Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUSRE24865 E
Publication typeGrant
Publication dateSep 6, 1960
Filing dateJul 9, 1949
Publication numberUS RE24865 E, US RE24865E, US-E-RE24865, USRE24865 E, USRE24865E
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Ion exchange materials and method of
US RE24865 E
Abstract  available in
Images(1)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

Sept. 6, 1960 w. JUDA ErAL I Re 24,865

ION EXCHANGE MATERIALS AND METHOD 0F MAKING AND USING THE SAME Original Filed July 9, 1949 Ohms (x /0) ways.

United States Patent ION EXCHANGE MATERIALS AND METHOD OF MAKING AND USING THE SAME Walter Juda and Wayne A. McRae, Lexington, Mass.,

assignors, by mesue assignments, to Iouics Incorporated, Cambridge, Mass., a corporation of Massachuseits Original No. 2,636,851, dated Apr. 28, 1953, Ser. No. 103,784, .luly 9, 1949. Application for reissue Sept. 3, 1959, Ser. No. 824,146

72 Claims. (Cl. 204-98) Matter enclosed in heavy brackets fl appears `in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

KCl solution, of less than 1.5 X10-1 ohm-1 per cm. This potential is determined at 25 C. in the system: 35 caloruel saturated 0.1 M membrane 0.01 M saturated electrode KCl KCl KO1 KG1 solution solution solution solution diffusion diiusion protected. protected The poor conductivity of such membranes necessitates the use of thin and structurally weak membranes of not more than .030 to .050 mm. thickness, in order to effect the transfer of ions therethrough.

These collodiou membranes have been examined and tested, and both types of such membranes exhibit only very weak base exchange and anion exchange properties, respectively. Moreover, even the most effective of these membranes have low total acid numbers ranging from l to 3.3 (as titrated in a solution of the prepared collodion in an organic solvent with alcoholic potassium hydroxide) corresponding to 0.01 'to 0.033 milliequivalent of acid per gram of dry collodion. Of this amount of total acid, only a fraction of one per cent is available for base exchange. This large discrepancy between the total acid and exchange capacity accounts for the very weakly acid character of collodion membranes, which is due to the preponderance of acid groups having very low dissociation constants. Similarly, the protamine type of impregnated electropositive collodion membranes are only weakly basic.

Ion-exchange materials have been made of organic resins, but these have been produced solely in the conventional form of beads or granules of small particle size, averaging usually considerably below 1/s in diameter, or in respect of the largest dimension of each particle. These small granular exchangers have been and could therefore only be used in systems in which they were either contacted with the solution until equilibrium was reached or the solution was percolated through a stationary bed of the exchanger granules. In this case, ion exchange necessarily consisted merely of the transfer of ions from the solution tonto the resin and from the resin back Reissued Sept. 6, 1960 "ice y into the same solution. Hence, in order to exchange ions between two different solutions, it was necessary to first exhaust the capacity of the exchanger by means of a first solution and then regenerate the exchanger by contacting it with a second solution. This method of operating cation exchangers has the disadvantage of being non-continuous and uneconomical in that it requires substantial exhaustion ofthe exchange materials in each half of the cycle.

It is an object of this invention to provide ion-exchange materials, in the form of coherent, uniform, permselective structures of increased electrical conductivities, of substantial ion exchange capacities and of strongly acid and/or strongly basic and/or substantially dissociated salt characteristics. lt is a further object to prepare such ion-exchange materials, in an integral, uniform solid, unfractured structure and with substantial crosssectional dimensions or areas-greater, f-or example, than those of beads or granules-and at least one quarter inch or more in at least one dimension. It is also an object of the invention to provide `a method of preparing such permselective coherent structures and of applying the same to the useful arts. Other objects of the invention will appear from the following disclosure.

It is found by the present invention that ion-exchange materials may be made which are not only more effective in their function of effecting ion-exchange but which may also acquire the novel additional function of effecting, both ion-exchange and ion-regeneration, progressively and simultaneously-and hence, continuously--so long as a difference of ion characteristics or ion concentration is maintained across or through the ion-exchange mate rial or medium.

A criterion for these additional functions is that the calomel electrode ion-exchange material shall be comprised in a coherent and relatively uniform structure, containing water in an amount at least 15% by weight of the dry exchange material, and also contain (or consist of) in integrated association therewith, an ion-exchange component which is substantially insoluble in water but which is freely dissociable therein, the ion-exchange component being oriented with respect to its dissociable ions so as to present a predominant proportion or amount of the same in the exposed surfaces of the structure o-r interface between the ion-exchange material and the aqueous-filled voids. The ion-exchange component is preferably substantially water insoluble and characterized by having one of its ions, upon dissociation, remain integral with and fixed to the coherent polymeric matrix of the ion-exchange material, while the other ion, upon dissociation, is released as a mobile, active ion, into the aqueous filled voids of the ion-exchange material or medium. That is to say, in general the structures of this invention comprise, as an essential part extending substantially throughout, a predominant arnount of an ion-exchange resin which resin may be defined as an insoluble, infusible, synthetic organic polymeric matrix having dissociable ionic groups chemically bonded thereto and having water in gel relationship therewith. An important feature of the structures of this invention is the presence of the gel water in an amount of at least 15% of the weight of the dry ionexchange resin, whereby this structure is rendered highly conductive electrically.

The membrane or diaphragm which is thus formed by the ion-exchange material or medium of the present invention is therefore typically of a coherent, uniform, conductive permselective structure, such as a continuous gel,

in contrast to impermeable or non-conductive films or membranes or non-uniform, gelatinous precipitates or granular exchange materials of the prior art.

The permselective structure of the present invention may comprise or be composed of a binder material, with which the ion-exchange material is integrally associated, the ionic groups of the ion-exchange material being in oriented, dissociable relation with respect thereto and to the aqueous phase of the structure. The permselectve struc-ture of the invention may be composed of polymerized organic segments which are chemically combined with each other to constitute a coherent uniform structure, but which are also chemically combined with and form a part of the molecules of the ion-exchange component, per se. More particularly, the polymerized component is combined with the xed ion of the ion-exchange component, which is oriented with respect to the polymerized component so as to be predominantly in the outer surface of the structure. Upon dissociation of the ion-exchange component, the fixed ion remains in the solid exposed surface of the structure, while the other ion becomes a mobile active ion, liberated in the aqueous filled voids.

A representative and preferred procedure for the preparation of such ion-exchange diaphragms of the present invention is to dissolve `or disperse appropriate polymerizable organic compounds, in water, and then to effect polymerization, and especially curing to the water-insoluble stage, and preferably to the final stage of curing which is to be effected, of the thus dispersed reagents, in the aqueous medium as by heat, pressure, `and the like (without segregation `or evaporation), whereupon the resulting polymer is constrained to cure to 1an integrated gel formation, throughout the dispersion, thereby to constitute a coherent structure, membrane or diaphragm of `a shape and dimensions corresponding to those of the dispersion in which such curing takes place.

