CA1268083A - Method for depositing a fluorocarbonsulfonic acid polymer on a support from a solution - Google Patents

Method for depositing a fluorocarbonsulfonic acid polymer on a support from a solution

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Publication number
CA1268083A
CA1268083A CA000530402A CA530402A CA1268083A CA 1268083 A CA1268083 A CA 1268083A CA 000530402 A CA000530402 A CA 000530402A CA 530402 A CA530402 A CA 530402A CA 1268083 A CA1268083 A CA 1268083A
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Prior art keywords
polymer
temperature
solution
support
catalyst
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CA000530402A
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French (fr)
Inventor
Charles W. Martin
Bobby R. Ezzell
John D. Weaver
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Dow Chemical Co
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Dow Chemical Co
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00Post-polymerisation treatments
    • C08F6/06Treatment of polymer solutions
    • C08F6/12Separation of polymers from solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08Ion-exchange resins
    • B01J31/10Ion-exchange resins sulfonated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • B01J37/0203Impregnation the impregnation liquid containing organic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32Addition reactions to C=C or C-C triple bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32Addition reactions to C=C or C-C triple bonds
    • B01J2231/323Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52Isomerisation reactions
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/3154Of fluorinated addition polymer from unsaturated monomers

Abstract

ABSTRACT

This invention discloses improved heterogeneous acid catalysts and a method for preparing these catalysts. A heterogeneous acid catalyst has been prepared by treating a carrier material with a solution containing a fluorocarbonsulfonic acid polymer dissolved in a suitable solvent, removing the solvent, and heat treating the coated carrier in such a way so as to prevent the polymer from being leached off the carrier.
The final heat treatment of the composition to prevent the polymer from redissolving comprises an improvement in the preparation of a heterogeneous catalyst.
33,960-F

Description

~4693-3982 ~Z680~33 AN IMPROVED METHO~ FO~ DEPOSITING A
FLUOROCARBONSULFONIC ACID POLYMER ON A
SUPPORT FROM A SOLUTION

The polymers of interest to this invention are substantially fluorinated and have pendant ohains containing sulfonic acid groups or derivatives of sulfonic acid groups. The sulfonic acid groups exhi~it extraordinarily high acid stren~th compared to sulfonic acids that are not fluorinated. Therefore, these materials are very useful as strong acid catalyst and have been shown to be effective in catalyzing many different reactions, such as: hydration of olefins and epoxides, dehydration of alcohols, alkylation and acylation of aromatic hydrocarbons, isomerization and :15 alkylation of paraffins, nitration of organics, pinacolone rearrangements, esterification of a carboxylic acids, hydrolysis of carboxylic acid derivatives, and Diels-Alder condensations.

Fluorocarbon polymers with sulfonic acid pendant groups have advantages over other types of acid catalysts in that the fluorocarbon portion gives extraordinary chemical and thermal stability, as well as almost complete insolubility in most systems.
- 25 Therefore, the polymer can be used as a heterogeneous 33,960-F _1_ : ~.

~ . .
,. ,. . ~ . :

~8~83 catalyst and can be recovered very easily and reused.
Since the reaction occurs on or near the catalyst surface, the amount of surface area must be maximized to obtain optimum efficiency, defined as activity per unit weight of catalyst. This is especially important when con~idering fluorocarbon polymers because of their relatively high cost. One factor that has prevented wide-spread use of these materials as catalysts is their high costs. Their manufacture requires more specialized technology and a larger capital investment than for conventional ion exchange catalysts. It is for this reason that the catalytic efPiciency of such a product must be maximized. As noted above, the catalytic efficiency is defined as the a~ount of product produced divided by the amount of catalyst used. One technique of increasing the efficiency of a heterogeneous catalyst i5 to increase its surface area, thereby exposing more reactive qurface while involving less unused catalyst below the surface. The process of this invention of
2~ applying a thin coat of polymer catalyst to a carrier increases the ratio of active surface area to weight of polymer, compared to that for an unsupported polymer catalyst.
In the prior art, increasing the surface area of a fluorocarbon polymer has been accomplished by several methods, all of which have inherent disadvantages. By decreasing the particle size of a solid, the surface are is increased. However, the disadvantages of using a ~ine particulate catalyst include poor flow dynamics, plugging problems, loss of catalyst include poor flow dynamics, plugging problems, loss of catalyst by entrainment, and more difficult catalyst recovery.

