PROCESS OF WELL CONTROL BY MEANS OF GEL FORMATION

Abstract: A process for forming a polymeric solution or gel having a viscosity of at least about 50,000 cps which includes forming a solvent system of an organic liquid and a polar consolvent, the polar consolvent being less than about 15 wt. % of the solvent system, the viscosity of the solvent system being less than about 1,000 cps; dissolving a neutralized sullonated polymer in the solvent system to form a solution, the concent­ ration of the neutralized sulfonated polymer in the solution being 0.1 to 20 wt %, the viscosity of the solution being less than about 20,000 cps; and adding about 5 to about 500 vol. % water to the solution having a viscosity less than aboit 20,000 cps, the water being immiscible with the solution and the polar cosolvent transferring from the solution phase to the water phase thereby causing the viscocity of said solution to increase from legs than 20,000cps to geater than 50,000 cps.

Description: The present invention describes a process which permits (1) the preparation of polymer solutions of sulfon ated polymers in organic liquid having reasonably low viscosities (i.e., less than 20,000 cps), (2)the preparation C'- extremely viscous solutions or geis from s'ch solutions by the simple process of mixing water with the polymer solution and (3) the reversion of such viscous solutions or gels to relatively low viscosity mixtures by the reincorporation of polar cosolvents which are water immiscible at a desired stage. These operations are achieved by the use of the appropriate concentration of polymers having low concentrations of ionic groups present, preferably <RTI ID=1.9> metal sulfonate groups. Such polymers are described in detail in a number of U.S. Patents (U.S. 3,836,511; 3,870, 841; 3,847; 3,642, 728; 3,921,021). These polymers possess unusual solution characteristics some of which are descrioed in U.S. Patent 3,931,021. Specifically such poly mers such as lightly sulfonated polystyrene containing 2 mole % sodium sulfonate pendant to the aromatic groups are typically not soluble in solvente commonly employed for polysyrene itself. However, the incorporation of modest levels of polar cosolvents permit the rapid dissolution of such ionic polymers to form homogeneous solutions of moderate viscosity. In the present process, the role of the polar to solvent is that of solvating the ionic groupe whils the main body of the solvent interacts with the polymer backbone. For examole, xylene is an excellent solveant for the polystyrene backbone and when combined with 5i methanol readily and rapidly will dissolve the previosly described lightly sulfonated polystyrene. A still further object of the invention is to employ the process as an integral part o± well control procedure: with are initiated when unwanted pore fluid influxes have entered the wellbore from subterrancen formati.ons. A thin fluid solution, separated from the water base drilling mud by suitable fluid scacers, could be cir culated don the drill DiDe string and out through the jet nozzles in the drill bit. UDon contacting water in the drill pipe-formation annulus, a viscous gel would be formed that could prevent further pore fluid moverment and avoid the risk of a catastrophic well blowount. This type of proce dure would have several advantages over current, conven tional well control methods hic rely on the hydrostatic gradient of a heavy fluid placed in the annulus to control the well in the event of pore fluid influxes. The present invention relates to a profess for forming 2 polymeric solution having a viscosity of at least 50,000 cps which comprises forming a solvent sys tern of an organic liquid and a polar cosolvent, the polar cosolvent being less than 15 wt. 7Ó of the solvent System, theviscosity of the solvent system being less than 1000 cps: dissolving a neutralized sulfonated polymer in the solvent system to for:n a solution, the concentration of the neutral- ized sulfonated polymer in the solution being 0.1 to 20 wt. 7o, wr viscosity of the solution being less than 20,000 cps and adding 5 to 500 vol. Z water based on the volume of organic liquid plus polar cosolvent to the solution having a viscosity less Luan 2G,000 cps, water