In such dispersion, polymerization and curing-if the polymerizing reagent materials possess or form a dissociable component-it is found that the aqueous dispersion effects and maintains the orientation of such component outwardly from the polymerizing and curing components toward and into the aqueous or dispersing phase, and that the polymerizing components tend t-o aggregate into and form a homogeneous continuous, solid, and ultimately coherent phase, occluding the aqueous phase.

Moreover by maintaining the liquid aqueous dispersing phase present and eiective throughout the polymerization-without evaporation and without segregationthe cured polymer acquires and retains a gel structurecharacterized by an extensive interface between the cured polymeric structure and the gel water-in the interfaces of which the dispersed, oriented, dissociable components are concentrated, and maintained subject to dissociation into a fixed ion therein, and a mobile active ion, which is free to migrate into and throughout the aqueous phase or gel Water.

It is found that in order to effect and preserve these relationships and the free permeability of the solidified gel structure, throughout, the aqueous medium should form at least 15%, by Weight, of the weight of the dry ion-exchange component, and should not at any time be allowed to become less, as by dry-ing, etc., lest the continuous coherent structure of the whole should be disrupted or its exposed electric or surface characteristics and ion-exchange function be interfered with or destroyed.

The formation of organic polymers under the usual conditions of curing, of the prior art-wherein media are used other than water, or from which water, if present, is allowed to segregate or escape-does not permit orientation of the components or result in a continuous permselective structure, but in one which is subject to rm impervious solidication and even fracture (non-aqueous resinous beads) upon shrinkage, or otherwise. Either a continuous ion-impermeable structure or a fractured structure would be unsuitable for thet purpose of the present invention. l

By the present procedure, the ion-exchange resin, Whether it constitutes a chemical component of the polymerized structure, or is physically associated therewith, is incorporated integrally and simultaneously with the initial curing of the structure with its dissociable component directed to and into the aqueous phase of the dispersion and of the resulting gel.

It has now been found, for example, that solid, physically stable structures, including membranes, diaphragms, sheets, rods, tubes, vessels and objects of many different shapes (having at least one and more particularly at least two dimensions greater than MW) can be prepared presenting Water-insoluble, coherent, ion-exchange materials of high specic conductivities. According to this invention such ion-exchange materials are of high specic conductivities, exceeding .5 102 ohm1 cm.1 and of high capacities, and contain substantial amounts of dispersed Water, not less than 15% of the weight of lthe air dry exchanger material and up to such proportions as might mechanically interfere with its uniform, coherent or permselective characteristics.

Such coherent structures may generally be made by casting, molding (including compression molding, if without substantial loss or segregation of the water component) and other conventional means of providing large continuous coherent structures of thermosetting or thermoplastic resins, except that the structures of this invention are made and maintained in aqueous media and/or an atmosphere of substantially saturated humidity, so as to prevent evaporation. In this manner the active groups attached to the polymeric organic matrix and oriented with respect to the interfaces thereof are partially or cornpletely dissociable in the internal gel Water into fixed ions of one sign linked to the polymer and into mobile ions of opposite sign. The latter are exchangeable ions and the main or substantially sole carriers of electric current.

In order to obtain the above high conductivities with active groups of relatively low dissociation constants between 105 and 10-3, when measured in the form of one resin-forming ingredient in aqueous solution prior to condensation or polymerization, it is necessary to provide a high density of such groups, that is, unusually high exchange capacities, exceeding 3 milliequivalents (m. eq./ gram) per gram of dry exchanger. 0n the other hand, in the case of ion-exchangers having the preferred strongly dissociated active groups (i.e. having a dissociation constant above 10x-3) smaller exchange capacities, of not less than 0.3 milliequivalent per gram of dry exchanger have now been found to be entirely adequate to give the above conductivities'.

It has further been found that the preferred coherent resinous materials containing at least 15% of internal gel Water and having an exchange capacity exceeding 0.3 milliequivalent per gram of dry exchanger, said capacity being substantially due to active acid and/or basic and/or salt groups having a dissociation constant greater than l0-3 undergo electrolysis when subjected to direct currents in a sutliciently strong electric field, as evidenced by the appearance of electrolysis products at the electrodes. To give a simplified picture of this novel type of electrolysis, it is believed that the mobile ions carry the primary portion of the current and that they are presumably discharged at the electrode, whereas the fixed ions of opposite sign presumably decompose some of the gel water thereby producing an equivalent amount of secondary mobile ions which discharge on the other electrode. These preferred materials capable of undergoing electrolysis may therefore be designated as solid, coherent synthetic resinous permselective ion-exchange electrolytes, of strongly acid or strongly basic or substantially dissociated salt character.

ySuitable active acidic functional groups linked to a` polymeric matrix include -SO3H, -COOH and the like,

SQ-,H being preferred because of its high dissociation cons-tant exceeding l0*3 in suitable resin-forming compounds. The exchangeable hydrogen ion may be partially or completely substituted by other substantially dissociated cations such as the alkali metal ions, the alkaline earth metal ions--namely, calcium, strontium, barium and radium-and also silver, copper, magnesium and ammonium ions, and the like. Typical polymeric matrices to which the functional groups are linked include phenolaldehyde resins; polystyrene-divinylbenzene copolymers and the like. Similarly suitable active basic groups linked to polymerio matrices include quaternary ammonium hydroxides- R1 RzN-OH amino groups, the guanidyl group,

HN=C

the dicyandiamidine group and the like organic nitrogen containing basic groups.

Quaternary ammonium hydroxide groups, the guanidine and the dicyandiamidine residue are among the preferred basic groups because of their high dissociation constant exceeding lU-3. Typical polymers to which active basic groups are linked include the urea-formaldehyde type resins, the melamine-formaldehyde type resins, the polyalkylene polyamine formaldehyde resins and the like. The exchangeable hydroxyl ions may be partially or completely substituted by other substantially dissociated anions such as Cl, NO3, S04- and the like.

The permselective character of the coherent ion-exchange structure of this invention, and more particularly of the coherent ion-exchange electrolytes is shown by the observation that they have either a characteristic concentration potential of the order of 55 millivolts when measured in a concentration cell by means of the calomel electrode system previously described, or an appropriately modified concentration potential measured by means of a different thermodynamic system, such as silver-silver chloride electrodes immersed in two different solutions without salt bridge. It has further been discovered that their high conductivities and their physical stability make possible a great variety of novel applications in which diaphragms comprising coherent ion-exchange electrolytes are used as a barrier to separate two or more solutions of electrolytes, for example, for the purpose of transferring ions of one sign at the substantial exclusion of ions of the opposite sign. Such systems comprising ion-exchange electrolyte diaphragms separating at least two solutions of electrolytes may either be used as such in a variety of applications relying primarily on their ion-exchange properties or they may be used in electrolytic cells. More particularly we prepare and ,use solid diaphragms comprising solid ionexchange electrolytes and we separate by means of these diaphragme and ion-permeable membranes two solutions containing either at least two different concentrations of the same species of ions; or at least two diiferent species of ions, thereby effecting exchange of ions of one charge between two solutions at the substantial exclusion of exchange of ions of the opposite charge, and/or exchange of small ions with the substantial exclusion of exchange of large ions. We may enhance the eifectiveness and the rates of such exclusive exchanges by applying electric fields across the two solutions separated by ion-exchange diaphragms.

