CA1103693A - Overtreated higher dialkyl dimethyl ammonium clay gellants - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Novel higher dialkyl dimethyl ammonium clays, of superior gellant effectiveness in oxygenated organic liquids, can be produced by the over-treatment of layer and chain type mineral clays via ion exchange reactions.
For example, a layered dioctadecyl dimethyl ammonium montmorillonite, a superior gellant for alkyd resin based coatings, is prepared by the reaction of sodium montmorillonite with a 12 to 25% excess of the corresponding quat-ernary chloride beyond the known ion exchange capacity of the clay. The overtreatment is preferably carried out in a mixtureof water and organic solvent which disperses the clay and dissolves the quaternary ammonium salt.

Description

li~ 369 3 1 Th~s invention relates to novel organophilic

2 quaternary ammonium clay compositions, namely higher di-

3 alkyl dimethyl ammonium clays, having layer and chain type

4 ætructures. More particularly, this invention relates to s overtreated gellant derivatives of layered clays having a 6 high ion exchange capac-ty and their method of preparation.
7 The present derivatives of such clays are produced by 8 treating mineral clays with a 12 to 25% excess amount of 9 the corresponding ammonium salt. Such overtreated ammonium clays, particularly montmorillonites are superior gellants, 11 e.g.~ for alkyd resin based coatings.
12 Layered quaternary higher dialkyl dimethyl ammon- ~
13 ium clays containing ammonium groups equivalent to the ion 14 exchange capacity of the starting inorganic clay are known thixotropic gelling agen~s ~or toluene and other hydrocarbon 16 solvents containing aromatic components. Their properties 17 and applications were reviewed by J. W. Jordan and F. J.
18 Williams in an article, entitled "Organophylic Bentonites III, 19 Inherent Properties" [Journal K~lloid-Zeitschrift l37, 40-48 ~ (1954)]. The compositions and their uses are largely 21 covered by patents of J. W. Jordan which are assigned 22 to the National Lead Company, i.e. NL Industries. One 23 of the basic patents issued to Jordan, i.e. U.S. Patent 24 No. 2,531,440, provides a good summary of the state of the art as it relates to the present invention.
26 The above-referred Jordan patent states, from ~ column 4, line 72 to column 5, l;ne 26~ that when preparing 28 ~mmonium clay gellants, such as the higher dialkyl dimethyl ammonium montmorlllonites, optimum gellant composltions are ~ obtained by using equ~valent reactants. The term "equiv-31 alent" means that the clay reactant is contacted wi~h amounts 32 sf the am~onium salt reactant which correspond to the ion 2 ~ ~ ~