being immiscible with the sulution and the polar consolvent trans ferring from the solution phase to the water phase thereby causing Lhe viscosity of said solution to increase rapidly from less than 20,000 cps to a high Viscosity for example agreater than 50,(O cp':. if the boiling point of the organic liquid is greater than that of water or the polar cosolvent, the solution or gel having a high viscosity (eg greater than 50,000 cps) can be heated to 2 temperature greater tan the boilin point of water and the polar cosolvent but less than that of the organic liquid thereby isolating a gel of the neutralized sulfonated DolNmer in the organic liquid, vihen the polar cosolvent and water are boiled off. The formed gel can be further heated to a temperature above the boiling point of the organic liquid thereby removing part of the or genic liquid from the liquid so as to cause formation of a more rigid gel. Alternatively, the solution having a high vis cosity (eg greater than 50,000 cps) can be heated to a tempera- ture above the boiling point of the organic liquid, polar cosolvent and water thereby removing the organic liquid water and polar solvent from said gsl so as to cause for:na- tion of the solid neutralized sulfonated polymer. The gel can be coated onto a substate of an article sic?. ac a cloth fabric, a polymeric material, glass, ceramic, metal or wood prior to the heating of the gel. Men the gel -s subse quently heated a solid neutralized sulfonated polymeric coating will form on the surface of the substrate. Alterna tively, the gel could be placed into an opening of the article thereby forming a solid plug within the opening upon application of heat to the gel. The gel could also be inserted into the bore of an elongated ember such as a pipe thereby forming a plug in the pipe uton application of heat to the gel. The article could also be suspended in the solution having the viscosity of less than 20,000 cps and thereby be encaosulated in the solution having a high viscosity (eg greanter tli.,n 50,000 cps) hen the water is added to the solution having a viscosity of less than 20,000 cps. When the solution having a high viscosity is formad by the addition of water to the Colu tion having a viscosity less than 20,000 cps, the polar co solvent rapidly transfers from the solution or gel phase to the aqueous water which is immiscible with the solution phase. Tic water can be remeved from the solution phase by conventional liquid extraction methods. The formation of the solution having a iGh viscosity of for ample 50,000 cps from the solution having a viscosity less than 20,000 cps can be quite rapid e.#. of the order oi less thr.n 1 minute to about 24 hours, more usually less thn 1 minute to about 30 minutes, ad most usually less tban 1 minute to about 10 minutes; however, this depends on temperature, shear, solvent type, etc. The component materials of the present process include a neutralized sulfonated polymer, an organic liquid, a polar cosolvent and water. In general, the sulphonated polymer comprises from 10 to 200 meq. pendant sulphonate groups per 100 grams of polymer, more preferably from 10 to 100 meq. pendant sulphonate groups. The polymers utilized in the present invention have sulphonic acid groups which have bcn neutral- ized with basic materials selected Groups IA; TIA, IB and IIB of the Periodic Table of the Elements, lead, tin and antimony, as well as ammonium and amine counterions, Sulphonated polymers which are subject to the process of the invention are unlimited and include both plastic and elas tomeric polymers. Specific polymers include sulfonated polystyrene, sulfonated t-butyl styrene, sulfonated etyle copolymers, sulfonated propylene copolymers, sulfonated styrene/acrylonitrile copolymers, suifonated styrene/methyl methacrylate copolymers, sulfonated block copolymers of styrene/ethylene oxide, sulfonated polyisobutylene, sulfonated ethylene-propylene terpolymers, sulfonadet polyisoprene, sul fonated elastomers and their copolymers, sulfonated polyvinyl toluene and sulfonatod polyyinyl tolene copoly mers. Neutralization of the cited polymers with appro priate metal hydroxides, metal acetates, octal oxides cr ammonium hydroxide etc. can be conducted