrafluoroethylene (TFE) and methyl perfluoro(4,7-dioxa-5-methyl-8-noneate) (EVE) having an equivalent weight of 1,037 and melt flow of 25.5 10 at 270C. The extruder was operated at 20 rpm with a barrel discharge temperature of 278C.
The hopper to a second extruder, which had a 1 1/4" diameter barrel, was charged with cubes of a copolymer of tetrafluoroethylene (TFE) and perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PSEPVE) having an equivalent weight of 1,090 and a melt 1Ow of 31.4 at 2S0C. This extruder was operated at 11 rpm with a barrel discharge ~emperature of 288C. The common chamber and die temperatures were maintained at 277C.
A coextruded two-layered film was produced at the rate of 2.5 cm/sec t5 ft/min~. The total thickness of the coextruded film varied from 127 to 178 microns.
A piece of this film was hydrolyzed in a bath containing 30% dimethylsulfoxide (DMSO; and 11%
potassium hydroxide for 20 minutes at 90C. The film was rinsed and dried. Microtomed cross-sections were prepared across the width of the film, stained with Malachite green, and the relative thickness of the layers measured with a microscope.
The layer containing the carboxylic copolymer was continuous across the width of the extruded film and its thickness was 18~ of the total.

A sample of the hydroly2ed dou~le layered film was mounted in a chloralkali cell having an active area of 45 cm between a dimensionally stable anode and a mild steel expanded metal cathode. The cell was operated at 80C with current of 3.1 KA/m . The anolyte salt content was held at 200 gpl. Water was added to the anolyte to maintain the concentration of caustic produced at 32 + 1%.
After 5 days of operation, the cell was operating at 95.1~ current efficiency and 3.68 volts. On the fifth day the membrane was subjected to a simulated failure of the brine feed. The brine was shut off to the cell while electrical power, water to the catholyte and temperature control were maintained.
After 5 hours of continued operation, the anode chamber was half empty and the residual anolyte contained only 1-2~ NaCl and the cell voltage had increased to 5.0 volts. The cell was then shut down, dissembled, and the membrane was inspected. The membrane was in perfect condition with no evidence of separation of the layers.

The extrusion conditions of Example 1 were repeated except that the speed of the first extruder 25 was ~educed to 10 rpm. A coextruded two-layered film was produced at the rate of 2.5 cm/sec (5 ft/min).
The total thickness of the coextruded film varied from 100 to 152 microns.
A sample of this film was hydrolyzed and 30 examined microscopically as in Example 1. The layer containing the carboxylic polymer was continuous across the width of the extruded film and its thickness averaged 9~ of the total thickness of the film.

A sample of the hydrolyzed film was mounted in a laboratory cell with the side containing the carboxylic polymer toward the cathode. After 5 days of operation, it was performing at 94.9% current efficiency and 3.65 volts. The membrane was subject to a simulated failure of the brine feed as in Example 1. Upon inspection and examination, the membrane was in perfect condition with no evidence of blistering.
COMPARATIVE EXAMPLE A
-A film was extruded from the TFE/PSEPVE
copolymer used in Example 1, except that the polymer had an equivalent weight of 1100 and gave a film with a thickness of 100 microns. A quantity of TFE/EVE
copolymer of 1080 e~uivalent weight was extruded separately to yield a film of 50 micron thickness. A
sample of each of the above films was chosen and these samples were then pressed together to exclude air between the layers and thermally bonded by passing through a thermal laminator supported on a continuous web of a porous release paper through which vacuum was app]ied. The temperature of the laminator was controlled so that the temperature of the laminate reached 230-235C at the end of the heated zone.
This thermally bonded double layer film was then hydrolyzed and tested in a laboratory cell as in Example 1. After a similar period of 5 days, the membrane was performing at 97.5% current efficiency and 3.61 volts, producing 32 + 1% Na~H. The cell was operated for a total of ~2 days, at which time the membrane was subjected to a simulated failure of the brine feed system as in Example 1. Upon cell disassembly and inspection of the membrane, it was found to be extensively blistered. Approximately 75%
of the area in the active area of the cell was covered with liquid-filled pockets or blisters. I'he separations had occurred at the interface of the TFE/PSEPVE and the TFE/EVE layers.