~0 3S9 3 1 exchange capacity of the clay. The ion exchange capacity 2 of the clay is obtained by determining the amount of ammonium 3 acetate which reacts with the clay when an excess of ammoniu~
4 acetate is used as a reactant. See R. P. Graham and J. D.
S Sullivan 3. Am. Ceram. Soc., 21, 176-183 (1938). The value 6 of the ion exchange capacity is expressed in miliequivalents 7 per 100 g. dry clay (me).
8 Furthermore, Jordan in U.S. Patent No. 2,531,440 9 describes from column 4, line 72 to column 5 line 10 and in Examples 1, 2, 4, particularly Example 4, that an advan-11 tageous method for the preparation of his compositions con-12 sists of reacting a dilute aqueous dispersion of sodium 13 montmorillonite with the quaternary ammonium salt.
14 The exchange of the sodium and calcium cations of a Wyoming montmorilionite, i.e.~bentonite, having an ion 16 exchange capacity o~ 92 m.e. by various amounts of quaternary 17 dimethyl dioctadecyl ammonium chloride was studied in 18 aqueous media by J. L. McAtee of the National Lead Co. He 19 reportedin American Mineralogist, 4, 1230-1236, (1955) that ~ only sodium ions were exchanged by the quaternary ions up 21 to and at the 90 m.e. quaternary salt treatment level. At 22 the next higher treatment levels, 118 and 140 m.e. about 10 23 me calcium ion ~nd an additional 2 me sodium ion were ~4 exchanged.
~5 McAtee did not disclose either the properties of 26 the overtreated clays or their uses. Ho~ever, J. W. Jordan 27 reported pre~iously [J. Phys. Colloid Chem. 53, 294-305, 28 (1950) at page 304] that the swelling in nitrobenzene of a higher dialkyl dimethyl montmorillonite, i.e., dodecyl hexa-~ decyl dimethyl ammonium bentonite, was adversely affected 31 by overtreatment. Since the swelling o organo-clays 32 usu~lly parallels their gelling ability, this Jordan publi-il~36g3 1 cation is an indication of the adverse effects of overtreat-2 m~nt on gelling e~ficacy. A similar adverse indication is 3 ~rovided in another paper by J. W. Jordan, B. J. Hook and 4 C. M. Finlayson (J. Phys. Coll. Chem. _, 1196-1207 (1950) S at page 1203) on the gel streng.h of toluene thickened by primary octadecyl ammcnium bentonites of varying treatment 7 level.
8 The ion exchange reactions of clays having a layer 9 or chain type structure by treatment with up to a 100% excess of ammonium salts in Cl to C3 alcohol media were broadly dis-11 closed in British patent No. 1,190,383 in 1966 by B.J.
12 Fowler. Although this disclo9ure was all inclusive, no 13 specific quaternary ammonium salt reactant or product was 14 named or described.
A recent monograph entitled "The Chemistry of 16 Clay Organic Reactionst' by B.K.G. Theng - a Holstead Press 17 Book published by J. WilRy & Sons, New York (1974) particu-18 larly Chapter 5, pages 224, 22g to 232, makes it clear ~hat 19 the effect of clay overtreatment depends on the structure ~ of the ammonium salt reactants. W~th regard to the properties 21 of the organic ammonium clay products Theng stated that the 22 hydrophilic character reaches a minimum, i.e. the lipophilic ~ chsrActer a maximum at the ion exchange capacity. That 24 means that on the basis of the prior art no improved organo-philic gellants were expected from the overtreatment of clays.
26 In contrast to the prior art, it h~s now been dis-27 covered that novel higler dialkyl dimethyl ammonium clays, part~cularly montmorillonites of unexpectedly desirable gel~ant properties in oxygena~ed organic liquids are ob-~ talned if the level of clay overtreatment is kept within 31 certain limits. In studying the inter~ction of such over-32 treated clays with organic liquids of varying polarity, it _ 4 _ 1~ 3~ 3 l was discovered that they depend on clay overtreatment. As 2 a result, the discoveries of the present invention have led 3 to overtreated clay gellants for some organic liquids which 4 co~ld not be gelled by known clay gellants.
The novel compositions of the present invention 6 h~ve a surprisingly high ammonium cation and low anion con-7 tent in relation to the inorganic clay part. The inherent 8 gelling properties of the novel compositions are surprisingly 9 different and superior to those of the related prior ~rt compositions, e.g., the novel gellants are more effective in ll non-hydrocarbons especially high molecular weight li~uids 12 used for coating such as alkyd resins. This is a most im-13 portant unexpected effect. The related prior art compositions l4 are more effective in hydrocarbon solvents. In the prior art, only the hydrocarbon gelling effect of the prior art composi-16 tions was known.
17 The improvement of the gelling ability of the over-18 treated compvsitions of the present invention in oil based coatings free from aromatic hydrocarbon solvents is of par-~ ticular importance due to current environmental considerations.
21 Aromatic hydrocarbons such as toluene which were considered 22 key coating components in known organo clay gellant inter-23 actions are to be essentially eliminated from environmentally 24 acceptable coatings. The present overtreated clays provide new possibilities for the formulation of acceptable thixo-26 tropie coatings.
n It was furthermore found in the present invention 28 th~t the improved, overtreated higher dialkyl dimethyl ammon-~um clays can be advantageously prepared us~ng a mixture of ~ water and a polar organic liquid such as isopropanol as re-31 action me~ia. Such media lead to an unexpectedly increased 32 degree of ion exchan~e. This in turn results in having an i ~ 3~93 1 increased amount of the quaternary ammonium salt component 2 in the form of the aluminosilicate rather than the chloride 3 derivative.
4 Quaternary higher dialkyl dimethyl ammonium mont-S morillonite clay products containing ammonium ions in a con-6 centration equivalent to the ion exchange capacity of the 7 starting clay are known gellants for aromatic hydrocarbons.
8 The orgsnophilic properties of such gellants depend on the 9 polar character of the liquid to be gelled. This observation led to this work, extending the study of correlations between 11 gellant effectiveness and solvent polarity to overtreated 12 clays.
13 In one aspect of the present invention, there are disclosed quaternary higher dialkyl dimethyl ammonium mont--morillonite clay compositions of layer and chain type structure 16 which contain ammonium ions in a concentration ranging ~rom 17 about 12 to about 25% above the ion exchange capacity of the 18 clay as expressed in milliequivalents per lO0 g. dry clay and 19 as determined by the amount of ammonium acetate which reactswit~.
the c~y whenan excessof smmonium acetate is used as a reactant.
21 In another aspect of the present invention thexe 22 is provided a process for preparing quaternary higher dialkyl 23 dimethyl ammonium clay compositions comprising, reacting a 24 quaternary ammonium dialkyl dimethyl ammonium compound and a clay in reaction media comprising a mixture of water and a 26 polar organic liquid.
27 In the ~ollowing, novel overtreated higher dialkyl 28 dimethyl ammonium clays and their prepara~ion are disclosed.
It is sho~n that such overtreated clays, particularly mont-morillonites, containing a 12 to 25% excess of the quater-31 nary ion, have unexpectedly superior gellant properties in 32 oxygenated organic compounds, such as alkyd type polyesters, ~ 369 3 1 although they are inferior in aromatic hydrocarbons such as 2 toluene.
3 The quaternary higher dialkyl dimethyl ammonium 4 clays useful in ~he present inv~ntion can be represented by the general formula: -6 R~ n~
7 / N+(CH3)2 Clay o X
8 R m _ 9 wherein R is an independently selected C8 to C3s saturated n-alkyl group. It is preferred that R ranges from Cl4 to C2~.
11 In the most preferred case R ranges from Cl6 to Clg. It is 12 specifically preferred that R be a hydrogenated tallow group.
13 The term "Clay" designates a layered or fibrous crystalline 14 al~nil~osilicate of high ion exchange capacity and mineral crigin. Sodium and unsubstituted ammonium al~minosilicates 16 having 25 to 200 milliequivalent (me) of exchan~eable cations 17 per lO0 g. ~re preferred. ~ven more preferred are clays ~8 having ion exchange capacities ranging from 50 to 170 me 19 per lQ0 g. The most preferred clays have 80 to 120 mP ion ~ exchange capacity per lO0 g. Layered type clays are structur-21 ally preferred, particularly the three layer class. It is 22 most preferred to use a montmorillonite type clay in the 23 sod;um-salt form.
24The symbol "X" represents an anion selected from the ~roup conslsting of chloride, Cl to Clg carbaxylate, 26 ~ulfate) C2 to C8 dialkyl phosphate or phosphite, Cl to Cl8 27 sulfonate such as ormate, octanoate, dimethyl phosphate, ~8 d~utyl phosphite, methanesul~onate, dodecylbenzenesulfonate.
X is preferably ehloride or acetate and most prefera~ly ~ chloride.