by means well knewn in the zrt. Por example, the sulfonation process as with butyl rubber containing a small 0.3 to 1.0 mole % unsatura- tion can be conducted in a suitable solvent such as toluene with acetyl sulfate as the sulfonating agent such as described in U.S. Patent No. 3,836,511. lNle resulting sulfon- ate derivative can then be neutralized with 2 number of different neutralization gents such as sodium phenolate anc; similar metal salts. The amounts of such neutralization agents employed will normally be equal stoichiometrically to the amount of unneutralized sulfonate in the polymer plus any unreacted reagent which still is Dresent. It is preferred that the amount of neutralizing agent be equal to the molar amount of sulfonating sgent originally employed plus 10% more to ensure full neutralization. The use of more of such neutralization agent is not critical. Sufficient neutralizaticn agent is necessary to effect at least 50% neutralization of the sulfonate groups present in the polymer, preferably at least 90% and most preferably essentially complete neutralization of such sulfonate groups should be effected. The degree of neutralization of said ionomeric groups may vary from 50 to 500 mole % preferably 90 to 200%. Most preferably it is preferred that the degree of neutral izat.ion be substantially complete, that is with no substantial free acid present and without substantial excess of the base other than that needed to ensure neutralization. Thus, it is clear that the polymers which are utilized in the present invention comprise substantially neutralized pendant grouss and, in fact, an excess of the neutralizing material ray be utilized without defeating the objects of the present invention. The ionomeric polymers of the present invention may vary in number average molecular weight from 1,000 to 10,000,000, preferably from 5,000 to 500,000, most preferably from 10,000 to 200,000. These polymers may be nrepared b7 methods known in the art: for example, see U.S. Patent No. 3,642,728. It is evident that the polymers covered wlthin this invention encompass a broad class of hydrocarbon polar mer systens. It is important that the hydrocarbon poly mer backbones (in the absence of the ionic groups) be soluble in the organic liquind the viscosity of which is to be controlled. To achieve the desired solubility, it 'e required that the polymer to be employed possess a degree of Dolarity consis- tent with that solvent. This solubility relationship can readily be established by anyone skilled in the art simply b appropriate tests (e.g., Polymer Handbook, Edited by Brandrup and Emmergut, Interscience Publishers, 1967, sec tion IV-341). In the absence of appropriate polymer-solvent compatibility knowledge, this can be determined experimen- tally by observing whether the selected polymer will be scl- uble in the solvent at a level of 1 g. polymer per 100 ml solvent. If the polymer is soluble, then this demonstrates that it is an aDpropriate backbone for modification with ionic groups to achieve the objectives of this invention. It is also apparent that polymers which are too polar will not be soluble in the relatively nonpolar organic liquids of this invention. Therefore, only those polymer backbones (i.e., as measured in the absence of ionic groups) having a solubility parameter less than 10.5 are suitable in this invention. This precludes the use of such polymers as poly vinyl alcohol, polyacrylonitrile, etc. Also highly crystal line polymers are to be avoided since they tend not to be soluble in the relatively nonpolar organic liquids employed herein. Therefore, acceptable polymers employed in this ifl vention must possess a level of crystallinity of less than 25%. Thus, these acceptable polymers can be considered sub stantially noncrystalline. The preferred ionic copolymers for use in the present invention, e.q., sulfonated polystyrene and substi tuted derivatives thereof, may be prepared by the procedures described in U.S. Patent No. 3,870,841. The sulphonated polymers are incorporated into the organic liquid at a level of from 0.1 to 20 weight % preferably from 0.2 to 10 weight %, most preferably from 0.5 to 5 weight % based on the organic liquid and the polar cosolvent. The