33,960-F -2 ~Z~8l~83
3-As an example of one prior art enhancement~ the fluorocarbon can be extruded into tubing while it is in the thermoplastic sulfonyl fluoride (S02F) form, then converted to the sulfonic acid. Extrusion into tubing re~uireq expensive, specialized equipment and careful handling of the fragile material during processing and reactor assembly. Furthermore, the mechanical strength of the polymer is such that tubing with a wall thickness less than about 0.005 inches (0.125 mm) becomes impractical. This results in only a modest surface area to weight ratio.
The polymer in the thermoplastic sulfonyl fluoride form can be melt deposited onto a solid substrate, and then the surface layer can be converted to the sulfonic acid. This process also requires specialized equipment to form the catalyst to the desired qhape of the substrate. Only the portion of the polymer on the surface is used in the catalytic process since the subsurface portion must remain in the S02F
form to remain bonded to the substrate. This is an inefficient use of the expensive polymer because the surface area is small compared to the amount of polymer below the surfaceO
Although it is considered substantially insoluble, dilute so~utions of the fluorocarbon polymer in the sulfonic acid form can be prepared. These solutions can then be used to coat supports to make 3 catalyst pellets, for in~tance~ But the process of dissolving the polymer converts it from a substantially insoluble species to a species that is very soluble in many polar solvents. Thus, supported catalysts prepared by this method in the prior art have only limited 33,960-F -3-utility because the polymer redissolves very eaqily in many solvents.
One aspect of the present invention is the surprising discovery that a polymer having sulfonic acid groups can be deposited onto a support from a solution, as described above, and then annealed at an elevated temperature, thereby rendering the polymer insoluble.
This annealing step unexpectedly reduces polymer leach during a reaction, thereby resulting in a more durable and long lasting catalyst. By supporting the polymer on a carrier, the surface area of the catalyst is increased, and this in turn improve~ the catalytic efficiency and lowers the cost of the catalyst.
This invention discloses improved heterogeneous acid catalysts and a novel, unobvlous method of preparing these catalysts. The method of preparation involves treating a carrier material with a solution, which contains a fluorinated polymer dissolved in a suitable solvent, such polymer having sulfonic acid functional groups; removing the solvent involved in the prior step; and heat treating or annealing the coated carrier in a faYhion to prevent the polymer from being leached from the carrier. The final heat treatment, or annealing, of the composition com?rises the improvement in the preparation of a heterogeneous catalyst in that the step increases the resistance of the polymer to being leached from the carrier surface and it results in 3 a more durable, and there~ore more efficient acid catalyst. In addition, other polymer coated articles~
such as ion specific electrodes, prepared by the techniques described herein also would be greatly improved.

;~ ' 33,960-F -4-..... ~ : ' . , ~

~Z6~ 3 The polymers that are applicable to this invention have structures that include a substantially fluorinated carbon chain that has attached to it side chains that are also substantially fluorinated and contain sulfonic acid groups or derivatives of sulfonic acid groups. There may be other side chains present that do not contain sulfonic acid groups, if desired, such as fluorinated alkyl or ether chains with no other functional group attached to them. There also may be atoms present in these chains other than carbon and fluorine, such as oxygen, chlorine, and bromine.
Example~ of these polymers are those described in U.S.
Patents 3,282,875; 4,32g,435; 4,330,654 and 4,358,545.
The fluorocarbon portion of the polymer molecule contributes such desirable properties as high thermal and chemical stability and low solubility. The sulfonic acid groups exhibit extraordinarily high acid strength compared to sulfonic acids that are not fluorinated.
Therefore, these materials are very useful as strong acid catalysts and they have been shown to be effective in catalyzing many different types of reactions.
Typical polymers that may be ùsed in this invention have the general structure described below:

33,960-F _5_ , ~

~2~ 33 (CF2-CF2)a~IF-CF2)b(1CF-CF2)C
~ f]m ~n (CF2)dY (CF2)eZ"

where:
Y is S03H, or any group easily converted to S03H;
Z, Z', and Z" are independently F, Cl, Br, CF3, CF2Cl, or fluorinated alkyl;
the ratio o~ a~b varies from 2 to about 50;
c is 0 or greater than 0;
m and n are independently 0 to 4; and d and e are 2 to 5O
In the identified variables, the value of a variable at one location in the formula does not limit the value at another location in the ~ormula. At the various occurrences of the m, n, d or e, the values can be equal or different The same is true of the radical Z at the various locations. In that sanse, the value3 are said to be "independent".
- Since reactions involving heterogeneous cataly~is occur on or near the surface o~ the catalyst, the surface area mu~t be maximized to get maximum catalytic efficiency. Several attempts at this have been made in the prior art, but each attempt results in 33,960-F -6-inherent disadvantages. In this invention, novel and unobvious processes are disclosed for supporting a sulfonyl functional fluorinated polymer on a support, thereby creating a catalyst with more active surface area and improved durability.

The polymer is usually produced in the sulfonyl fluoride form, which is thermoplastic and can be melt fabricated by conventional techniques, such as extrusion or pressing. After it is hydrolyzed to the acid Porm, the polymer is not nearly as thermoplastic as it was originally, and it is therefore difficult to fabricate into useful shapes and forms. It cannot be melt extruded, although some softening occurs above 150~C.
However, it i9 possible to dissolve the polymer by heating it with an aqueous alcohol, particularly 50 percent a~ueou~ ethanol, to about 250~C or higher for several hours in a high pressure autoclave. This converts the polymer from a species that is substantially insoluble to a species that is very soluble in any polar solvents. The resulting mixture may not be a true solution, but instead may be dispersion of finely divided partlcles. In this invention, "polymer solution" is also understood to encompass dispersions. These solutions can be filtered through a 0.2 micrometer filter. Other solvents and mixtures may also be effective in dissolving the polymer.
3 In this invention, the polymer is deposited on the carrier by soaking the carrier in the polymer solution and then removing the solvent. Ordinarily, i~
this composition is treated again with a polar solvent, even at ambient temperature, the polymer redissolves very quickly. Thus, such a composition is not useful as 33,960-F -7-, .. ., :.

~ZB~ 83 a heterogeneous catalyst in many applications. However heating the composition to a sufficient temperature for a suf~icient time renders the polymer insoluble and preventq it from redis~olving. Such a composition i3 much more useful as an acid catalyst due to itY improved durability. This process can be reversed by repeating the high temperature dissolution in 50 percent ethanol in order to recover the polymer from the carrier.
Reducing the solubility by heating the polymer can be referred to as an annealing process. Annealing probably can occur at any temperature abo~e the glass transition temperature of the polymer, which occurs around 20C to 50C for most fluorocarbons of interest here. But the vi3cosity of the polymer is very high, especially below about 150C, and the time required for the polymer to anneal is prohibitively long at low temperature. Also, the qtability of most typiaal polymers decreases markedly above about 300C. These practicalitles define lower and upper limits on the process step. Therefore, the annealing temperature - preferably is above 100C, more prefer~ably between 150~
-- and 300C, and most preferably between 200C and 225C.
At 225C, annealing is eqsentially complete within one hour.

