arcilla organofilica polarizada

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United States Patent [19]

Finlayson et al.

[ 1 I ]

[45]

4,287,086Sep. r, 1981

[54] VISCOUS ORGANIC SYSTEMSCONTAINING AN ORGANOPHILIC CLAYGELLANT WITHOUT AN ORGANICDISPERSANT THEREFOR

[75] Inventors: Claude M. Finlayson; John W.Jordan, both of Houston, Tex.

[73] Assignee: NL Industries, Inc., New York, N.Y.

[21] Appl. No.: 749,323

[22] Filed: Dec. 10, 1976

Related U.S. Application Data

[63] Continuation-in-part of Ser. No. 573,967, May 2, 1975,abandoned.

[5 I] Int. CI.3 BOIJ 13/00; C10M 1110;ClOM 5/04

[52] U.S. CI 2521316; 252/8.5 P;252/8.55 R; 252/28; 252/309; 260/448 C

[58] Field of Search 252/316, 309 B, 8.5 P,252/28; 260/448 C

[56]

2,531,4272,859,2342,966,5063,133,0723,537,994

References Cited

U.S. PATENT DOCUMENTS11/195011/195812/19605/196411/1970

Hauser 252/316 XClem 252/28 XJordan 260/448 CShibe, Jr. et al. 252/316 XHouse 252/28 X

Primary Examiner-Richard D. LoveringAttorney, Agent, or Firm-Gary M. Nath

[57] ABSTRACT

The viscosity of liquid organic systems is increased byadding thereto an organophilic clay gellant which is thereaction product of a smectite clay having a cationexchange capacity of at least 0.75 milliequivalents per

gram and from 1.00 to less than 1.20 milliequivalents pergram of clay of a methyl benzyl dialkyl ammonium salt,wherein the two alkyl groups independently containfrom 16 to 18 carbon atoms, and from 0% to I% waterin the absence of a polar organic dispersant for thegellant.

12 Claims, No Drawings



proximately 10 0 0 to 325 0 C., preferably 27 5 0 to 30 0 0 C.,for a sufficient period of time to form the desired prod-uct. Formulation times of 3 to 48 hours are typical at300 0 C. depending on the particular smectite being syn-thesized, and the optimum time can readily be deter-mined by pilot trials. Representative hydrothermal pro-

cesses for preparing synthetic smectites are described inthe following U.S. Pat. Nos., incorporated herein byreference: Granquist 3,252,757; Neumann 3,586,478;Orlemann 3,666,407; Neumann 3,671,190; Hickson3,844,978; Hickson 3,844,979; Granquist 3,852,405;Granquist 3,855,147.The cation exchange capacity of the smectite clay

can be determined by the well-known ammonium ace-15 tate method.

The organic compounds useful in the practice of thiswhere 0.55;::;;x;: :;;.10,f;::; ;4and R is selected from the invention are quaternary ammonium salts containinggroup consisting of Na, Li, NH4, and mixtures one methyl radical, one benzyl radical, and two alkylthereof; 20 radicals each independently containing from 16 to 18

carbon atoms. Preferably the alkyl radicals are hydro-genated tallow radicals, i.e., C n H2n+1 where n is 16o r18.The salt anion is preferably selected from the groupconsisting of chloride and bromide, and mixturesthereof, and ismore preferably chloride, although otheranions such as acetate, hydroxide, nitrite, etc. , may bepresent in the quaternary ammonium salt to neutralizethe quaternary ammonium cation. The methyl benzyldialkyl ammonium salt may be represented by the for-

30 mula:

34,287,086

already in this form. This can conveniently be done bypreparing an aqueous clay slurry and passing the slurrythrough a bed of cation exchange resin in the sodiumform. Alternatively the clay can be mixed with waterand a soluble sodium compound such as sodium carbon- 5ate, sodium hydroxide, etc., and shearing the mixture

such as with a pugmill or extruder.Smectite clays prepared synthetically by either apneumatolytic or, preferably, a hydrothermal synthesisprocess can also be used to prepare these novel organic- 10clay complexes. Representative of such clays are thefollowing:

Montmorillonite

bentonite

where O<x< 1.10, O<y< 1.10, 0.55;::;;(x+y);::;; 1.10, 25f;::;;4and R is selected from the group consisting ofNa, Li, NH4 and mixtures thereof;

beidellite

where 0.55;::;;x;::;; .10, O;::;;y;::;;O.44, ;::;;4and R is se-lected from the group consisting of Na, Li, NH4

and mixtures thereof; 35hectorite

40where 0.57;::;;;::;; 1.15, f;::;;4and R is selected from thegroup consisting of Na, Li, NH4, and mixturesthereof;

saponite

where 0.58;::;;x;::;;1.18, 0;::;;y;::;;0.66,;::;;4and R is se-

lected from the group consisting of Na, Li, NH4, 50and mixtures thereof;

stevensite

where 0.28;::;;x;::;;.57, f;::;;4and R is selected from thegroup consisting of Na, Li, NH4, and mixturesthereof.

These clays may be synthesized hydrothermally by .60forming an aqueous reaction mixture in the form of aslurry containing mixed hydrous oxides or hydroxides

of the desired metals with or without, as the case maybe, sodium (or alternate exchangeable cation or mixturethereof) fluoride in the proportions defined by the 65above formulas and the preselected values of x, y, and ffor the particular synthetic smectite desired. The slurryis then placed in an autoclave and heated under autoge-nous pressure to a temperature within the range of ap-

4

where RI=CH3, R2=C6H5CH2, R3 and R4 are alkylgroups containing from 16 to 18 carbon atoms; andwhere M- is preferably selected from the group con-sisting of Cl+, Br+, N02""', OH-, C2H302-, and mix-tures thereof.The preferred quaternary amine for use in the prac-

tice of this invention is methyl benzyl dihydrogenated45 tallow ammonium chloride. Each hydrogenated tallow

radical contains sixteen or eighteen carbon atoms and,by virture of the hydrogenation, are alkyl radicals.The alkyl radicals may be derived from other natural

oils including various vegetable oils, such as corn oil,

soybean oil , cottonseed oil, castor oil, and the like, andvarious animal oils or fats. The alkyl radicals may bepetrochemically derived such as from alpha olefins.Many processes are known to prepare the methyl

benzyl dialkyl ammonium sali, used in the present in-ss vention. Generally one skilled in the art would prepare

a dialkyl secondary amine, for example, by the hydroge-nation of nitriles, see Young U.S. Pat. No. 2,355,356;form the methyl dialkyl tertiary amine by reductivealkylation using formaldehyde as the source of themethyl radical, see Shapiro et. al. U.S. Pat. No.3,136,819; and thereafter form the quaternary aminehalide by adding benzyl chloride or benzyl bromide tothe tertiary amine, see Shapiro et. al. U.S. Pat. No.2,775,617.The organo-clays of this invention can be prepared

by admixing the clay, quaternary ammonium compoundand water together, preferably at a temperature withinthe range from 10 0

0 F. to 1800 F., more preferably 140

0



4,287,0865

F. to 1700

F. for a period of time sufficient for the or-ganic compound to coat the clay particles, followed byfiltering, washing, drying and grinding. In using theorgano-clays in emulsions the drying and grinding stepsmay be eliminated. When admixing the clay, quaternary 5

ammonium compound and water together in such con-centrations that a slurry is not formed, then the filtrationand washing steps can be eliminated.

Preferably the clay is dispersed in water at a concen-tration from about 3% to 7%, the slurry centrifuged to 10remove non-clay impurities, the slurry agitated andheated to a temperature in the range from 140

0

F. to170

0

F., the quaternary amine salt added in the desiredME ratio, preferably as a liquid in isopropanol or dis-persed in water, and the agitation continued to effect 15the reaction.

The amount of the methyl benzyl dialkyl ammoniumsalt added to the clay for purposes of this inventionmust be sufficient to impart to the organophilic clay theenhanced dispersion characteristics desired. The ME 20ratio is defined as the number of milliequivalents of theorganic compound in the organoclay per 100 grams ofclay, 100% active clay basis. The organophilic clays ofthis invention must have a ME ratio from 100 to lessthan 120. At lower ME ratios the organophilic clays 25

produced are not effective gellants in the process of thisinvention even though they may be good gellants whendispersed in a conventional manner with polar organicdispersants, etc. At higher ME ratios the organophilicclays are poor gellants. However, it will be recognized 30that the preferred ME ratio, within the range from 100to less than 120, will vary depending on the characteris-tics of the organic system to be gelled by the organo-philic clay.