sulphonated polymers of the present invention may be prepared prior to incorporation into the organic solvent or by neutralization of the unneutralized sulfonate in situ. For example, preferably the unneutralized sulfo- nate is neutralized immediately after preparation. For example, if the sulfonation of polystyrene is conducted in. solution, then the neutralization of that unneutralized sulfonate can be conducted immediately following the sulfona ticn procedure. The neutralized polymer may then be isolated by means well known to those skilled in the art. i.e., coagulation, steam stripping, or solvent evaporation, ke- cause the neutralized polymer has sufficient thermal stbil- ity tobe dried for employment at a later time in the process of the present invention. It is well known that the unneu tralized sulfonate derivatives do not possess good thermal stability and the above operations avoid that problem. It is also possible to neutralize the unneutralized suffocate of these polymers in situ: however, this is not a preferred operation, since in situ neutralization required preparation of the unneutralized sulfonate in the organic liquid which is to be subjectad to the present prr- cess, or the unneutralized sulfonate of the polymer must be dissolved in said organic liquid. The latter aop- proach may involve handling of the unneutralized sulfonate of a polymer which has limited thermal stability. Therefore, it is quite anDarent that the preparation aid isolation of a neutralized sulphonared polymer atterds the maximum latitude in termulation, less problems in handling poly mers of limited thermal stability and maximum control ower the final mixture of sulphonated poly# polar cosolverit and organic liquid. The organic liquids, which may be utilized in the present invention, are selected with relation to the sulphonated polymer and vice-versa. The organic liquid is an aromatic hydrocarbon, ketone, chlorinated aliphatic hydrocarbon, aliphatic hydrocarbon, cyclic aliphatic ether, aliphatic ether, aliphatic ester or d mixture thercof. Specific examples of organic liquids to be employed with various tyres of polymers are: Polymer Or,ganic Liquid Sulfonated polystyrene benzene, toluene, ethyl benzene, methylethyl ketone, xylene, styrene, ethylene dichloride, methylene chlor ide sulfonated poly-t-butyl- benzene, toluene, xylene, styrene ethyl benzene, styrene, t butly styrene, aliphatic oils, aromatic oils, bexne, hetone, decane, nonane, pen tane sulfonated ethylerte- aliphatic and aromatic solpropylene terploymer vents1 oils such as Solvent "100 Neutral", "150 Neutral" and similar oils, benzene, diesel oil, toluene, xylene, ethyl benzene, pentane, hex ane, heptane, octane, iso octane, nonane, decane, aro matic solvents, ketone sol vents sulfonated styrene-methyl- dioixane, halogenated alimethacrylate copolymer phatics, e.q., methylene chloride, tetrahydrofuran sulfonated poly-isobutylene saturated aliphatic hydro- bons, diisobutylene, triiso butylene, aromatic and alkyl- substituted aromatic hydro carbons, chlorinated hydxo- carbons, n-butyl ether, n amyl ether, methyl pleate, aliphatic oils, oils pre dotninantly paraffinic in na- ture and mixtures containing naphthenic hydrocarbons "Sol vent 100 Neutral", "Solvent 150 Neural" and all related oils, low molecular weigh; ; polymeric oils such as squa- lene, white oils and process oils having 60% or less aro matic content sulfonated polyvinyl toluene tolyene, benzene, xylene, cyclohexane, ethyl benzene, styrene, methylene, chloride ethylene dichloride. The method of the prcscnt: invention includes incorporating a polar cosolvent into the mixture of organic liquid and monomer, to solubilize the pendant ionomeric groups. The polar consolvent will have a solubility parameter of. at least 10.0, tore preferably at least 11.0 and is water miscible and may comone from 0.1 to 40, preferably .5 to 20 weight % of the total mixture of organic liquid, ionomeric polymer and lar consolvent. The solvent system of polar cosolvent and organic liquid in which the neutralized sulfonated polymer is dissolved contains less than 15 wt. % of the polar cosolvent, more preferably 2 to 10 wt. %, and most preferably 2 to 5 wt. %. The viscosity of the solvent system