31The symbols m and n are positive integers, with 32 the proviso that m is greater than n. The symbol "m" repre-1 ~`369 3 1 sents the number of quaternary ammonium cations in the com-2 position and the symbol "n" represents the number of negative 3 changes on an aluminosilicate moiety, i.e., particles which 4 are balanced by exchangeable cations n the starting inorganic S clay. The symbol "n" is related to ion exchange capacities 6 -of clays as discussed in the monograph entitled "Clay 7 Mineralogy" by R. E. Grim, published by McGraw Hill, Inc.
8 New York (1968). These ion exchange capacities are usually 9 known on the basis of the extent of the sodium clay plus excess ammonium acetate reaction.
ll As a consequence, the compositions can contain some 12 X anions, e.g., chloride anions, to help to preserve the prin-13 ciple of electroneutrality of salts. The symbol "k" in 14 the formula represents the number of anions. As such, "k"
can range from 0 to m-n. It is, however, preferred that k 16 be 1 to 50. The difference between n and m is preferably 17 5 to 30. Most preferably, k ranges from 12 to 25.
18 In the case of a typical Wyoming sodium montmor-19 illonite, the values of the above numbers may range as ~ follows: n = 80-100; m = 102-116, preferably 105 to 111;
21 k ~ O to 20, preferably 1 to 10. Optimum products are de-22 rived in ion exchange reactions by maximi~ing the value of 23 m and minimizing that of the k.
24 Exemplary clay compositions are dioctyl, ditetra-decyl, dihexadecyl, dioctadecyl, diheptadecyl, dîelcosyl, 26 d~docosyl, ditriacontyl and dipentatriacontyl, dimethyl 27 ammonium derivat;ves of montmorillonite, hectorite, atta-pulgite, vermiculite, etc.~ containing, e.g. chloride anions.
In terms of overtreatment, the novel overtreated ~ clays preferably contain 12 to 25 excess, more preerably a 31 15 to 20% excess of the quaternary ion moiety.

~lV3693 1 The quaternary higher alkyl dialkyl dimethyl ammon-2 ium clay can be prepared by reacting a clay, preferably 3 sodium clays with an excess of a higher dialkyl dimethyl 4 ammonium salt, above the known ion exchange values as in-dicated by the following reaction scheme:
6 m 1R2N~(CH3)~] X + lClzyn ] n/Y MeY
7 m [R2N+(CH3)2] Clayn~lOkx~ + n/y MeX~
8 wherein Me is Na, K, NH4, Ca, Mg preferably Na, NH4, most 9 preferably Na, y is 1 or 2, preferably 1 and the other symbols h~ve meanLngs previously de.ined. When X is monovalent, m 11 has the same value as k.
12 The type of clay mineral to be used may vary with 13 the intended use. Among the preferred clays are those having 14 crystalline, layer type structures. For optimum gelling properties, it is best to use a three layer type montmoril-16 lonite which exhibits good swelling properties in water and 17 a high ion exchange capacity. However, some non-swelling 18 clays, when converted to the ammonium salt form, will swell 19 in organic liquids and give rise to thixotropic colloidal ~ dispersions. The latter clays such as the two layer type 21 kaolinltes can be also used. Another useful clay is the 22 chain structure type attapulgite. The clays ~articularly 23 contemplated are the alkali metal and alkali earth metal 24 montmorillonites, e.g~ sodium and potassium, montmorillonites particularly of the Wyoming type, most specifically naturally 26 occurring sodium montmorillonite.
27 These clays are particularly characterized by an 28 unbalanced crystal lattice, are believed to have negative charges which are normally neutralized Sy inorganic catio~s.
~ As found in nature, therefore, they exist as salts of the 31 clay aeid with bases such as the alkali or alkaline~earth 32 metal hydroxides. The base-exchange capacities of the vari-_ g _ ~ 3~93 1 ous clays enumerated generally range from about 25 to about 2 lO0, based upon milliequivalents of ammonium acetate exch~nge-3 able base per lO0 grams of clay. The montmorillonites have 4 comparatively high base-exchsnge capacities, viz., 60-lO0.
Attapulgite has substantial base-exchange capacity, viz., 6 25-35. Generally, the clays of higher base-exchange capacities 7 are particularly preferred. . :
8 Surprisingly, the preferred products of the present 9 ~nvention, having inherently better gelling proper~ies, are prepared when the reaction is carried out in a mixture of a 11 polar organic solvent and water rather than in water alone.
12 The organic solvent is preferably mi~cible with the water and 13 is preferably selected from the group of Cl to C12 alcohols, ketones, ethers, nitriles, sul~ones, carboxylic acids, car-boxylic esters and amides. Solvents in the Cl to C4 range 16 are preferred, particularly, the alcohols. Exemplary sol-17 vents are methanol, dodecanediol, methyl ethyl ~etone, di-18 methyl ether, dioxane, furane, ace~nitrile, pyrrolidone, dimethyl sulfone, acetic acid, methyl acetate, di~ethyl form-amide. Isopropanol is most preferred.
~21 The ratio of the solvent to water in the reaction 22 media is not critical, provlded that the quaternary salt re-23 actant is dissolved and the starting clay is dispersed in the 24 medium. The preferred solvent to water ratio ranges ~rom a-bout l:20 to about 2:l, more preferably from about l:lO to 26 about l:3.
27 The unexpected effect o~ the solvent chemically manifests itself in higher conversions, i.e., higher values of the m and lower values of the k in the product. This ef-~ fect is particulzrly critical when making the novel composi-31 t~ons having an excess of the quaternary ammonium groups.
32 The react;on does not depend on the ten.perature.