Further, we use coherent ion-exchange diaphragms of high conductivity and permselective membranes in the construction of primary and secondary (storage) electromotive force cells in which the diaphragm or membrane.

separates two solutions of different electrochemical potential.

Representative examples of the specific preparation and applications of the ion exchange medium or materials, in accordance with the invention, will be described, reference being had to the accompanying drawings, in which:

Figure l is an elevational diagrammatic view of an assembly of a rod of the ion-exchange material between two columns of mercury for the passage of an electric current therethrough;

Fig. 2 is an elevational diagrammatic cross-section of a cell containing a diaphragm of the ion-exchange material therein as a separator or barrier between two electrolyte solutions;

Fig. 3 is a visualized detail cross-section of a submicroscopic portion of the ion-exchange medium illustrative of the coherent solid structure thereof and of the intervening continuous gel water dispersed therethrough and occluded therein, which are of the order of molecular dimensions; and

Fig. 4 is a graph representing the variation in elective resistance of an ion-exchange medium of this invention with respect to alternating electric current of differing frequencies.

EXAMPLE l Preparation of membranes of phenol sulfonic acid-formaldehyde The impregnating, low molecular weight polymer was prepared as follows:

Pants by weight Aqueous phenol sulfonic acid (65%) 50' Aqueous formaldehyde (35.4%) 24.7

The acid and the formaldehyde are shaken together and partially polymerized at 50 1C. in a closed container (to retain the moisture and formaldehyde). This precuring requires lVz to 2 hours after which the viscous mixture was used to impregnate reinforcing webs such as Saran, Vinyon, glass cloth, and similar materials resistant to strong acids. It was poured into a mold to form the cast disks. The curing (until the polymer turned dark brown or black) was carried out at JC. in a closed system and in the presence of moisture. This process required from two hours to two days depending upon the quantity and geometry of the polymerizing mass.

The special characteristics of the cured material both cast and impregnated have been entered into the appended table. Precured material was preserved in a refrigerator at 5 C. for weeks at a time with no deleterious eect.

Before using, the diaphragm was conditioned by soaking in water to bring the water content to the saturation Value and thereafter maintained in wet condition throughout, for purposes of testing and use. A similar procedure was followed in all of the following examples.

In the course of measuring the conductance of the diaphragm, it was found that the specific conductivity (1.4 l0*l ohm*1 cmrl) of the diaphragm in equilibrium with l N hydrochloric acid was greater than that of the 1 N hydrochloric acid (O.36 10-1 ohm-1 cmrl) itself.

It may also be observed that in preparing the ionexchange materials of the above and following examples (and also of organic polymeric ion-exchange materials in general, in accordance with the present invention) the time and/or temperature and other conditions of curing may be considerably extended Without substantially altering, the electrical and/ or surface characteristics of the. resin solong as the Water component is maintained.

EXAMPLE 2 Preparation of molded diaphragms of Amberlite IRC-50 Amberlite IRC-50 is identied by the maker as a synthetic cation-exchanger in the form of white opaque in fournn'nutes.v Alow moleculanweight polymer `was obtained by heating to 40 C. forabout forty-veminutes. This polymer was then usedto impregnate Saran and to prepare cast diaphragms. for the cast material were 75 C. and twelve hours in the presence of moisture. The curing of impregnated material was done at a higher temperature, 90 C., and also in the presence of moisture.

TABLE Oharacteris- Capacity tlc concen- Conductivity Moisture (Milliequiv- K ave Material Form tration of structure percent of alents per (order of potential (ohms1 cm.-1) bone-dry gram magni- (millivolts) material bone-dry tude) material) @est +55 o. 9-14 10-1 114 1. 5-1. 7 7 10-2 Strongly amd caliomxchngef f Example L {impregnated seran +51 4. 5 5. s x 10-Aq 114 1. 5-1. 7 7 10-2 weakly acid cation-exchanger of Example 2 feast'.j +29. 2 g 13g i0 3 X 10-16 0 1 '10* Strongly basi@ amon'exchaugef 0f Example 3 (impregnated Saran a2. 4. 5-5. 5 1o-2 121 s. o 3 10-1 strongly acid cation-exchanger of Example 4 east +16. 3. 5 X 10-2 45 l. 5-2 10'1-10-2 [strongly basic anion-exchanger 0f Example 5 .do 52. 4. 7 X 10-2 58 0. 8-1. 4 10-1-10-2] beads exhibiting the extremely high capacity of 10.0- EXAMPLE 4 10.2 milli-equivalents per dry gram deriving its exchange capacity form weakly acid carboxylic acid groups and preparano gggieoqfaphmgms 0f was used in the preparation of a cast disk as follows:

Parts Amberlite IRC-50 (containing 20% water) 50 Polystyrene solution in benzene [solution]) 50 The resin is pulverized in a hammer mill, sieved to liner than 100 mesh, made into a slurry with the polystyrene solution, transferredto thevv mold, and cured at 50 C. The tnal product, containing 20% Water on the basis of the weight of Wet resin, as lindicated above, accordingly contained 25% water on the basis of the Weight of dry resin.

In an alternate procedure, 50 parts of Amberlite IRC-50, with about 27% moisture and ner than 100 mesh, were mixed with 50 parts of a 25% solution of polystyrene in benzene, poured intoV a 3.5 inch vPetri dish and allowed to cure, as above.

In general, the kuse of electrically non-conducting inert binders for powdered resinous ion-exchangersl such as the polystyrene of this example, reduces inherently the conductivity of the cast or molded products. While products containing moderate amounts of such binders may be useful for many purposes, excessive amounts (eg. amounts exceeding 30% by weight of the dry exchangematerial), usually cause such an increase in electrical resistance as to render the products useless for the purposes of this invention.

Satisfactory diaphragms have also been molded using this type of binder and, for example heat (120 C.), pressure (2500 lbs/sq. in.), and thirty minute time of curing. Thus an alternative procedure, for formingl structuresv comprising granules of :an ion-exchange resin and a binder therefor, is to combine the granules (containing at least 15% Water) and the binder material, and effect solidification ofthe binder material with the granules embedded therein,under conditions substantially preventive of the escape` of water from the granules.

EXAMPLE 3 Preparation of melamine-guanidine formaldehyde diaphragms Parts Melaminev 126 Guanidine carbonate 90 Aqueous formaldehyde (35.4%) 243 Aqueous hydrochloric `acid (37%) 162 'I'he melamine and guanidine carbonate were combinedwith the acidfand the formaldehyde was added to the mixture. At 110 C. the material polymerized with- The (strongly acid) sulphonated copolymer of styrene and divinylbenzene, which is described by W. C. Bauman and I. Eichhorn under thename of Dowex 50 in the Journal of the AmericanChemical Society, volume 69, page 21830 (1947) and also by DAlelio in U.S. Patent 2,366,007, was used in the preparation of a cast disk as follows:

The commercial resin, obtained as 100-200 mesh beads was cast 'into disks by means of heat and a binder. The

binder used vwas phenolsulfonic acid formaldehyde.