The compo3ition of the carrier is not critical, and the properties that are considered desirable for a carrier may vary in different applications. Properties th~t may be important in some situations include high surface area, high crush ~trengthl high porosity, chemical resistance, thermal stability, and low co~t.
In all cases, the carrier must be resistant to the Yulfonic acid polymer solution and to the high temperature reached during the annealing procedure 33,960-F -8-~;~68~3 g Some representative materialq that could ~erve as carrier~ include alumina, silica, zeolites, silicon carbide, silica-alumina, porous glass, ceramic, spinel, clay and carbon. The preferred weight ratio of polymer to ~upport is between 0.001 and 0.50. There may be instances in which the compositions prepared by the procesqes of this invention may be used ~or applications other than acid catalysis. In theQe instances, the inert carriers may be of some form or material other than those described above.
The following examples are illustrative of certain specific embodiments of this invention.
Example 1 This procedure describes the preparation o~ a ~olution containing a ~luorinated polymer having sulfonic acid functional groups. The polymer used in Example 1 to 5 has the structure:
(CF2CF2)a(C,FCF2)b o where the ratio a/b is -~uch that the equivalent weight of the polymer is about 930 gm/equivalent.
A glass lined stirred autoclave was charged with 150 ml of 95 percent ethanol, 150 ml of water, and 3 15 gm of the fluorinated polymer. The autoclave wa~
~ealed and heated to 250C with vigorous stirring for three hours~ It was then cooled to room temperature and vented. Afterward~, the autoclave contained in a light brown9 slightly turbid liquid. The contents were filtered through a coarse filter ~40 to 60 micrometer3) 33,9~o-F _g_ .

lZ6B0~3 1 o--and again through a fine filter (4 to 5.5 micrometers) to obtain a clear, slightly colored solution. By titration with 0.01N NaOH, the acid capacity of the solution was determined to be 0.0740 milliequivalents/gm. This corresponds to approximately 6.9 weight percent polymer in the solution.
Example 2 This example discloses the process of annealing a polymer to reduce or eliminate the solubility of the polymer. The solvent was evaporated from approximately 10 gm of a solution of polymer prepared as described in Example 1, leaving a brown solid residue. Upon addition of 5 ml of ethanol, the residue redissolved very readily without heating or agitationO The solvent was again removed and the flask containing the residue was heated to 155 to 165C for about three days. After cooling, ethanol was added to the residue. There was no apparent dissolution of the residue. This vividly demonstrates the change in solubility of the polymer induced by the heat treatment, or annealing.
ExamDle 3 In this example, the ef~ect of annealing a coated catalyst is demonstrated. An alumina catalyst support was dried and then soaked for 20 minutes in the polymer solution of Example 1. The excess liquid was decanted and the coated support was dried under vacuum for one hour at about 50 to 75C. The acid capacity was determined by titrating a portion o~ the coated product with ~tandard NaOH. A second portion was washed in boiling ethanol for 30 minutes, dried at 100C under vacuum for two hours and then titrated. A third portion 33,960-F -10-:
... ..

261 31~

was baked at 100C for 24 hourq prior to undergoing the ~ame treatment a~ the second portion. A fourth portion was baked at 200C for one hour prior to undergoing the same wash and dry treatment. The results of these procedure~, described in Table I, show that one ef~ect of annealing the supported polymer cataly~t is reduced solubility of the polymer. Without annealing, hot ethanol leached all of the polymer from the support.
Table 1 Acid Capacity Polymer Portion Annealin~ Solvent meq/gm Coat 1 None None 0.0271 2.03 wt %
2 None Hot ethanol 0.0 0.0 3 100, 24 hr Hot ethanol 0.0102 0.94
4 200, 1 hr Hot ethanol 0.0189 1.77 Example 4 The effect of annealing a coa~ted catalyst support for extended periods of time at 1 to 5C i3 demonstrated in this example. A solution containing 9.4 weight percent polymer in 50 percent ethanol was prepared as in Example 1. An alumina catalyst ~upport was soaked in this solution and the solent was removed under vacuum. In each of three runs, the coated support 3û wa~ he~ted to 175C for the time indicated in Table II
and then was divided into two portions. One portion was titrated while the other portion was washed with boiling ethanol for 30 minutes, dried at 10ûC under vacuum for two hours, and titrated. The results described in 33,960-F