1~3~93 1 From the practical point of view it is carried out below the 2 boiling point of the solvent mixture and above the fr~e2ing 3 point of water. Preferred temperatures are between 10 and 4 90. Slightly elevated temperatures between 40 and 80 are even more preferred since they result in an increased solu-6 bility of the quaternary salt reactants.
7 The ratio of the quaternary salt reactant to the 8 clay corresponds to the ratio of m to n in the product. Sur-9 prisingly, the ammonium group is essentially quantitatively incorporated into the product. The ammonium salt is prefer-11 ably used as a solution. This is added to the suspension of 12 the clay at as fast a rate as practicable. A salt solution 13 may be combined with a clay suspension in a flow system to 14 produce the reaction mixture.
The reaction is very fast. The combination of the 16 reactants results in an immediate sharp increase of the vis-17 cosity of the clay mixture. Within a few minutes this is 18 followed by a reduction of the viscosity due to the separation 19 o~ macroscopic product particles. me product is usually ~ separated within a few hours ~y filtration and may be washed 21 before drying. The particle size of the dry product is usua~-22 ly reduced below 200 mesh size by kno~m me~ns of pul~-erizing 23 and milling before or during its use.
24 The reaction does not depend on the concentration of the reactants. However, to prepare the preferred composi-26 tions in a practical manner it is important to have the 27 clay in the form of well stirrable colloidal suspension.
The clay concentration is preferably 0.5 to 10%, more prefer-~ ably 1 to 5%. The quater~ary salt is preferably in solution of a concentration o~ preferably 3 to 80% more preferably 31 to 20Z.

1 The properties of the products are largely de-2 pendent on their microstructure. For example, in the-case 3 of the layered montmorillonite derivatives, a characteristic 4 of the microstructure is the interplanar spacing. m is is S the repeat distance between the aluminosilicate layers.
6 It has been found that in the case of the overtreated clays, 7 this distance is surprisingly dependent on the number of 8 carbon atoms of the higher n-alkyl substituents of the g quaternary ammonium moieties. Such a dependence in the C14 to Ci8 alkyl range is in contras~ with the prior art observa-11 tions by Jordan on monoalkyl ammonium clays of the same carbon 12 range. This indicates an unexpected difference between the 13 m~crostructure of overtreated ammonium clays and the stoichi-~4 ometric compositions repor~ed previously. The microstructure presently found is due to a certain orientation of the higher 16 alkyl groups between the aluminosilicate layers in a manner 7 described for quaternary phosphonium clays by A. A. Oswald 18 ~n U.S. Patent No. 3,929,849.
9 The novel compositions are unexpectedly useful as ~ thixotropic components of polar organic liquids of preferably 21 nonhydrocarbon character? more preferably oxygenated organic 22 compounds, particularly polyesters wherein related prior art 23 compositions are not effective. The present compositions 24 ~re speci~ically useful in the so-called alkyd resins. The latter are polyesters derived from ~atty acids such as 26 ~tearic acid, polyols such as glycerol or glycol and di~ar-27 boxylic acids such as phthalic anhydrlde.
~ Certain types o alkyds, the so-called long oil 29 alkyd resins are the most commonly used base for general purpose industrial coatings. Such base resins are usually 31 ~iluted with minor amounts of a hydrocarbon solvent. For 32 example, 3V~/~ of mineral spirits may be employed.

i~3693 The present compositions in general will provide im-proved thixotropic compositions in polyesters including un-saturated polyesters such as those described in U.S. Patent No. 3,974,125 by Oswald and Barnum. Among other oxygenated compounds are as examples polyalkylene terephthalates, nylon type polyamides, epoxide resins. An example of nonhydro-carbons containing no oxygen is polyvinylchloride.
Related prior art thixotropic gellants are known to interact with the ~ydrocarbon solvent. The present gellants surprisingly interact with nonhydrocarbons. The latter ac-tivity depends on the presence of excess quaternary ammonium groups in the present compositions. Dependent on the amount of this excess, the activity of the present compositions shows an unexpected optimum. The ~mmonium excess in the optimum composition is dependent on the structure of the quaternary ammonium moiety, the aluminosilicate and the anion present.
~XAMPLE 1 Preparation of Higher Dialkyl Dimethyl Ammonium Montmorillo-nite Compositions Having About 10~ Excess of the Ammonium Moiety Quaternary C8 to C22 dialkyl dimethyl ammonium deriva-tives of a Wyoming montmorillonite were prepared via reac-tions of the corresponding ammonium chlorides with sodium montmorillonite in the manner disclosed in Example 1 of U.S.
Patent ~o. 3,974,125.
The sodium montmorillonite used was Georgia Kaolin Co.'s Mineral Colloid BP a refined clay of the composition corres-ponding to the summary formula:
(Si Alo 66).A13 lgFe 0 37 1~g0.54 20 4 0.10 o.o This clay (MCBP) was indicated to have an ion exchange capa-city of 90 milliequivalents (me) per 100 g dry clay In the il~36g3 1 present work, however, 99 me of the quaternary s.1ts per 2 100 g clay was used. , 3 The quaternary ammonium chloride reactants were 4 laboratory chemicals purchased from Lachat Chemicals.
In general, water-isopropanol mixtures were used 6 as reaction media. Mixtures of the same concentration were 7 used to disperse the clay and to dissolve the quaternary 8 s~lt. The concentration of the quaternary reactant solution 9 was 10%. The concentration of the clay in the overall re-action mixture was 2%. With the increasing length of the 11 hi~her alkyl substituents of the quaternary salts, their 12 water solubility decreased and, consequently, the isopropanol i3 concentrations employed increased from 0 to S~/O.
14 Both the clay suspension and the quaternary solu-tion were kept at 50C. At that temperature the quaternary 16 reactant was added all at once to the clay suspension which 17 was being stirred at a high rate. This resulted in an im-18 mediate large increase of the viscosity followed in 2-3 min-19 utes by a thinning of the solvent and the formation of the ~ product precipitate. Stirring at 50C. was continued for 21 30 minutes. The mixture was then filtered with suction at 22 the same temperature. The products were washed for filtra-23 tion three times on the Buchner-funnel by fresh aqueous iso-24 propanol of the composition used in the reaction. The fifth wash employed water. At the 30 g. starting clay level the 26 volume of liquid for one wash was 300 ml. Products having 27 increasing alkyl substituents were increasingly hydrophobic and easy to filter. The washed, filtered products neverthe-less still had a water content o~ about 90%. They were ~ dried under 0.1 mm pressure either at ambient temperature 31 or a~ 60C. The dry products were ball milled overnight and 32 then passed through a 200 mesh screen. Thereafter, they il~ 369 3 1 were analyzed and evaluated. T heir interplanar spacings of 2 the 001 reflection by X-ray and elemental compositions are 3 shown in Ta~le I.
4 The interplanar spacing of the-products as de-termined by X-ray diffraction analysis, i.e., the repeat dis-6 tance between the layers, was much larger than that of the 7 starting clay, l~Avs. l~Aor greater. The interplanar dis-8 ` tance of the products was increasing with the length of the 9 higher alkyl substituents of the quaternary nitrogen. In the case of the C8 to C16 derivatives the change of this dis-1l tan~e per two carbon increase or the alkyl substituents was 12 decreasing. Overall the definite changes in the C14 to Clg 13 alkyl range were in contrast with the observations of 14 Jordan on monoalkylammonium mon~morillonites of the same range. Jordan reported no change whatsoever in this 16 region ~ournal o Physical and Colloid Chemistry 53, 2~7 17 (1950)]. This indicates an unexpected difference between 18 the microstructurP of the present ammonium clays and of those 19 reported previously. This microstructure is apparently dif-~ ferentiated ~y the various orientations of the higher alkyl 21 groups between the aluminosilicate layers.
22 As it is also shown by Table I, the found elemental 23 composition`of the clays was in fair agreement ~ith the cal-24 culated compositions assuming the attachment of all the ammon-ium groups to the clay. The chlorine content of the products 26 is low indicating that the clay undergoes the reaction with 27 the large higher dialkyl dimethyl ammon~um ion beyond 28 it~ prior art ion exchange capacity.