is less than 1,000 cps, more preferably less than 800 cps and most preferably less than 500 cps. Normally, the polar cosolvent will be a liquid at room temperature: however, this is not a requirement. It is preferred but not required that the polar cosolvent be soluble or miscible with the organic, liquid at the levels employed in this invention. The polar cosolvent is a water soluble al cohol gamine, di- or trifunctional alcohol, amide, acetamide, phospiate, lactone or a mixture thereof. Especially preferred polar cosolvents are aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, 1, 2propane diol, monomethyl ether of ethylene glycol, and nethylformamide. The amount of water added to the solution cf neutralized sulfonated polymer, organic liquid and polar cosolvent having a viscosity of less than 20,000 cps, is 5 to 500 vol. % of water, more preferably 10 to 300 vol. % water and most preferably 10 to 200 vol. % watur based on the volume of organic liquid plus polar cosolvent. In the case of reversion of the Dolymeric gel by the addition of water immiscible polar cosolvent, the concentration of polar cosolvent added is 0.5 to 30 wt. %, more preferably 1 to 20 wt. %, and most preferably 2 to 10 wt. %. EXAMPLE Solutions were prepared at 5% (5 gms/100 ml) concentrations of 2 mole eíO sodium sulfonated polystyrene (S-PS) in 5% methanol/xylene (vol/vol) and 5% hexanol/xylene, and of sulfonated EPDM (about 1.0 mole % zinc sulfonate) in 5% isopropanol/heptane and 5% methanol/xylene. To 50 ml samples of each solution, varying per centage levels of water (by volume) were added while stirring rapidly with a high speed stirrer. Brookfield viscos- ities of the stock solutions and each. sample after water addition were obtained at 250C. Viscosity data are summarized on Table I for the S-PS solution: Table 2 for the sulfe-EPDM solutions. S-PS The addition of water to S-PS in methanol/xylene produces a milky solution or gel. Viscosity increases CR- poncntially from about 8 cps for the stock solution to 384, 000 cps with 14% water added. Beyond this level of water addition, solid gels were obtained with viscosities above the range of the Brookfield measuring capability. Excess water was seen to separate from the thickened solutions at water levels of 10% and above. The solution viscosity of the S-PS in hexanol/ xylene stock solution as considerably higher (458 cps) than the methanol/xylene solution. The addition of 1 and 2% water resulted in milk solutions with slight increases in viscosity (612 cps at 2% water level). At a level of 14% water, viscosity has increased to only 914 cps. This experiment clearly demonstrates that the use of a water immiscible alcohol such as hexanol does not provide a gel as shown above with methanol. Sulphonated EPDM The solution of Sulphonated EPDM isopropanol/heptane displayed phase separation upon standing into two indistinct lavers which made viscosity readings somewhat erratic. The addition of water followed by agitation nermitted reproduc- ible readings over a range of water levels. This solution, therefore, was examined by removing 50 ml samoles, adding aliguots of watter and stirring vigorously. At weter addition levels of 6 to 12%, uniform solutions resulted and viscositier were obtained. At levels of 14 water and atove, addtion became too thick for viscosity mesurements. The solution of Sulphonated EPDM/methanol/xylene. examined as above. water was added t 50 ml samples at levels of 6,8,10 and 12%. Milky, thick solution were obtained up to the 10% water level and viscosities obtained. At a level of 12% water solid gelation occurs. The preceding experiments demonstrate conclusivaly that the process envisaged for these sulphonated polymers in mixed solvents is useful in preparing gels. It is also evi- dent that this process is applicable Lo a number of differ ent polymer backbones containing pendant metal sulfonate groups. For example, copolymers of butadiene or isoprene with metal sulfonate containing vinyl monomers would also be useful in this Invention. The preferred level of metal sulfonate groups pendant to the polymer backbone Is in the range of 10 meq./lO0 gm up to 200 meg./100 gm os polymer. Similarly, the level of polymer in the mixed solvent