A sample convenient test has been devised to illus- 35

trate the enhanced dispersion characteristics of the or-ganophilic clays utilized in this invention and the resultsobtained in utilizing the process of this invention. Thetest is conducted by mixing the organophilic clay witha conventionally refined low VI oil at a concentration 40of 4.5% by weight for 0.5 minutes using a Fisher Scien-tific Co. DYNA-MIX mixer operating at 1800 rpm. Theviscosity of the oil-gellant mixture is then obtained ..Longer mixing times may be undertaken. Thereafter0.12% water is added to the mixture and the mixing is 45continued. The viscosity of the mixture is periodicallydetermined, generally after 6-9 minutes. A BrookfieldRVT Viscometer is used to obtain the viscosity al-though any suitable viscometer can be used. Under

these low shear conditions in the absence of a polar 50organic dispersion aid the much greater dispersibility ofthe organophilic clays of this invention as compared topreviously known organophilic clays can be readilydemonstrated. Generally, the organophilic clays pre-pared from approximately 100% active clay (containing 55essentially no impurities) will produce a gel having a 10rpm Brookfield viscosity of at least 20,000 centipoiseswhen dispersed at a concentration of 4.5% in a hydro-carbon oil having a viscosity index less than about 20

60

6with a mixer operating at 1800 rpm for 6 minutes in thepresence of 0.1-0.5% added water.

The process of this invention can be carried out atelevated temperatures. However, it is preferred that theprocess be conducted at temperatures less than 85° c.,more preferably at ambient temperatures.

The following examples illustrate the process of thisinvention and the benefits afforded through the utiliza-tion thereof, but are not to be construed as limiting theinvention except as discussed herein.

The smectite clays used are hectorite and Wyomingbentonite. The hectorite clay was slurried in water andcentrifuged to remove essentially all of the non-clayimpurities. The Wyoming bentonite clay was slurried inwater, centrifuged to remove essentially all of the non-clay impurities, and ion-exchanged to the sodium formby passing the slurry through a bed of cation exchangeresin in the sodium form. Several samples of methylbenzyl dihydrogenated tallow ammonium chloride sup-plied by ENENCO, Inc. were used to prepare the Of-

ganoclays in the examples. The molecular weight ofthese samples ranged from 619 to 644 and the percentactivity, in isopropanol, varied from 60% to 81.5%. Theconventionally refined oil and the solvent refined oilshad the following properties:

ConventionallyRefined

SolventRefined

Gravity, 'API @ 60 F.

Viscosi ty, SUS @ 100 F.Viscosi ty, SUS @ 210 F.Viscosi ty IndexIndex of RefractionFlash Point, 'F.Pour Point, 'F.

2050053121.5085

390-5

30.440058981.4811

4605

EXAMPLE I

The organoclays listed in Table A were prepared byheating the clay slurry to a temperature within therange from 150

0

F. to 1700

F., adding while stirring theclay slurry, the indicated amount of the indicated qua-ternary ammonium chloride which had been previouslymelted for convenience in handling, and continuing thestirring for approximately 45 minutes, followed by fil-tering, washing, drying at 140

0

F., and grinding.These organoclays were evaluated in the convention-

ally refined oil in the ease of dispersion test describedwhich dramatically indicates the improved ease of dis-

persion of these thickeners as compared to similar Of-ganoclay thickeners.

The data in Table A indicate the sharp increase in theease of dispersion of organoc1ays prepared from methylbenzyl dihydrogenated tallow ammonium chloride andthese smectite clays when the amount of this quaternaryammonium compound was in the range from 100 toabout 120 milliequivalents per 100 grams of clay. Thedata also illustrates the much superior dispersion char-acteristics of the inventive organoclays as comparedwith organoclays prepared from somewhat similar butdifferent quaternary ammonium compounds.