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~ o 1 EX~PI.E 2 2 Prepa ation of nuaternary Ditallo~ Dimethyl Ammonium Mont-mori~lonite Compositions Having About 0 to 30% Excess of 3 The Ammonium ~Ioiety 4 The refined montmorillonite of Example 1 was also S reacted with various quantities of a technical hydrogenated 6 ditallow dimethyl ammonium chloride derived from hydrogenated 7 tallow oil. As such~ a quaternary hiOher dialkyl dimethyl 8 ammonium chloride was used wherein 50% of the alkyl groups 9 had 18 carbon atoms 35Z was C16 and 5% C14. This product was obtained from the Ashland Chemical Company under the B 11 trade~o~e Adogen 442-75. This co~ercial product composi-12 tion had 75% quaternary salt, 20% isopropanol and 5% w~ter.
13 At room temperature the product is a waxlike solid, but it j4 is easily melted to provide a cle2r liquid mixture. The quaternary salt is not significantly soluble in cold water 16 but it is readily soluble in aqueous isopropanol. The prep-ara~iol and analyses of Adogen-442-7~ modified montmorillon-18 ites are summarized in Table II.g The ditallow dimethyl ammonium montmorillonites of Table II were deri ~ by using various quantities of the 21 quaternary s21t reagent per 100 g. dry clay, ranging from 2? amounts corresponding to the ion ex~hange capacity (90 me) 23 to 35% excess (121 me). Some of the clay modifications were carrled out in water, others used a 4 to 1 mixture of water and isopropanol. The large scale reactions were run at am-~6 bient temperatures (Seq. Nos. 2-4). The labor~tory prepara-tions were carried out at 55-60C. in ~he manner described ~n the previous example (Seq. Nos.5~9). The concentration of the clay in the reaction mixtu~;e ran~ed from 2 to 3%. The ~ Ado~en 442-75 was added either as ~h or as a 5-10% solution 31 in a liquid having an identical eomansition with the clay 32 dispersion medium.

~lV3693 1 ' The analysis of a commercial dimethyl ditallow ammonium clay product of the Georgia l'aolin Co., Astr~ton~-3 40, is shown for comparison under Sequence No. 2 of Table I.
4 Pilot plant preparations were carried out using a sodium montmorillonite slurry (Seq. Nos. 2 ~nd 3) in equivalent 6 and excess amounts. This slurry was prepared from a crude 7 sodium montmorillonite clay mined and dried in Wyoming.