Parts Dowex 50 (calculated as bone dry) 100 40 Aqueous phenolsulfonic racid (65%) 25 Aqueous formaldehyde (35.4%) 12.5

The phenolsulfonic acid and formaldehyde Wereshaken together and addedto the Dowex 50. The resulting slurry was transferred [poured] into a mold and cured at 105 C. in an atmosphere saturated with water vapor.

[EXAMPLE 5 Preparation of molded diaphragms of Amberlite IRA-400 This commercial resin, obtained as 20440 mesh beadsV was cast into disks by means of. heat and a binder. The binder used was melamine-guanidine formaldehyde.

5 Parts Amberlite IRA-400 (containing 30% of water) 100 The low molecular weight melamine guanidine formaldehyde polymer prepared in accordance with the procedure of Example 3 20 Water 80 The binder was dissolved in the water by heating, and

the resulting viscous solution added tothe beads of Amberlite IRA-400. This slurry was poured into a mold and cured at C. in an atmosphere saturated with water vapOrJL The curing conditionsv 9 EXAMPLE 6 Electrolysis in the ion-exchange medium Parts Sulfuric acid (95.5%) 100 Phenol 79 Formaldehyde (37%, in water) 129 The phenol was melted and heated to 95 C., the sulfuric acid added land the mixture heated at 140 C. for two hours and then cooled to`15 C. The phenol-sulfuric acid mixture was added to the formaldehyde which had been cooled to C., additional cooling being provided to keep the temperature below 20 C. The resulting mixture may be stored for weeks fat C.

The unpolymerized liquid was poured into a cylindrical glass mold and polymerized at 60 C. until dark in color. The rod was conditioned by soaking in distilled water until substantially all water-soluble reagents were removed. The resulting cation exchange rod 1 (Fig. 1), 5.2 cm. long and 1.2 cm. in diameter, was mounted between the rods of glass tubes 2, 3, in a rubber tubing 4 as shown. The glass tubes 2, 3, were filled with mercury at 5 and 6 into which were dipped platinum electrodes 7 and 8. A direct current of 4 milliamperes developed when a potential of 6 volts was imposed on the system, the current being carried ionically in the cast rod, for a constant D.C. potential varying slightly with time giving rise to an evolution of hydrogen gas at the mercuryexchanger interface adjacent to the positive terminal. Much of the oxygen combined with the mercury at the interface to give oxides of mercury. If the rod is kept wet with water, the electrolysis may be continued. Measuring the volume of evolved hydrogen at constant pressure gives a measure of the number of coulombs passed by the electrical circuit. The system may be used as a convenient coulombmeter.

Upon `closing the circuit an instantaneous very high current of 0.04 iampere was observed which dropped to the steady value given above. This unusual behavior illustrates the novel nature of this type of electrolysis.

EXAMPLE 7 The novel electrical properties of cast ion-exchange materials for the measurement of frequency of an electric field Parts Sulfuric acid (95.5%) 8 Phenol 100 Formaldehyde (37%) 130 The phenol and sulfuric acid were mixed together, heated at 130 C. for three hours, cooled to 15 C. and added to the formaldehyde which had been chilled to 0 C., additional cooling being provided to keep the temperature below 20 C. The mixture was a reddish-brown, oily liquid. It may be stored for weeks at 5 C. The liquid was poured into a cylindrical glass mold and polymerized `at 60 C. until black in color. The resulting rod was conditioned by soaking in distilled Water and then in 2 N HC1 and finally was washed free from HCl with distilled water. The resistance of this Water-satunated rod was measured in a direct current, and in alternating currents of varying frequencies. It was found to decrease at a rate of 4.7 103 ohm-seconds per cycle in the range of 1,000 to 20,000 cycles per second, the variation being shown in the gnaph of Figure 4. This method permits one to measure the frequency of an applied alternating current by measuring the resistance of a calibrated resin rod.

EXAMPLE 8 Continuous ion-exchange between two electrolytes Parts Sulfuric acid (97%) 10S Phenol 100 Formaldehyde (37% in water) 130 The phenol and sulfuric acid were mixed together and heated #at 120 C. for four hours, cooled to 15 C. and added to the formaldehyde which had been cooled to 0 C. Additional cooling was provided to keep the temperature below 20 C. The mixture may be stored for weeks at 5 C. without excessive polymerization.

A rod was made of this material by pouring it into a cylindrical glass mold and curing at 60 C. until solid and dark in color. The resulting resin cylinder was drilled out on a lathe to give a tube 4.5 cm. long, 0.9 cm. outside diameter and 0.3 cm. inside diameter. This tube was mounted in a glass cell. A solution of 0.02 N CaCl2 was circulated through the inside of the tube at 12.5 cc./min. for 24 hours and a solution of 0.2 N NaCl on the outside at 2.5 cc./min. for 24 hours. Transfer of cations took place almost to the exclusion of anions.

A reinforced diaphragm was made by impregnating Vinyon lter cloth with unpolymerized exchanger and curing at C. for 10 minutes in a moisture saturated atmosphere. The resulting diaphragm was suitably mounted in a glass vessel to give a vertical partition. A 0.1 N CaClz solution was put in one compartment and a 0.1 N KNO3 solution in the other. The rate of exchange of calcium ions between solutions was l.6 l02 mg. per ft. hour. This was considerably greater than the nate of exchange of chloride ions which was 2.5 X 103 mg. per ft. hour.

EXAMPLE 9 Application of ion exchange diaphragms to the sodium chloride electrolysis cell Preparation of ion-exchange diaphragm: Parts Sulfuric acid (95.5%) 141 Phenol Formaldehyde (37% in water) 180 The sulfuric acid wlas added to the phenol at 95 C. and the mixture heated at C. for two hours and cooled to room temperature. The formaldehyde was cooled to 0 C. and the mixture of phenol and sulfuric acid added, additional cooling being provided to keep the temperature of the mixture below 20 C. The temperature was then reduced to 5 C., yat which temperature the mixture may be stored for weeks without polymerization. The mixture was a viscous, oily liquid of reddishamber color.

The mixture was poured into a cylindrical glass mold and heated at 50 C. until solid and dark in color. The resulting resin cylinder was saWed into disks, and the disks were washed in distilled Water until the wash water was sulfate free and'one of the disks 9 was then used in au electrolysis cell 10 diagrammatically shown in Fig. 2.

The diaphragm was 0.3 cm. in thickness with an area of 0.7 cm?. The anolyte was a saturated NaCl solution, the catholyte 25 cc. of 0.16 N NaOH, the current 20 milliamperes at 6 volts.

At the end of 24 hours there was no chloride in the catholyte (silver nitrate test) and the concentration of NaOH in a total volume of 22 cc. was then 1.52 N.

We have found the conductance of this cast phenolsulfuric acid formaldehyde diaphragm to be 33x10-2 ohms-1 cm.1.