. .
- ., .. ~ . . ' ~ """ ~ ' -12- ~6~3 Table II show the positive effect of longer annealing time at 175C on polymer leach.
Table II

~efore Ethanol Wash After Ethanol Wash Anneal RunTime Acid Polymer Acid Polymer Capacitv Coatinq ca~acitY Coatin~

l24 hrs0.0577 meq/gm 5.36 wt ~ 0.0279 meq/gm 2.60 wt 248 hrs~.0557 5.17 0.0348 3.23 1~ 372 hr~0.0526 4.89 0.0495 4.60 Exam~le 5 A support with a polymer coating is u~ed a~ an acid cataly~t in this example. A cataly~t composition wlth a polymer coat of 2.42 weight percent ~acld capacity 0.0260 meq~gm) was prepared as in Example 3 and annealed at 250C for one hour. It was loaded into three reactor tubes and heated to 150C. Diethylene glycol was pumped into the first of the reactor~.
1,4-Dioxane was identified in the effluent of the fir~t reactor. A solution of diphenol ether and dodecene was fed into the second of the reactors. The major product of thi9 second reactsr was dodecylphenyl phenyl ether.
Propylene and water were fed to the third reactor.
2-Propanol waQ collected in the effluent of the third reactor. These varied use~ confirm the utility of the novel catalyst of this invention.
~ hile the foregoing is directed to the preferred embodiments of the present invention, other and further embodiment-Q of the invention may be devi~ed without departing from the ba~ic ~cope thereof, and the scope thereo~ is determined by the ~laims which follow.

33,960-F -12-: . .. .

; ,: .~.

Claims (14)

THE EMBODIMENT OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. The method of supporting a fluorinated polymer having pendant chains containing sulfonic acid groups, on a support, comprising the steps:
(a) soaking a substrate with a solution that contains a fluorinated polymer having pendant chains containing sulfonic acid groups;
(b) removing the solvent from the mixture;
(c) heating the remaining composition to above the glass transition temperature of the polymer for a sufficient time to render the polymer insoluble.
2. The method of Claim 1 wherein the temperature is above 100°C.
3. The method of Claim 1 wherein the temperature is between 150°C and 300°C.
4. The method of Claim 1 wherein the temperature is between 200°C and 225°C.
5. The method of Claim 1 wherein the temperature is about 225°C.

33,960-F -13-
6. The method of Claim 1 wherein the solution that is used to soak the support contains a fluorinated polymer having pendant chains with the structure:
where Z is F, Cl, Br, CF3, CF2Cl, or fluorinated alkyl;
m is 0 to 4;
d is 2 to 5.
7. The method of Claim 6 wherein m is 0 and d is 2.
8. The method of Claim 1 wherein the solvent is an alcohol or a mixture of an alcohol and water.
9. The method of Claim 8 wherein the alcohol is ethanol.
10. The method of Claim 1 wherein the dissolved polymer passes through a 0.2 micrometer filter.
11. The method of Claim 1 wherein the support is resistant to the sulfonic acid polymer solution and to the temperature to which it is heated.
12. The method of Claim 11 wherein the support is alumina, silica, zeolites, silicon carbide, silica-alumina, porous glass, ceramic, spinel, clay or carbon.
13. The product prepared by the method of Claim 1.
14. The process of using the product prepared by the method of Claim 1 as an acid catalyst.

33,960-F -14-
CA000530402A 1986-02-25 1987-02-24 Method for depositing a fluorocarbonsulfonic acid polymer on a support from a solution Expired - Fee Related CA1268083A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US832,627 1986-02-25
US06/832,627 US4661411A (en) 1986-02-25 1986-02-25 Method for depositing a fluorocarbonsulfonic acid polymer on a support from a solution

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