can be varied over a wide range which is fro about 1 weight pe- cent up to 2Q weight percent. Similarly, the alcohol level varies from below 2 percent to less than 15 weight percent based on total solvent (hydrocarbon solvent and alcohol). It has generally been observed that increasing the amount of water with the polymer solution increases the strength of the gel. Levels of water in excess of 50 volume percent have been employed successfully and higher levels can be employed. The preferred levels of water are not believed to be critical provIded that levels of greater than 5 volume percent are employed (based on volume of hydro carbon-alcohol solution). In addition, to the variables delineated abexie, other additives can be employed to increase gel strength, if desired. For example, the addition of clays, fillers (calcium carbonate, zine oxide), carbon black and the 11k:' can be employed to strengthen the gels. The experiments described heterofore are concerned only with the preparation of a gel and not its reversion. It has been observed that the of the present invention. can be dispersed simply by the addition of a polar cosolvent which is miscible with the hydrocarbon phase and immiscible with water. Thus, a gel formed from sulfonated polystyrene [5% of S-PS contai ning 2 mole % sodium sulfonate in metha- nol/xylene (95/5)1 by nixing with about 40 vol. % water if a stiff gel. The addition of about 5 volume oercent of he.;- anol-1 to the entire mixture followed by agitation provides a fluid ernulsion of very low viscosity. This reverse process can be effected with those alcohols and molar cosoivents which are not water miscible and, thcreforc, are promarily dissolved in the hydrocarbon phase. TABLE 1 VISCOSITIES OF SULFO-POLYSTYRENE SOLUTIONS* AT VARIOUS WATER CONTENTS WITH METHANOL AND HEXANOL AS COSOLVENTS C% H2O 1% H2O 2% H2O 4% H2O 6% H2O Alcohol RPM Vis-UL RPM Vis-UL RMP Vis-NO2 RPM Vis-No2 RPM Vis-No4 Methanol 60 7.7 12 40.6 60 403 1.5 10,360 12 33,350 30 7.4 6 39.4 30 402 .6 9,900 6 12 6.5 3 39.4 12 350 .3 10,000 3 32,000 RPM Vis- RPM Vis- RPM Vis- RPM Vis- RPM Vis No.2 No.2 No.2 No.2 No.2 Hcxanol 12 458 30 570 30 612 30 654 30 705 6 460 12 570 12 600 12 655 12 705 3 464 6 570 6 '590 6 660 6 690 * 95% xylene / 5% Alcohol (V/V) containing 5% by weight of sulfonated Polystyrene (2 mole percent sodium sulfonate) was employed as starting solution. TABLE 1 Continued: VISOSITIES OF SULFO-POLYSTYRENE SOLUTIONS* AT VARIOUS WATER CONTENTS WITH METHANOL AND HEXANOL AS COSOLVENTS 8% H2O 10% H2O 12% H2O 14% H2O Alcohol RPM Vis-No4 RPM Vis-No4 RPM Vis-No4 RPM Vis-No4 Methanol 6 90,200 1.5 338,800 1.5 284,000 1.5 384,000 3 91,400 .6 335,000 .6 278,000 .6 386,000 1.5 84,000 .3 340,000 .3 260,000 .3 380,000 RPM Vis- RPM Vis- RPM Vis- RPM Vis No. 2 No. 2 No. 2 No. 2 Hexanol 30 738 30 774 30 860 30 914 12 735 12 775 12 860 12 915 6 690 6 750 6 840 6 890 * 95% xylene / 5% Alcohol (V/V) containing 5Z by weight of sulfonated Polystyrene (2 mole percent sodium sulfonate) was cmployed at starting solution. TABLE 2 VISCOSITIES OF SULFONATED ETHYLENE/PROPYLENE DIENE TERPOLYMER SOLUTIONS* AT VARIOUS WATER CONTENTS IN TWO SOLVENT SYSTEMS 0% H2O 6% H2O Alcobol/Solvent RPM Vis- RPM Vis No. 4 No. 4. ISOPROPANOL/HEPTANE 60 60 3,200 ERRATIC 3 READINGS 30 3,600 12 5,5CO RPM Vis-UL RPM Vis-No. 4 METHANOL/XYLENE 30 116 12 32,00? 12 123 6 43,500 6 123 3 64,000 * SULFONATED EPDM CONTAINED about 1 mole percent zinc sulfonate or about 30 milliequivalents sul fonate/100 gms. polymer and was dissolved at a level of 5 weight percent in 95/5 solvent/alcohol mixture. TABLE 2 CONTINUED VISCOSITIES OF SULFONATED ETHYLENE/PROPYLENE DIENE TERPOLYMER SOLUTIONS* AT VARIOUS WATER CONTENTS IN TWO SOLVENT SYSTEMS 8% H2O 10% H2O 12% H2O RPM Vis- RPM Vis- RPM Vis No. 4 No. 4 No. 4 Alcohol/Solvent 60 6,500 30 16,040 12 33,900 ISOPROPANOL/HEPTANE 30 6,500 12 20,500 6 47,500 12 9,500 6 28,400 3 70,000 RPM Vis- RPM Vis- RPM Vis No. 4 No. 4 No. 4 6 83,500 .6 71,000 METHANOL/XYLENE 3 117,000 .3 824,000 Too Gelled 1.5 170, 000 * SULFONATED EPDM CONTAINED about 1 mote percent zinc sulfonate or about 30 milliequivalents sul fonate/100 gins. polymer and was dissolved at a level of 5 weight percent in 95/5 solvent/alcohol mixture.