TABLE A

4.5% Organophilic Clay

10 rpm Brookfield Viscosity. cporganophili c Cl ay

ME 0% Water 0 .12% Water

Quaternary Ammonium Chloride Clay Ratio 0:5 Minutes 6 Minutes 9 Minutes

Methyl benzyl dihydrogenatedtallow Hectorite 87.5 480 -(2) 1,000



4,287,0868

TABLE A-continued4.5% Organophilic Clay

Organo[>hilic Cla:t 10 r[>m Brookf iel d Viscosit :t, c [>.

ME 0% Water 0 .12% Water

Qua te rnar y Ammon ium Chlo ride Clay Ratio 0.5 Minutes 6 Minutes 9 Minutes

Methyl benzyl dihydrogenatedtallow Hectorite 92.4 4S0 2,000

Methyl benzyl dihydrogenatedtallow Hectorite 97.2 560 9,000Methyl benzyl dihydrcgenatedtallow Hectorite 99.1 560 11,200Methyl benzyl dihydrogenatedtallow Hectorite 99.7 11,200Methyl benzyl dihydrogenatedtallow Hectorite 103.S 7,000 4S,4OO 5S,400Methyl benzyl dihydrogenatedtallow Hectorite 104.3 35,200 50,000Methyl benzyl dihydrogenatedtallow Hectorite 106.5 6,720 4S,000Methyl benzyl dihydrogenatedtallow Hectorite IOS.0 2,040 49,600 64,400Methyl benzyl dihydrogenatedtallow Hectorite 110.5 1,040 33,000 46,SOOMethyl benzyl dihydrogenatedtallow Hectorite 112.9 S90 44,000 67,600Methyl benzyl dihydrogenatedtallow Hectorite 115.0 3,400 33,600 34,SOOMethyl benzyl dihydrogenatedtallow Hectorite 117.9 21,000Methyl benzyl dihydrogenatedtallow Hectorite 124.9 13,000Methyl benzyl dihydrogenatedtallow Bentonite 91.5 400 400Methyl benzyl dihydrogenatedtallow Bentonite 96.9 3,200Methyl benzyl dihydrogenatedtallow Bentonite 102.6 2,SSO 36,SOO 44,000Methyl benzyl dihydrogenatedtallow Bentonite 106.0 9,2S0 51,200 50,000Methyl benzyl dihydrogenatcdtallow Bentonite 111.0 20,000 30,400 25,000Methyl benzyl dihydrogenatedtallow Bentonite 114.4 15,500

Methyl benzyl dihydrogenatedtallow Bentonite 120.2 14,600Methyl benzyl dihydrogenatedtallow Bentonite 123.6 6,SOODimethyl dihydrogenatedtallow Hectorite 95.2 3,400Dimethyl dihydrogenatedtallow Hectorite 102.9 3,400Dimethyl dihydrogenatedtallow Hectorite IOS.S 4S0 12,500Dimethyl dihydrogenatedtallow Hectorite 117.0 440 440

Methyl Trihydrogenatedtallow Hectorite 95.8 4,SOOMethyl Trihydrogenatedtallow Hectorite 101.9 4,400Methyl Trihydrogenatedtallow Hectorite IOS.5 640 3,320Methyl Trihydrogenatedtallow Hectorite IIS.5 7,400Benzyl Trihydrogenatedtallow Hectorite 95.5 5,000Benzyl Trihydrogenatedtallow Hectorite 101.4 4,SOOBenzyl Trihydrogenatedtallow Hectorite 107.9 1,480 4,000Benzyl Trihydrogenatedtallow Hectorite 119.9 5,600Dimethyl benzyl hydrogenatedtallow Hectorite 117 560Dimet hyl b enzyl hydrogenat ed ta ll ow Bentonite 96.6 400Dimethyl benzyl hydrogenatedtallow Bentonite 101.9 200Dimethyl benzyl hydrogenatedtallow Bentonite 111.1 400Dimethyl benzyl hydrogenatedtallow Bentonite 120.5 400Methyl benzyl dihydrogenatedtallow (1) 111.0 S,SOO 41,600 42,SOO

(1) 1:1 weight ratio of n e e t o ri I eand bentonite(2) - indicates the data was not obtained