A portion of the double layered film from Example 1 in the unhydrolyzed state was laid on top of an open weave fabric prepared from monofilaments of a mel~-extrudable perfluorocarbon resin tPFA).
Below the cloth was placed a 50 micron film of TFE/PSEPVE copolymer of 1100 equivalent weight. This sandwich was then passed through a thermal laminator supported on a continouus web of a porous release paper with vacuum, The temperature of the laminator was adjusted so that the temperature of the laminate reached 230-235C at the end of the heated zone. The perfluorocarbon resin fabric was embedded or encapsulated in the TFE/PSEPVE copolymer~ The laminate was hydrolyzed as in Example 1 and found to have greatly improved tear resistance over the unreinforced double layer films of Examples 1-2 and Comparati~e Example A.
A portion of this laminate was evaluated in a laboratory cell as in Example 1. After two days the performance was 95.2~ current efficiency and 3.81 volts, operated at 80C, 3.1 KA/m , 200 gpl NaCl in the anolyte and 32 + 1~ NaOH. The anolyte concentration was then reduced to 115 gpl salt in the anolyte to simulate the partial stoppage of brine flow to the anolyte chamber. The cell was operated for an additional 26 days at this high salt depletion and then shut down and the membrane examined. ~o separation or blisters in the membrane wexe found~

A coextruded double layer film was prepared using the general procedure of Example 3, but with a 1~

different type of reinforcing cloth. The cloth consisted of a warp and fill of 20 threads per inch of a 200 denier polytetrafluoroethylene fiber and 40 threads per inch of a 50 denier rayon. In the lamination procedure, a 25 micron film of the 1100 equivalent weight TFE/PSEPVE copolymer was used below the cloth instead of the 50 micron film used in Example 3.
After hydrolysis the laminate was evaluated in a cell under the same conditions as Example 1 After 9 days its performance was 95.3% current efficiency and 3~69 volts. After 11 days the membrane was subjected to a stoppage of the brine feed as in Example 1. The cell was restarted and the laminate continued to perform at 95-96% current efficiency and 3.70 volts. After 30 days the cell was shut down and disassembled. Upon inspection, the membrane appeared to be in perfect condition with no blisterin~ apparent.
COMPARATIVE EXAMPLE B
Separate films of 50 micron TFE/EVE and 100 micron TFE/PSEPVE wre pressed together as in Comparative Example Ao This composite was then used to prepare a fabric-reinforced laminate as in Example ~5 3. After hydrolysis the performance of the membrane was evaluated in a cell where after 5 days it was performing at 95~ current efficiency and 3.9 vol~s under the conditions of Example 1. This membrane was sub]ected to a simulated falure of the brine feed system as in Example 1. Upon removal from the cell and inspection, the membrane was found to be extensively blistered with approximately 50% of the area in the active area of the cell covered with liquid-filled pockets or blisters.

Claims (16)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for the preparation of a multilayer cationic ion exchange membrane by heating at least two substantially incompatible melt-fabricable fluorinated polymers containing pendant side chains having functional groups selected from sulfonyl and carboxyl to a temperature above the melting point of the polymers, bringing the molten polymers into contact while each is at a temperature above the melting point of the polymer, coextruding the polymers into a composite film, cooling the resulting composite to a temperature below the melting points of both of the films, and subsequently converting the functional groups to ionizable functional groups.

2. A process of claim 1 wherein two polymers are extruded.

3. A process of claim 2 wherein one polymer contains sulfonyl functional groups and the other polymer contains carboxylic functional groups.

4. A process of claim 2 wherein both polymers contain sulfonyl functional groups and differ in equivalent weight by at least 200.

5. A process of claim 1 wherein the extrusion temperature is maintained at about from 260 to 330°C.

6. A process of claim 1 wherein the multilayer membrane is extruded to a total thickness of about from 25 to 250 microns.

7. A process of claim 6 wherein the multilayer membrane is extruded to a thickness of about from 75 to 150 microns.

8. A process of claim 1 wherein the composite is laminated to a reinforcing web prior to converting the functional groups to ionizable functional groups.

9. A coextruded cation exchange membrane resulting from the process of claim 1.

10. A coextruded cation exchange membrane resulting from the process of claim 8.

11. In an electrolytic cell having an anode, a cathode, and a cation exchange membrane separating the anode and the cathode, the improvement wherein the cation exchange membrane consists essentially of a coextruded cation exchange membrane resulting from the process of claim 1.

12. An electrolytic cell of claim 11 wherein the gap between the anode and the cathode is no greater than about 3 mm.

13. An electrolytic cell of claim 12 wherein the cation exchange membrane is in contact with at least one of the anode and cathode.

14. A process of claim 1 further comprising applying to at least one surface of the multilayered cationic ion exchange membrane a gas- and liquid-permeable porous layer of electrocatalyst composition.

15. A process of claim 1 further comprising applying to at least one surface of the multilayered cationic ion exchange membrane a gas- and liquid-permeable porous non-electrode layer.

16. A process of claim 1 further comprising applying to at least one surface of the resulting multilayered cationic ion exchange membrane at least one gas- and liquid-permeable porous layer selected from electrocatalyst composition and non-electrode material.