Claims: CLAIMS 1. A process for forming a polymeric solution or gel having a high viscosity which comprises: (a) forming a solvent system of an organic liquid and a polar cosolvent, said organic liquid being an aromatic hydrocarbon, an aliphatic hydrocarbon, a chlorinated aliphatic hydrocarbon, a ketone, a cyclic aliphatic ether, tn aliphatic ether, an aliphatic ester, a paraffin oil or a mixture thereof, said polar cosolvent having a solubli- ity parameter of ai: icast 10.0 and being a water soluble alcohol, amine, di- or tri functional alcohol, amide, phosphate, lactone, an acetamide or a mixture thereof, said polar cosolvent being less can about 15 wt. % of said solvent system, the viscosity of said solvent system being less than about 1,000 cps; (b) dissolving a neutralized sulfonated polymer in said sol nt system to form a solution, the concentration of ssi.d neutralized sulfone ated polymer in said solution being 0.1 to 20 wt. %, the viscosity of said solution being less than 20,000 cps, the polymer having a backbone which has a solubility parameter of less than 10.5, the polymer having a level of crystallisity of less than 25% and the sulphonated polymer having been neutralized with cations of Groups IA, IB, TIA or IIB oi the Periodic Table of Elements, or lead, tin, antimony or ammonium or amine cations; and (c) adding 5 to 500 volume % water based on the volume of organic liquid plus polar cosolvent to said solution, said water being immisc- ible with said solution, whereby said polar cosolvent transfers from said solution to said water causing the viscosity of said solution or suspension to increase from less than 20.000 eps to a high viscosity. 2. A process according to claim 1, which comprises heating said solution having a high viscosity to a temperature greater than the boiling point of water and said polar cosolvent, but less that of said organic liquid thereby isolating a gel of said neutralized sulfonated polymer in said organic liquid. 3. A process according to claim 2, which includes heating said gel to a temperature alcove the boiling point: of said orgnnic liquid Lliercby removing said organic liquid from said gel to for a solid neutralized sulfonated polymer. 4. A process according to claim 2, which includcs depositing said gel on a substrate and heating said gel to a temperature above said boiling point of said organic liquid, thereby forming a coating of said neutralized sulfonated polymer on said substrate. 5. A process according to claim 4, which comprises suspending n article in the solution having a viscosity less than 20,000 cps, thereby permitting said gel to be encapsulaLed within said solution having a high viscosity upon the addition of water to said solution having a viscosity less than about 20,000 cps. 6. A process according to claim 1, which comprises separating said water from said solution having a high viscosity thereby forming gel of said neut-ralized sulfonated polymer in said organic liquid 7. A process according to claim 1 which is carried out in the prsc.ncc of an elongated member having a bore therein and wherein said solution having a high viscosity is formed within said bore. 8. A process according to any one of the preceding claims whercin said solution having a high viscosity has a viscosity of greater than 50,000 cps. 9. A process according to any one of the preceding claims, wherein said sulphoiiated polymer is sulphonated EPDM terpolymer or sulphonated Butyl rubber. 10. The product of the process according to any one of the preceding. c1.ajms.

Inventors: KLEIN, ROBERT R., LUNDBERG, ROBERT D., MAKOWSKI, HENRY S., O'BRIEN, DENNIS E.
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1979
Main classification: C08L23
IPC codes: B01J19, C09K8, C08J3