EXAMPLE 2

Various types of the organophilic clay gellants pre-pared in Example 1 were evaluated as grease thickenersat a concentration of 6% by weight in the convention-ally refined oil in the presence of 0.1% and 0.3% water. 45The greases were prepared by mixing the gellant, oiland water together for thirty minutes using a drill pressequipped with pitched sweep blades rotating at 450

rpm. The resulting batch was then milled through aTri-Homo disperser with a rotor to stator clearance of 500.001 inch. The ASTM penetrations of the greases, aftersetting overnight, were obtained after working thegreases 60 and 10,000 strokes in an ASTM motorizedgrease worker assembly. The data obtained are given inTable B. These gellants were also evaluated in a con- 55ventional heated grease preparation process utilizing4% by weight acetone as a polar organic dispersant forthe gellant. The greases were prepared by mixing thegellant, oil and acetone together for 30 minutes, heatingto 250· F. with continued mixing to drive off the ace-

tone, cooling to 1800

F. and adding 0.1 % water withcontinued mixing, and milling as above. The data ob-tained for these greases, which are not an illustration ofthis invention, are compared with the data for thegreases in Table B since these greases have the samecomposition.

The data indicate that the organophilic clays contain-ing an amount of methyl benzyl dihydrogenated tallowammonium cation in excess of 100 ME per 100 grams of

clay were very efficient thickeners for this oil at ambi-ent temperatures using only a small modicum of wateras the dispersant. The data also indicates that the or-ganophilic clays having ME ratios in excess of 100 dis-perse readily in the absence of a polar organic disper-sant to produce greases having a penetration ("yield" orviscosity) which is equivalent to that obtained for thegreases prepared with the dispersant, whereas at lowerME ratios the organophilic clays produce greaseswhich are definitely inferior to the greases preparedwith the dispersant.

TABLE B

Organo[>hilic Cla:t Pr oce ss of This Inventi onQuaternary ASTM Penetrations, mm X 10 (2)

Ammonium ME 0.1% Water 0.3% Water

Chloride Clay Ratio 60X 10,000 X 60X 10,000 X

MB2HT (I) Hectorite S7.5 440+' 402 433

Prior Art Proc ess

ASTM Penetrations,mm X 10

0 .1% Wa ter

60X 10,000 X

345 367



4,287,08610

TABLE B-continuedPrior Art Proce ss

Organol2hil ic Cla;t Proc ess of Thi s Inventi on ASTM Penetrations,

Quaternary ASTM Penetrations, mm X 10 (2) mm X 10

Ammonium ME 0.1% Water 0.3% Water 0.1% Water

Chloride Clay Ratio 60X 10,000 X 60X 10,000 X 60X 10,000 X

MB2HT Hectorite 92.4 384 417 384 422 329 354MB2HT Hectorite 97.2 334 350 320 363 278 304MB2HT Hectorite 99.1 309 343 299 345 275 300MB2HT Hectorite 103.8 252 285 245 294 245 267MB2HT Hectorite 108.0 236 264 214 250 245 265MB2HT Hectorite 112.9 262 301 262 321 292 318

(1) Methyl benzyl dihydrogenated tallow( 2) Greases " too thin " to measure h ave p en etrati ons great er than 440.

The 102.6 ME ratio organobentonite thickener ofExample 1 was evaluated as a thickener/suspendingagent in an invert emulsion (water-in-oil) drilling fluidat a concentration of 4 pounds per barrel (42 gallons).The drilling fluid had the following composition: 154parts diesel oil , 129 parts water, 68 parts calcium chlo-ride, 8 parts DURA TONE HT, fluid loss control addi-tive, 15 parts INVERMUL emulsifier, and 2 parts E-ZMUL emulsifier. Standard rheology data were obtained

TABLE C 50 on the drilling fluids after mixing with the organophilic--------------------- clay for 15 minutes with a multimixer. The data ob-

5% Gellant In A Conventionally Refined Oil tained are given in Table E. The data indicates that thisOrganol2h il ic Cla ;t Gel lant organophilic clay is an excellent thickener for invert

emulsion drilling fluids.

TABLEE

EXAMPLE 3

The organophilic clay of Examples 1 and 2 preparedfrom hectorite reacted with 108ME/100 grams of clayof methyl benzyl dihydrogenated tallow ammonium 20

chloride was evaluated as a grease gellant in the samemanner as in Example 2 except that the concentration ofwater was varied from 0% to 0.4%. The ASTM pene-trations after working the greases 60 and 0,000 strokeswere as follows: 250% water-259, 259; 0.1% water-236, 264; 0.2%

water-230, 275; 0.3% water-214, 250; 0.4% wa-ter-243, 275.