Hence, this cell is superior to the conventional diaphragm caustic cell in producing chloride yfree caustic. It is superior to the mercury cell in producing chloride free caustic in that it involves no mercury.

EXAMPLE l0 Permselective diaphragms in the construction of primary electric cells Preparation of the diaphragm:

Parts Triamino triazine (melamine) 126 Guanidine carbonate 90 Hydrochloric acid (37% in water) 135 Formaldehyde (37% in water) 300 The guaUidinecarbOnateand triamino triazine (melamine) were, mixed ,together andthe hydrochloric acid added andthen ,the formaldehyde. A piece of Vinyon cloth was impregnated in the warmed unpolymerized mixture and cured at 110 C. for 10 hours. The polymer was colorless and transparent. The impregnated cloth was converted to thev sulfate form by soaking in an. excess ot 0.5 N Na2SO4 solution, the excess solution was removed and the diaphragm then mounted as a vertical partition in a glass vessel. One cornpartmentwas lled with a saturated solution of zinc sulfate and theother with a saturated solution of copper sulfate. A zinc plate wasv immersed in the zinc sulfate solution and a copper plate inthe copper sulfate solution. After four days there .was no visible coatingof copper on the Zinc electrode. The areaof the diaphragm was 6 square inches andthe thickness was `0.04 inch. The open circuit voltage. at 22 C. was 1.050 volts and did not vary more than 2% in the range -8 C. to 25 C. The internal resistance of the cell was 24 ohms at 22 C. The internaltresistance of the cell. was decreased to 7 ohms by substituting cupric and zinc. chlorides with a diaphragm conditioned with, 0.5 N NaCl. This type of cell is commonly referred to as a Daniel cell.

We claim:

l. As an article of manufacture, a solid unfractured structure vhaving at least two dimensions each in excess of 0.25 inch, and lcomprising as an essential part extending substantially throughout said structure, a predominant amount of an ion exchangey resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissocialble ionic groups chemically bonded to saidrn-atrix, and water in gel relationship with said matrix; said groups having, a dissociation constant of at least 10-5 and being present in an amo-unt. of at least 0.3 milliequivalent per` graml of dry resin, and said-water being present in an amount of at least 15% of the weight of the dry resin.

2. As an articleof manufacture, a solid unfracturedl sheet `havingtwo dimensions each in excess of 0.25 inch, and comprisingas an essential part extending substantially throughout said sheet, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and ywater in gel relationship with said matrix; said groupshaving a dissociation constant of at least 10-5 and being present in an amount of at least 0.3V milliequivalent per gram of dry resin, andsaid Iwater being present in an amount of at least of the weight of the dry resin..

3. As an article of manufacture, a solid unfractured membrane [structure] having at least two dimensions eachV in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said membrane [structurel a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic` polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water` in gel relationship with said matrix; said groups having a dissociation constant (K) of at least 10w5, said groups being present in an amount of at least 3.0` milliequivalents per gram of dry resin when Kis between 10*5 and l0-3 and in an amount of at least 0.3 milliequivalent per gram of dry resin when K is 10-3 or greater; and said water being present in an amount of at least l5 percent of the weight of the dry resin.

4. The article defined by claim 3 wherein the water is present in an amount of at least 25 percent of the weight of dry resin.

5. As an article of manufacture, a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure, a predominant amount of a homogeneous continuous phase of an ion ex. change resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groupsv chemically bonded to said matrix, and Water in gel relationship with said matrix; said groups having a dissociation constant (K) of at least 10ml, said groups being present in an amount of at least 3.0 milliequivalent per gram of dryresin when K is between 10-5 and 10-3 and in an amount of-at least 0.3 milliequivalent per gram of dry resinwhen vK-islO-3 or greater; and said water being presentin an; amount of at least l5 percent of the weight of the dry resin.

6. The article defined by claim 5 wherein `the water is present in an amount of at least 25 percent of the weight of dry resin.

7; As an article ofrnanufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising as yan essential part extending substantially throughout said sheet, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric. matrix, dissociable ionic groups chemically bonded to `said matrix, and water in gel relationship with said matrix; said groups having a dissociation constant (K) of at least 105, said groups being present in an amount of atleast 3.0 milliequivalents per gram of dry resin when K is -between 10-5 and 10-3 and in an amount of at least 01.3 milliequivalent per gram ot dry resin when K is l0h3 or greater; and `said water being present in an amount of 'at least l5 percent of the weight of the dry resin.

8. The article defined by claim `7 wherein the ion exchange resin is a homogeneous continuous phase.

9. The article defined by claim 8 wherein the Water is present in an amount of at least 25 percent of the weight of dry resin.

10. The article deiined by claim 7 wherein the water is present in an amount of at least 25 percent of the weight of dry resin.

l1. As an article of manufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising in combination a reinforcing web and as an essential part extending substantially throughout said sheet, a` predominant amountof an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, `dissociable ionic groups chemically bonded to said matrix, and water in Vgel relationship with *at least 15 percent of the weight of dry resin.

l2. The article deined by claim ll wherein the ion exchange resin is a homogeneous continuous phase.

13. The article detined by claim l2 wherein the water is present in an amount of at least 25 percent lof the weight of dry resin.

14. The article defined vby claim 11 wherein the water is present in an amount of atleast 25 percent of the weight of dry resin.

l5. As an article of manufacture, a solid unfractured sheet havingtwo dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said sheet, a predominant amount of a homogeneous continuous phase of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociableionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups having adissociation constant of at least 105 and being present in an amount of at least 0.3

milliequivalent per gram of dry resin, and said water being- `present in an amount of at least 15% of the weight of the each in excess of 0.25 inch, and comprisingas an essential f part extendingn substantially; throughout said [structure] eases membrane, a predominant amount of particles of an ion exchange resin, and an insoluble binder therefor, said resin comprising: an insobluble infusible synthetic organic polymeric matrix, `dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups having a dissociation constant (K) of at least 10-5, said groups being present in an amount of at least 3.0 milliequivalents per gram of dry resin when K is between 10-5 and 10-3 and in an amount of at least 0.3 milliequivalent per gram of dry resin when K is l-3 or greater; and said Water being present in an amount of at least 25 percent of the weight of the dry resin.

17. The article dened by claim 16 wherein the binder is a non-conducting material.

18. As an article of manufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said sheet, a predominant amount oi particles of an ion exchange resin, and an insoluble binder therefor, said resin comprising: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups having a dissociation constant (K) of at least -5, said groups being present in an amount of at least 3.0 milliequivalents per gram of dry resin when K is between l0'-5 and 10-3 and in an amount of at least 0.3 milliequivalent per gram of dry res-in when K is l03 or greater; and said water being present in an amount of at least 25 percent of the weight of the dry resin.