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_ ~0 -11~ 369 3 l ~ The crude clay (900 lb., i.e. 408 kg.) and ? Cal~on hexanetaphosphate dispersant additive (1.5 lb;, i.e.
3 680 g.) were mixed with water (1218 gal., i.e., 4610 liter) 4 for 30 minutes using a Strucher-Wells high speed mixer. The S large particle size impurities were then removed from the resulting water gel by passing it through a 100 mesh screen.
~ Thereafter, the finer impurities having a larger than 2 8 microns size were removed by a DeLaval centrifuge. The re-9 sulting stable dispersion had a pH of 8.1.
The refining of the crude clay of 8.8570 solids ll content resulted in a slurry of 3.12% concentration. This 12 slurry was prepared five days in advance. It was then kept 13 in a holding tank at 60C. since there was no provision for i4 heating the pilot plant reactor vessels.
In both of the pilot plant preparations, 200 gal.
16 of the slurry was used in a polyethylene tank. The Adogen 77 442-75 was melted at 50C. The mèlt was added over a 5 min.
18 period to the slurry which was sLirred at 160 rpm at 50C.-19 In the case of the 90 milliequivalent treatment, the addition o~ the quaternary salt (23.28 molesj resulted ~l only in a moderate thickening followed by a rapid viscosity decrease. In contrast, the 99 me. treatment (with 44.1 lbs.
Adogen 442 containing 25.6 moles quaternary salt) resulted ~4 in substantial but not excessive thickening.
~5 ~;fter about 35 minutes stirring both ammonium clay products were fil~er pressed. In the case of the lower treat-~7 ment a filter pressure of 30 lbs. was sufficient for getting ~8 a sufficiently moisture free cake. The more highly treated product required 60 lbs. ~or effecti~e filtration. ~lso, ~ the higher treatment resulted in a foamy~ slightly cloudy 31 rather than clear aqueous filtrate.
~2 Both ammonium clays were air dried overnight in an 1~0369 3 1 air blown heated oven after filtration. However, by accident 2 the overtreated clay was dried at 70 rather th2n 60C. This 3 had no apparent effect. After drying, both products were ~ pulverized.
S The analyses of the quaternary ditallow dimAthyl ammonium montmorillonites of Table I, in general, show that 7 the organic content of the clay products is increasing with 8 the level of treatment by the quaternary salt. This indicates 9 that the quaternary groups are retained on the cl~y in ~uan-1~ ti~ies in excess of the ion exchange capacity.
11 The found clay compositions ~Jere comp~red with com-12 positions calcul ted assumin~ either the reactio~ of only 13 equivalent or the reaction of all added ~uaternary salt.
~4 The comparison of the chlorine values showed that, in the case of treatment in isopropanol-water high excess, more 16 than an equivalent but not all the quatern2ry s~lt entered 17 the ion exchange (Seq. No. ~ and 9).
18 In water medium, the reactions were apparently con-9 versions limited as indicated by the relatively high chlor-ine contents (Seq. Nos. 2-4, 6). In these cases, much of ~1 the quaternary reagent remained in the chloride form. The ~2 difference caused by the substitution uf water by isopropano-~3 lic wate~ is particularly sho~m by the data of the fifth and ~4 sixth experiments. The chlorine content of the product was reduced to less than one-third when alcohol was present ~6 (Seq. Nos. 5 and 6). At the sa~e time the carbon content in-27 creased rather than decreased indicating that the retention 28 of the ammonium gr~lps on the clay was not adversely afected.
To learn about the change o the concentr2tion of ~ metal cations as a function of the treatment level several of 31 the clays of Table I were also analyzed or ~a, K and Ce.
32 The values found9 were then compared with those for the ~)3693 1 8t8rting ~ICBP clay: ~ .
~ Exp. TreatmentX-Ray Elemental Composition, 3 No. LevelSpacin~ Found, %
E metlO0 ~. A Na lC C2 - ~il 2.150 0.159 0.304 -6 2811-I 90 2~.4 0.386 0.099 0.058 7 2682-III 99 12.8 26.7 0.038 0.088 0.058 8 2690-III 110 12.6 31.5 Q.038 0.021 0.050 9 ~698-III 120 12.8 21.0 35.5 0.038 0.066 0.029 The comparison showed that up to the 120 me treat-11 ment level, the meta~ ion concentration was independent from 12 the degree of overtreatment. (The high ion concentrations 13 of the commercial products Astratone 40, ~7ere mainly due to 14 incomplete washing.) A significant, but minor change in the concentration of K and Ca seemed to occur at the 120 me 16 treatment level. -_ -17 The X-ray spacing o the clays of various treat~ent 18 level indic~ted changes in microstructure. With overtreatment, 19 an increased dO01 spacing is observed, indicating that the angle of the higher alkyl groups relative to the aluminosil-~1 icate layer is increased. Additional peaks are also observe~
22` in the spectr~. These peaks, the 12.7~ peak probably origin-23 ating from a d003 reflection, indicate new phase formation 24 on overtreatment.
T~E MET~IODS USED TO DETER~INE GELLI~IG ABILITY
26 All the gel test methods give somewhat different 27 results i organic clays of various p~rticle size are us~d.
28 Therefore, the dry, ball milled clays were all passed thrvugh 29 a 200 mesh screen before testing.
A The ~lkyd Resin Gel Test 31 ~lkyd resins are in general, polyesters derived 32 rom fatty acids, polyols such ~lycerol or glycol, and di-i~3693 carboxylic acids, usually phthalic anhydride. The resins used in the present tests were long oil alkyd resins, which are most commonly used for general purpose industrial coatings.
They were obtained from Reichhold Chemical under the name Beckosol* P-296-70 with a computer code number 10-045. The product contains 3~% mineral spirits as a solvent. The solid resin (70%) is derived using about 65~ soybean oil, 24%
phthalic anhydride and ll~ glycerol. As such, the product meets federal specification, classification TTR 2660A, Type Class A, vinyl compatible. Its Gardner-Holdt viscosity is Y-Z2. The viscosity of the products supplied was apparently significantly different on the Brookfield scale, when deter-mined using a number three spindle.
For the viscosity determinations, fluid is poured into a pint can where the viscosity readings are taken using a Brookfield viscometer with a number three spindle. The spin-dle is inserted to the near side of the jar and then moved to the center. Then viscosity readings are taken from low to high stirring rates: at 10 rpm after 40 seconds at this speed, at 20 rpm after 30 seconds, at 50 rpm after 20 seconds and at 100 rpm after 15 seconds. After the viscosity read-ings, the temperature in the rear side of jar is usually about 30 C. and at the center 35C.
In the alkyd resin gel tests, three batches of Beckosol*
P-296-70 were used. Their viscosity characteristics, as determined by the Brookfield viscometer, were somewha~
different as indicated by the following tabulation:
Batch Identification Brookfield Viscosities, cps, of Long of Resin Oil Alkyd Resins After 18-24 hours 30Beckosol* P-296-70 (at various Stirring Rates, rpm) (10) (20) (50) (100) * Trade Mar.;