EXAMPLE 4

An organohectorite clay containing 106.8ME methyl 30benzyl dihydrogenated tallow ammonium cation and anorganobentonite clay containing 102.6ME methyl ben-zyl dihydrogenated tallow ammonium cation were eval-uated as gellants at a concentration of 5% in the con- 35ventionally refined oil in the presence of 0.2% water.These organophilic clays were evaluated in a similarmanner in the presence of 2% acetone as a dispersantfor the organophi1ic clays. Thus greases were preparedby mixing the gellant, oil and either water or acetone 40together for 30minutes using the drill press as in Exam-ple 2, and milling the pre-gels obtained as in Example 2.The greases were evaluated as in Example 2. The data.obtained are given in Table C.The data indicates that the greases prepared contain- 45

ing only 0.2% water had a much lower penetration(higher grease "yield" or viscosity) than the greasescontaining the polar organic dispersant prepared by theprior art process.

Quaternary % ASTM Pene .,Ammonium ME % Ace- mm X 10

Cat ion (1) Clay Ratio Water tone 60X 10,000 X 55MB2HT Hectorite 106.8 0.2 0 285 321MB2HT Hectorite 106.8 0 2.0 332 368MB2HT Bentonite 102.6 0.2 0 300 341MB2HT Bentonite 102.6 0 2.0 328 362

EXAMPLE 5

Various organophilic clays were prepared using theprocedures given in Example 1 from sodium bentoniteand the indicated ME ratios of methyl benzyl dihy- 65drogenated tallow ammonium chloride. These organo-philic clays were evaluated as thickeners for the con-ventionally refined oil and the solvent refined oil using

the procedures given in Example 2. The data obtainedare given in Table D.The data indicates that the preferred concentration of

the quaternary ammonium compound is at least 100milliequivalents and less than 120 milliequivalents per100 grams of clay.

TABLEDASTM Penetrations,

ME % mm X 10

Oil Ratio Water 60X 10,000 X

Conventionally refined 87.9 0 373 390Conventionally refined 96.7 0 344 373Conventionally refined 100.3 0 299 345Conventionally refined 105.9 0 275 336Conventionally refined 114.5 0 345 382Conventionally refined 120.3 0 410 415

Solvent refined 87.9 0.3 440+Solvent refined 96.7 0.3 440+Solvent refined 100.3 0.3 358 402Solvent refined 105.9 0.3 305 342

Solvent refined 114.5 0.3 304 374Solvent refined 120.3 0.3 347 390

EXAMPLE 6

60

Organo Dri ll ing Flu id Rheolog ical Character ist ics

Bentonite Fann Apparent Yield Gel Stren~thThick- Viscosit;t Viscosity Point lb/looft

ener 600rpm 300 rpm cpo Ib/looft 2 10 sec. 10 min.

Example1,102.6 ME 160 110 80.0 60 37 44None 79 43 39.5 7 3 3

The examples indicate the remarkable resultsachieved utilizing the process of this invention, namely,that the viscosity of liquid organic systems is efficientlyincreased with an organophilic clay gellant in the ab-



11sence of a polar organic dispersant for the gellant. In-deed, it is preferred that the viscosity of the organicsystem obtained by the process of this invention is atleast equal to the viscosity which would be obtained ifthe organic system contained an effective dispersing 5amount of a polar organic dispersant for the gellant.This can be achieved for any particular organic systemby adjusting the ME ratio of the organophilic clay gel-lant to the optimum value for that system within therange from 100 to less than 120.We claim:1. A method of increasing the viscosity of a liquid

organic system in the absence of a polar organic disper-sant comprising mixing with said liquid organic systeman amount sufficient to effect said viscosity increase of 15an organophilic clay comprising the reaction product ofa methyl benzyl dialkyl ammonium compound and asmectite clay having a cation exchange capacity of atleast 75 milliequivalents per 100 grams of said clay,wherein said alkyl radicals independently contain from 20

16 to 18 carbon atoms, and wherein the amount of saidammonium compound is sufficient to impart to the or-ganophilic clay the enhanced dispersion characteristicsdesired, said amount of the ammonium compound beingfrom 100 to less than 120 milliequivalents per 100 grams 25of said clay, 100% active clay basis, and from 0% to1.0% water, wherein no polar organic dispersant forsaid organophilic clay is added to said organic system.2. The method of claim 1 wherein said alkyl radicals

are hydrogenated tallow radicals.3. The method of claim 1wherein there isadded from

0.1%-0.15% water.4. The method of claim 3 wherein said alkyl radicals

are hydrogenated tallow radicals.