19. The article deiined by claim 18 wherein the binder is a non-conducting material.

20. As an article of manufacture, a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure, a predominant amount of the combination of particles of an ion exchange resin and a binder which is an ion exchange resin, each of said exchange resins comprising: an insoluble infusibile synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups having a dissociation constant (K) of at least 10r5, said groups being present in an amount of at least 3.0 milliequivalents per gram of dry resin when K is between 10-5 and 10-3 and in an amount of at least 0.3 milliequivalent per gram of dry resin when K is l03 or greater; and said water being present in an amount of at least 25 percent of the weight of the dry resin.

21. As an article of manufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said sheet, `a predominant amount of the combination of particles of an ion exchange resin and a binder which is an ion exchange resin, each of said exchange resins comprising: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups having a dissociation constant (K) of at least 10i-5, said groups being present in an amount of at least 3.0 milliequivalents per gram of dry resin when K is between l0"5 and 10-3 and in an amount of at least 0.3 milliequivalent per gram of dry resin when K is l0n3 or greater; and said water being present in an amount of at least 25 percent o-f the weight of the dry l resin.

22. As an article of manufacture, a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups 14 having a dissociation constant of at least 10*3 and being present in an amount of at least 0.8 milliequivalent per gram of dry resin, and said water being present in an amount between about 58 and 138 percent of the weight of the dry resin.

23. As an article of manufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said sheet, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and Water in gel relationship with said matrix; said groups having a dissociation constant of at least 10-3 and being present in an amount of at least 0.8 milliequivalent per gram of dry resin, and said water being present in an amount between about 58 and 138 percent of the weight of the dry resin.

24. As an article of manufacture, a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidino, said groups being present in an amount of at least 0.8 milliequivalent per gram of dry resin; and said water being present in an amount between about 5 8 and 138 percent of the weight of dry resin.

25. The article delined by claim 24 wherein the ion exchange resin is a homogeneous continuous` phase.

26. As an article of manufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said sheet, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidino, said groups being present in an amount of at least 0.8 milliequivalent per gram of diy resin; and said water being present in an amount between about 58 and 138 percent of the weight of dry resin.

27. The article deiined by claim 26 wherein the ion exchange resin is a homogeneous continuous phase.

28. As an article of manufacture, a solid unfractured sheet having two idimensions each in excess of 0.25 inch, and comprising in combination a reinforcing web and as an essential pant extending substantially throughout said sheet, a predominant amount of an ion exchange resin which comprises: -an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidino, said groups being present in an amount of at least 0.8 milliequivalent per gram of dry resin; and said water being present in an amount between about 58 .and 138 percent of the weight of dry resin.

29. The article deiined by claim 28 wherein the ion exchange resin is a homogeneous continuous phase.

30. As an article of manufacture, a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure, a predominant amount of particles of an ion exchange resin, and an insoluble binder therefor, said resin comprising: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded Ito said matrix, and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidino, said groups being present in an amount of at least 0.8 rnilliequivalent per gram of dry resin; and said water being present in an amount between about 58 and 138 precent of the weight of dry resin.

31. The article deined by claim 30 wherein the binder is a non-conducting material.

32. As an article of manufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said sheet, a predominant amount of particles of an ion exchange resin, and an insoluble binder therefor, said resin comprising: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded lto said matrix, and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidino, said groups being present in an amount of at least 0.8 milliequivalent per gram of dry resin; and said water being present in an amount between about 58 and 138 percent of the weight of dry resin.

33. The article defined by claim 32 wherein the binder is a non-conducting material.

34. As an article of manufacture, a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure a predominant amount of the combination of particles of an ion exchange resin and a binder which is an ion exchange, resin, each of said exchange resins comprising: an insoluble infusible synthetic organic polymeric mixture, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidino, said groups being present in an amount of at least 0.8 milliequivalent per gram of dry resin; and said water being present in an amount between about 8 and 138 percent of the weight of dry resin.

35. As an article of manufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said sheet, a predominant amount of the icombination of particles of an ion exchange resin and a binder which is an ion exchange resin, each of said exchange resins comprising: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, yand dicyandiamidino, said groups being present in an amount of at least 0.8 milliequivalent per gram of dry resin; and said water being present in an amount between about 58 and 138 percent of the weight of dry resin.

36. As an article of manufacture, a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups being selected from the 'class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidino, said groups being present in an amount of at least 0.3 milliequivalent per gram of dry resin; and said water being present in an amount of at least 25 percent of the weight of dry resin.

37. As an article of manufacture, a solid unfractured sheet having two dimensions each in excess of 0.25 inch, and comprising as `an essential par-t extending substantially` throughout said sheet, a predominant amount of au ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidiuo, said groups being present in an amount of at least 0.3 milliequivalent per gram of dry resin; and said water being present in an amount of at least 25 percent of the weight of dry resin.

38. As an article of manufacture, a solid unfractured' sheet having Vtwo dimensions each in excess of 0.25 inch, and comprising in combination a reinforcing web and as an essential part extending substantially throughout said sheet, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in Igel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamindino, said groups being present in an amount of at least 0.3 milliequivalent per gram of dry resin; and said water being present in an amount of at least 25 percent of the weight of dry resin.

39. As an article of manufacture, a solid unfractured sheet having two dimensions each i-n excess of 0.25 inch, and comprising as an essential part extending substantially throughout said sheet, a predominant amount of particles of an ion exchange resin, and an insoluble binder therefor, said resin comprising: an insoluble inusible synthetic organic polymer matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix; said lgroups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicyandiamidino, said groups being present in an amount of at least 0.3 milliequivalent per gram of dry resin; and said water being present in an amount of at least 25 percent of the weight of dry resin.

40. The article defined by claim 26 wherein the ion exchange resin is a phenol sulfonate-aldehyde condens-ation product.

41. The :article defined by claim 29 wherein the ion exchange resin is a phenol sulfonate-aldehyde condensation product.

42. The article dened by claim 26 wherein the ion exchange resin is a sulfonated copolymer of styrene and divinyl benzene.

43. The article deiined by claim 37 wherein the ion exchange resin is a sulfonated copolymer of styrene and divinyl benzene.

44. The article defined by claim 32 wherein the ion exchange resin is a sulfonated copolymer of styrene and divinyl benzene.

45. The article delined by claim 39 wherein the ion exchange resin is a sulfonated copolymer of styrene and divinyl benzene.

46. The article `defined by claim 26 wherein the ion exchange resin comprises a copolymer of styrene and divinylbenzene having quaternary ammonium groups bonded to the aromatic nuclei.

47. The article defined by claim 37 wherein the ion exchange resin comprises a copolymer of styrene and divinylbenzene having Quaternary ammonium groups bonded to the aromatic nuclei.

48. The article defined by claim 32 wherein the ion exchange resin comprises a copolymer of styrene and divinylbenzene having quaternary ammonium groups bonded to the aromatic nuclei.

49. The article defined by claim 39 wherein the ion exchange resin comprises a copolymer of styrene and divinylbenzene having quaternary ammonium groups bonded to the aromatic nuclei.

50. The `article defined by claim l0 wherein the poly- 17 meric matrix comprises a copolymer of styrene and divinlylbenzene.