- 2~ -1~036g3 l The di~ferent batches of the resin showed different respon-2 ses ~o the higher dialkyl dimethyl ammonium clay gellants.
3 Therefore, strictly speaking, the data are comparable only 4 when the same batch of resin w~s used.
The response of these resins to organic clay gel-6 lants was de~ermined using available commercial quaternary 7 dimethyl dihydrogenated tallow ammonium clays, as standards, 8 h~ving equiv~lent amounts of the quaternary group on the 9 clay. The Astratone 40 standard is manufactured by the Georgia K~olin Co. starting with refined sodium montmoril-ll lonite, basically the same clay which was used in our 12 Examples 1 and 2. The Benton ~ 38 standard is manufactured 13 by N. L. Industries from refined sodium hectorite. The ef-14 fectiveness of the~e two a~monium clays in the three batches of alkyd resin was as shown by the following tabulation.
16 Brookfield Viscosities 17 Batch Identifi- o~ Long Oil Alkyd 18 - cation of Resin Resins After 1~-24 Hrs.
l9 Dimethyl Ditallow Beckosol P-296- At Various Stirring 20 Ammonium Clay 7~ Rates (r~m) (lO)(20j ~(50) ~l00 21 Astratone-40 ~ 60005400 5120 4940 22 Bentone-38 A 68006200 5680 5320 23 Astratone-40 B 32003100 3~40 2960 24 Bentone-38 B 44004000 3760 3540 Astratone-40 ~ 34003400 3280 3120 26 Bentone-38 C 44004200 3920 3740 27 In the test procedure, 1.25 g of ammonium clay is 28 slowly added to 88 g. resin, while stirring it with a high 29 speed, i.e., high shear mixer (with a drill press equipped with a circular Cowle's blade). Ater mixing for about two to 31 five minutes, a polar solvent mixture consisting o 95%
32 propylene carbonate and 5% water ls added in an amount e~ual-33 ing 33% of the clay while stirrin~ to give optimum dispersion ~ 25 -l and highest viscoslty. Thereafter, stirring is continued 2 for an additional five minutes. The resulting gel is then 3 thinned using a solvent, i.e., 10 g odorless mineral `spirit, 4 to reduce the viscosity. Viscosity measurements of the re-S ~ sulting mixtures are made in 18 to 24 hours after the air 6 bubbles formed during the stirring rose out of the liquid 7 gels.
8 B. The Toluene Gel Stren~th Test 9 - To 294 g. toluene placed into a Waring blender, 6 g.
io o higher dialkyl dimethyl ammonium clay is added in 45 sec-11 onds while it is stirred at a rate of about 10,000 rpm 12 (transformer setting 25). The resulting mixture is then l3 stirred at 15,000 rpm for 90 seconds (transformer setting li 100). The stirring rate is then reduced to 13,000 and 2.3 lS ml polar ~dditive, consisting of 95% co~mercial (i.e.~ 99%) 16 methanol 2nd 5% distilled water is added over 30 seconds.
17 The speed is then again increased to 15,000 rpm and the 18 stirring continued for a further 3 minutes.
l9 The gel is then poured into a pint jar which is ~ subsequently rocked and swirled for 3~ seconds to remove 2l most of the air bubbles. The jar is then capped tight and 22 put into a 25C. water bath. After fifteen minutes and 34 23 hours, viscosity readings are taken in the manner previously ~4 described. Eetween the 10 minutes and 24 hours reading, the jar is capped and set in a 25C. water bath until the 26 24 hour reading.
27 C. The Unsaturated Polyester Test 28 Unsaturated polyesters are polyesters of a dicar-boxylic ~cid and a diol having a maj or amount of olefinic un-~ saturation. Such esters are more extensively defined in U.S.
3l Patent 3~974,125. This patent also describes in detail the 32 styrene pre~el method used in the present test. Throughout - 26 _ i~LV3t~93 this wo~rk a common unsatura~ed po~yes~er derived via 2 the esterification of maleic anhydride, phthalic anhydride, 3 propylene glycol mixture was used. It is commercially~ pro-4 duced by the Reichhold Chemical Company and sold e.g. as a 60% polyester, 40% styrene liquid mixture under the number 6 ~ 33-072, 64005.
7 Styrene pregels were prepared usually at the 6%
8 higher dialkyl dimethyl ammonium clay gellant level by add-9 ing the appropriate quaternary clay having less than 200 mesh particle size to polymerization grade styrene stabil-11 ized ~ith 50 ppm t-bu~yl catechol. In a standard test, 12 3 g. of gellant and 50 g. styrene were place~ into a 9~5 13 cm high, ~.5 cm diameter metal can. The contents were then 14 ~tirred on a Rockwell Delta 6 Plus 6-15 in. drill press, B 15 equipped with a 5 cm wide "Cowles Blade~ at 725 rpm to ob-16 tain the pregel which was then usually employed for gelling 17 the p~lyester composition.
18 An 80% polyester - 20% styrene resin was used to 19 make gels containing 40% styrene by adding approximately one part pregel to three parts of the resin.
21 In a typical procedure 52 g. of the styrene pregel 22 was added ~o 148 g. of the liquid 80~/o polyester - 20% sty-23 rene mixture, using stirring by drill press as described 24 earlier. After 15 minutes stirxing, the resulting gels were closed to avoid evaporation, stored at ambicnt temper-26 a~ures and/or at 24C. Viscosity measuremen~s were carried 27 cut after 15 minutes and 24 hours using a Brookfield LVT
28 Viscome~er with a number 3 spindle at 6 and 60 rpm stirring 29 ~ate, generally at 24C.

~36g3 EXA~tPLE 3 t 2 Gelling Effectiveness of Various Higher Dialkyl Di~.ethyl 3 _ Ammonium ~Iontmorillonite Cleys in Alt;~ Resins 4 .The clay preparations of Example 1, containing 10% excess of the ammonium moiety were tested 8S gellants 6 in alkyd resins in the manner previously described. The 7 results are shown in Table III.