5. The method of claim 1 wherein the organophilic 35clay is selected from the group consisting of hectoriteand sodium bentonite.6. A method of increasing the viscosity of a liquid

organic system with an organophilic clay in the absenceof a polar organic dispersant for said organophilic clay 40to a value at least equal to the viscosity which would be

4,287,08612

obtained if said organic system contained a polar or-ganic dispersant for said organophilic clay comprisingmixing with said system an amount sufficient to effectsaid viscosity increase of an organophilic clay compris-ing the reaction product of a methyl benzyl dialkylammonium compound and a smectite clay having a

cation exchange capacity of at least 75 milliequivalentsper 100 grams of said clay, wherein said alkyl radicalsindependently contain from 16 to 18 carbon atoms, and

10 wherein the amount of said ammonium compound isfrom 100 to less than 120 milliequivalents per 100 gramsof said clay, 100% active clay basis, and from 0% to1.0% water.7. The method of claim 6 wherein said alkyl radicals

are hydrogenated tallow radicals.8. The method of claim 6 wherein there isadded from

0.1% to 0.5% water.9. The method of claim 8 wherein said alkyl radicals

are hydrogenated tallow radicals.10. The method of claim 6 wherein the organophilic

clay is selected from the group consisting of hectoriteand sodium bentonite.11. The method of claim 6 wherein the reaction prod-

uct is a smectite-type clay together with methyl benzyldihydrogenated tallow ammonium chloride.12. A method of increasing the viscosity of a liquid

organic system which comprises mixing with said liquidorganic system a sufficient amount of an organophilic

30 clay to increase the viscosity of the liquid organic sys-tem, said organophilic clay comprising the reactionproduct of methyl benzyl dihydrogenated tallow am-monium chloride and a smectite-type clay selected fromthe group consisting of hectorite and sodium bentonite,wherein the amount of methyl benzyl dihydrogenatedtallow ammonium chloride is from 100 to less than 120milliequivalents per 100 grams of said clay, 100% activeclay basis, and wherein no polar organic dispersant forsaid organophilic clay is added to said liquid organicsystem.

* * * * *

45

50

55

60

65



UNITED STATES PATENT OFFICE

CERTIFICATE OF CORRECTION

Inventor (s) C] allde M. Finlayson et alp

I t i s cer t i f ied tha t er ror appears in the above-ident i f ied patentand that sa id Let te rs Patent are hereby correc ted as shown below:

Column 11 line 32 "0.1%-0.15%"

should read --0.1%-0.5%--.

Signed and S!4lled this

Fust Day o f Decrmalm- 19fii

Attest:

GERALD J. MO§SINGHOff

Attesting Officer Commissioner of Patents and Trademarks





Inven tor(s) C] aude M. Finlayson et a1.

I t is cer t i f ied that error appears in the above-ident i f ied patentand that said Let ters Patent are hereby corrected as shown below:

Column 11 line 32 "0.1%-0.15%"

should read --0.1%-O.5l~-.

Signed and Scaled thisFirst Day o f December 1981r IS[All

Attest:

GERALDJ. MOSSINGHOFF

Atteslinl OJficer Commi ssio ne r o f P ate nts a nd Tradema rk s

•

•



GERALD J. MOSSINGHOFF



Patent N o. 4,287,086 Dated September 1, 1981

Inventor(s) Claude M. Finlayson et al.

It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

Column 11 line 32 "0.1%-0.15%"

s~ould read --0.~%-O.5%--.

ISEALI

~igncd and ~calcd thisFirst Day o f lHcember 1981

Attest:

Ailes/inK Officer Commi ssio ne r o f P ate nts a nd Trademarks

arcilla organofilica polarizada

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