51. The article defined by claim 26 wherein the ion exchange resin is a melamine guanidine condensation product.

52. In the method of forming 1a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, `and water in gel relationship with said matrix; said groups having a dissociation constant of at least l*5 and being present in lan amount of at least 0=.3 milliequivalent per gnam of dry resin, and said water being present in an amount of at least 15% of the weight of dry resin, the step of forming said solid structure under conditions substantially preventive of the escape of water.

53. The method of forming a solid unfractured structure having iat least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure a predominant amount of an ion exchange resin, comprising the steps of: forming an aqueous dipersion of material polymerizable into an ion exchange resin which comprises an insoluble, infusible synthetic organic polymeric matrix and dissociable ionic groups chemicallf)l bonded to said matrix, said groups having a dissociation constant in excess of *5 and being present in the amount of at least 0.3 milliequivalent per gram of dry resin said dispersion containing water in `an vamount of at least of the Weight of dry resin; and polymerizing said material to the insoluble infusible stage under conditions substantially preventive of the escape of Water from said dispersion.

54. The method of forming a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure a predominant amount of an ion exchange resin, comprising the steps of: forming an aqueous dispersion of material polymerizable into an ion exchange resin which comprises an insoluble infusible synthetic organic polymeric matrix and dissociable ionic groups chemically bonded to said matrix, said groups having a dissociation constant (K) in excess of 10-5, said `groups being present in `an amount of at least 3.0 milliequivalents per gnam of dry resin when K is between 10-5 and 10-3 and in an amount of at least 0.3 milliequivalent per gram of dry resin when K is 103 or greater; said `dispersion containing Water in an amount of at least 25% of the Weight of dry resin; casting said dispersion to the desired form; Iand polymerizing said material to the insoluble infusible stage under conditions substantially preventive of the escape of water from said dispersion.

55. The method of forming a `solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure a predominant amount of an ion exchange resin, comprising the steps of:` forming an aqueous dispersion of material polymerizable into an ion exchange resin which comprises an insoluble infusible synthetic organic polymeric matrix and dissociable ionic groups chemically bonded to said matrix, said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl, and dicy'andiarnidino, said groups being present in a concentration of at least 0.8 milliequivalent per gram of dry resin, said dispersion containing Water in an amount between about 58 and 138 percent of the weight of dry resin; casting said dispersion to the desired form; and polymepizing said material to the insoluble infusible stage under conditions substantially preventive of the escape of water from said dispersion.-

56. The method of forming a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure a predominant amount of an ion exchange resin, comprising the steps of: combining with a binder a predominant amount of particles of an ion -exchange resin which comprises an insoluble infusible `synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and water in gel relationship with said matrix, said groups having a dissociation constant (K) of at least l0-5, said groups being present in an amount of at least 0.3 milliequivalent per grani of dry resin when K is l03 or greater, and said Water being present in an amount of at least 25% of the Weight of dry resin; and forming said structure under conditions substantially preventive of the escape of water.

57. The method of forming a solid unfractured structure having at least two dimensions each in excess of 0.25 inch, and comprising as an essential part extending substantially throughout said structure a predominant amount of an ion exchange resin, comprising the steps off: combining particles of an ion exchange resin with an aqueous dispersion of material polymerizable into an ion exchange resin, each of said resins comprising an insoluble infusible synthetic o-rganic polymeric matrix, dissociable ionic groups chemically bonded to said matrix, and Water in gel relationship with said matrix, said groups having a disassociation constant (K) of at least 10-5, said groups being present in `an amount of at least 3.() milliequivalents per gram of dry resin when K is between l0*5 and 10-3 and in an amount of at least 0.3 milliequivalent per gram of dry resin when K is 103, or greater and said water being present in an amount of at least 25% of the Weight of dry resin; casting said mixture to the desired form; and polymerizing the dispersed material to the water insoluble infusible stage under conditions substantially preventive of the escape of water.

58. In an electrolytic system, a pair of compartments, a barrier separating said compartments, and electrical contacting means communicating with the interior of each of said compartments, said barrier comprising as an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and Water in gel relationship with said matrix; said groups having a dissociation constant greater than 10-5 and being present in an amount of at least 0.3 milliequivalent per gram of dry resin, and said Water being present in an amount of at least 15% of the weight of dry resin.

59. In an electrolytic system, a pair of compartments, a barrier separating said compartments, and electrical contacting means communicating with the interior of each of said compartments, said barrier comprising `as an essential part extending substantially throughout, a predominant amount of an ion sxchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said groups having a dissociation constant (K) greater than 10-5, said groups being present in an amount of at least 3.0 milliequivalents: per gram of dry resin for groups having a K between 10-5 and l0-3 and in an amount of at least 0.3 milliequivalent per gram ot dry resin for groups having a K of l03 or higher; and said Water being present in an amount of at least 25% of the weight of dry resin.

60. The system defined by claim 59 wherein the ion exchange resin is a homogeneous continuous phase.

6l. An electrodialysis cell comprising a pair of compartments, a barrier separating said compartments and electrical contacting means communicating with the in-4 terior of each of said compartments, said barrier comprising as an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded lo said matrix and water in gel relationship with said matrix; said groups having a dissociation constant (K) greater than 10-5, said groups being present in an amount of at least 3.0 milliequivalents per gram of dry resin for groups having a K between 10-5 and l0-3 and in an amount of at least 0.3 milliequivalent per gram orf `dry resin lfor groups having a K of l"3 or higher; and said water being present in an amount of at least 25% of the weight of dry resin.

`62. An electrodiialysis cell comprising a pair of compartments, a barrier separating said compartments and electrical contacting means communicating with the interior of each of said compartments, said barrier cornprising as an essential part extending substantially throughout, `a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl and dicyandiamidino and being present in an amount of at least 0.8 milliequivalent per gram of dry resin, and said water being present in an amount of be-tween about 58 and 138 percent of the weight of dry resin.

63. An electrodialysis cell comprising an anode compartment and a first electrode therein, a cathode compartment and a second electrode therein, and a barrier separating said compartments, said barrier comprising as an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said lgroups having a dissociation constant (K) greater than -5, said groups being present in an amount of at least 3.0 milliequivalents per gram of dry resin for groups having a K between 10-5 and l0*3 and in an amount of at at least 0.3 milliequivalent per gram of dry resin for groups having a K of 10-3 or higher; and said water being present in an amount of at least 25% of the weight of dry resin.

64. An electrodialysis cell comprising an anode compartment and a iirst electrode therein, a cathode compartment and a second electrode therein, and a barrier separating said compartments, said barrier comprising as an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymerio matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl and dicyandiamidino and being present in an amount ofv at least 0.8 milliequivalent per gram of dry resin, and said water being present in an amount of between about 58 and 138 percent of the weight of dry resin.

`65. In an electromot-ive cell adapted to provide a source of electromotive force between a pair of electrodes, a banier between said electrodes, said barrier comprising as an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble 4infus-ible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said groups having a dissociation constant (K) greater than 10x5, said groups being present in an amount of at least 3.0 mlliequivalents per gram of dry resin for groups having a K between 10-5 and 10-3 and in an amount yof at least 0.3 milliequivalent per gram of dry resin-forgroups having aK of 11)*3 20 or higher; and said water being present in an amount of at least 25% of the Weight of dry resin.

66. In an electromotive cell adapted to provide a source of electromotive forcev between a pair of electrodes, a barrier between said electrodes, said barrier comprising asY an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl and dicyandiamidino and being present in an amount of at least 0.8 milliequivalent per gram of dry resin, and said water being present in an amount of between about 58 and 138 percent of the weight of dry resin.

67. In a Daniel cell, a barrier separating the two solutions, said barrier comprising as an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemicallyy bonded to said matrix and water in gel relationship with said matrix; said groups having a dissociation constant (K) greater than 10-5, said groups being present in an amount of at least 3.0 milliequivalents per gram of dry resin for groups having a K between 105 and 10-3 and in an amount of at least 0.3 milliequivalent per gram of dry resin for groups having a K of 10-3 or higher; and said water being present in an amount of at least 25% of the weight of dry resin.

68. In a Daniel cell, a barrier separating the two solutions, said barrier comprising as an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl and dicyandiamidino and being present in an amount of at least 0.8 milliequivalent per gram of dry resin, and said water being present in an amount of between about 58 and 138 percent of the weight of dry resin.

69. A method of transferring ions of one charge from 'one electrolytic solution to another to the substantial exclusion of ions of the other charge comprising separating said solutions by means of a barrier and passing adirect electric current in series across said solutions and separating barrier, said barrier comprising as an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said groupsl having a dissociation constant greater than 10-5 and being present in an amount of at least 0.3 milliequivalent per gram of dry resin, and said water being present inV an amount of at least 15% of the weight of dry resin.

70. A method of transferring ions of one charge from one electrolytic solution to another to the substantial exclusion of ions of the other charge comprising separating said solutions by means of a barrier and passing a direct electric current in series across said solutions and Separating barrier, said` barrier comprising as an essentialpart extending substantially throughout, a predominantamount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrixy and water in gel relationship with said matrix; said groups having a dissociation constant (K) greater than l05, said groups being present in an amountr of `at least 3.0 milliequivalentsper gram of dry resin4 for groupsvhavingt a K between 10"5 and 10-3 and inanamQuntQfgat least'L 0.3 milliequivailent per gramv of dry resigrnfollgroups,1

having a K of -3 or higher; and said water being present in an amount of at least 25% of the weight of dry resm. A

71. A method of transferring ions of one charge from one eleotrolytic solution to another to the substantial exclusion of ions of the other charge comprising separating said solutions by means of a barrier and passing a direct electric current in series across said solutions and separating barrier, said barrier comprising as `an essential part extending substantially throughout, a predominant amount of an ion exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, dissociable ionic groups chemically bonded to said matrix and water in gel relationship with said matrix; said groups being selected from the class consisting of sulfonate, quaternary ammonium, guanidyl and dicyaudiamidino and being present in Yan [amount of at least 0.8 milliequivalent per gram of dry resin, and said water being present in an amount of between about 58 'and 138 percent of the weight `of dry resin.

72. The method of electrolyzing aqueous solutions of sodium chloride to produce a sodium hydroxide solution and chlorine, comprising contacting the solution of sodium `chloride with an anode and one side of the barrier, contacting the sodium hydroxide solution with `a cathode and the other side of the barrier, and passing an electric current between the anode and cathode, said barrier comprising as an essential part extending substantially throughout, a predominant amount of a cation exchange resin which comprises: an insoluble infusible synthetic organic polymeric matrix, ionic groups dissociable into a free mobile cation chemically bonded to said matrix, and water in gel relationship with said matrix; said ionic groups having a dissociation constant (K) of at least 10-5, said ionic groups being present in an amount of at least 3.0 milliequivalents per grain of dry resin for groups having a K between 105 and 104, and in amount of at least 0.3 milliequivalent per gram of dry resin for groups having a K of 10-3 or above; and said water being present in an amount of lat least 25 of the weight of dry resin.

References Cited in the le of this patent or the origlnal patent UNITED STATES PATENTS `461,965 Souther Oct. 27, 1891 665,625 Amwake Ian. 8, 1901 1,176,541 Gibbs Mar. 21, 1916 1,284,618 Dow Nov. 12, 1918 1,557,931 Grossmann Oct. 20, 1925 1,926,063 Rossiter et al. Sept. 12, 1933 1,931,954 Childs Oct. 24, 1933 1,998,539 Gams et al. Apr. 23, 1935 2,195,196 Wassenegger et al. Mar. 26, 1940 2,204,539 Wassenegger et al June 11, 1940 2,228,159 Wassenegger et al. Jan. 7, 1941 2,297,837 Loughnane Oct. 6, 1942 2,341,907 Cheetham et al Feb. 15, 1944 2,395,825 Hesler Mar. 5, 1946 2,434,190 Barnes J-an. 6, 1948 2,448,029 Huested et al Aug. 31, 1948 2,452,624 Zimmermann Nov. 2, 1948 2,500,113 Banks Mar. 7, 1950 f 2,500,149 Boyer Mar. 14, 1950 2,546,938 Bauman Mar. 27,. 1951 2,593,540 Cornwell et -al Apr. 22, 1952 2,614,976 Patnode Oct. 21, 1952 FOREIGN PATENTS 713,093 Germany Oct. 9, 1941 OTHER REFERENCES Primary Batteries, by Cooper, second impression (1920), pages 235, 236.

Modern Plastics, October 1945, pages 149, and 218.

Ion Exchange, by Nachod (1949), pages 48-50, 62 64 and 67.

Transactions of The Faraday Society, vol. 33 (1937), pages 1073-1081.

Helvetica Chimica Acta, vol. 23 (1940), pages 795-800.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3207708 *Feb 23, 1961Sep 21, 1965Gen ElectricProcess of making an ion exchange membrane
US3480495 *Jul 11, 1966Nov 25, 1969IonicsProcess for cementing ion-exchange material
US3497429 *Nov 28, 1966Feb 24, 1970Asahi Chemical IndElectrolytic method of manufacturing hydrodimer of acrylonitrile
US5679228 *Dec 13, 1995Oct 21, 1997Ionics, IncorporatedElectrodialysis including filled cell electrodialysis (electrodeionization)
US5679229 *Dec 16, 1996Oct 21, 1997Ionics, IncorporatedElectrodialysis including filled cell electrodialysis (electrodeionization)
US5814197 *Dec 16, 1996Sep 29, 1998Ionics, IncorporatedElectrodialysis including filled cell electrodialysis (electrodeionization)
US5861221 *Jul 27, 1994Jan 19, 1999Fraunhofer Gesellschaft Zur Forderung Der Angewandten Forschung E.V.Battery shaped as a membrane strip containing several cells
US20140027301 *Mar 14, 2013Jan 30, 2014Ohio UniversitySelective reductive electrowinning apparatus and method