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~1113693 The data of Table III show that all the higher dialkyl dimethyl ammonium clays had a gelling effect on the alkyd resins. The gelling effect of the dioctyl derivative (Seq.
No. 1) was particularly surprising since the prior art work-ers stated that the presence of higher than decyl group was necessary for a gelling effect.
Although all the clays tested were gellants not all of them had a significant thixotropic effect. Only the C14 to Cl~ derivatives increased the viscosity of the alkyds signif-icantly more at low than at high stirring rates (Seq. Nos.
4-6). Surprisingly, the hexadecyl derivative seemed to be the most effective thixotropic gelling agent.

Gelling Effectiveness of Ditallow Dimethyl Ammonium Montmor-illonite Clays in an Alkyd ~esin and in Toluene as a Function of Their Degree of Overtreatment.
. _ . .
The gelling effectiveness in an alkyd resin and in toluene of sodium montmorillonite treated with various quan-tities of Adogen 442-75 was examined by the test methods des-cribed earlier. The preparation of the variously overtreated clays was given in Example 2. In the present example, vis-cosities were determined in a general purpose long oil alkyd resin containing 1.4% o~ the experimental gellants and in toluene having 2% gellant concentrations.
The test results are given in Table IV. The table also shows the styrene swell, which is determined ~y slowly add-ing using a spatula 2 g. of an ammonium clay sample to 100 ml polymerization grade styrene. The styrene was contained in a 100 ml measuring cylinder of about 2.5 cm diameter. On the addition of the clay gelling agents, a spontaneous gelling occurred. The resulting gel volume of the clays was several-fold of the original by the time they fell to the bottom of the cylinder. The volume of the resulting bottom ~03693 1 gel "phase" was read after 15 minutes, 2 hours and 24 2 hours.
3 The viscosity data of the table show different re-4 sponses to overtreated clay gellants in alkyd resins and in S toluene. In the alkyd resin the moderately overtreated clay

6 showed optimum effectiveness when prepared in aqueous iso-

7 propanol (Seq. No. 3); Furthermore, severe overtreatment

8 did not significantly reduce the gel strength in the alkyd

9 (Seq. Nos. 4-6). In contrast, in toluene the moderately overtreated clay was effective only when prepared in water 11 (Seq. No. 2 vs. 3). The more severely overtrea~ed clays had 12 no significant gellant activity in toluene (Seq. Nos. 4-6).

_ 31 _ 693.

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_ 33 _ ~1~3693 1 The gel strengths in toluene are somewhat anal-2 ogous to the styrene swells. In the latter case as well 3 a high degree of overtreatment results in inferior effects.
4 It is felt that the hydrocarbon swelling and gelling activ-ity of completely or overreacted clays is inferior to those 6 ~nly substantially reacted. A similar behavior of am~onium 7 clays towards nitroben~ene was reported by Jordan with a 8 .comment of overtreating being deleterious.
9 EX~LE 5 Gelling Effectiveness of Dihydrogen2ted ~itallow Dimethyl 11 Ammonium ~lon~morillonite Clays in an Unsaturated Polyes~er 12 as a Function of Their Degree of Overtreatment.
13 The gelling effectiveness of various Astratone 40 14 type clays in a maleic and phthalic anhydride plus propylene glycol based unsaturated polyester was examined via the 16 styrene pregel method described earlier. This unsaturated 17 polyester is most often used for the preparation of glass re-18 inforced thermoset resins. In the present tests, the inal 19 gels contained 40% styrene which serves both as a solvent for the solid polyester and a crosslinking monomer.
21 The gels resulting from the experiments using 22 variously overtreated gellants were evaluated for their vis-23 cosity at 6 and 60 rpm. The viscosity data obtained and 24 the viscosity indices are shown in Table V.
The prepzration of the series of increasingly over-26 treaLed dihy~rogen2ted ditallow ammonium montmorillonite 27 gellants ~sed ~7as described in Example 2. The nonovertreated 28 Astratone 40 commercial control gellant of 9~ me treatment 29 level was also described previously.

- 34 ~

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1 The data of table IV show that the clay commer-2 cial gellant (Sequence No. 1) was generally less effective 3 both in terms of absolute viscosities and viscosity indices 4 than the overtreated clays (Sequence Nos. 2-6). The thixo-tropic effectiveness of the e~peri.mental clays was clearly 6 dependent on their tre~tment level. The relatively poor 7 perform2nce of the commercial clay was obviously a conse-8 quence of its low treatment level.
9 The optimum trestment level ~:Jas-in the~range of 110-115 milliequivalent dimetltyl ditallow ammonium chloride 11 per 100 g ~ry clay (Sequence Nos. 3,4). A comparison of 12 the viscosity values of the commercial clay with the op-13 timally treated clay sho~s rounded 60 rpm viscosities of 14 about 1500 versus 2000 ~nd viscosi~y indices of 2.0 versus 2.6. The be~ter performance of the optimally overtreated 16 clay seems particularly important in terms of the thixotropic 17 index, which is the most i~portant parameter in reinforced 18 plastics applications.
1~ The value of overtreatment in terms of the ammonium -clay gellant needed to achieve certain thixotropic properties 21 c~n be estimated from the response of the unsaturated poly-22 ester resin to different concentrations of the normal Astra-23 tone 40 gellant (E-2811-~). This concentration response is 24 shown by the follo~Jing tabulation.

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1 - A comparison of the data shows that in terms of 2 vi~cosities at 6 rpm increasing the Astratone 40 concentra-3 tion from 1.5~ to 2%, i.e. by 33%, achieves the performance 4 of the overtreated clay at 1.5%. However, increasing the 5 ~ Astratone 40 concentr2tion to 2% does not result in the same 6 high viscosity index which was obtained by 1.5% of the over-7 treated clay.
8 As evidenced from these examples, the overtreated 9 clays of the present invention are capable of providing im-proved thixotropic compositions ~hen they are admixed with 11 major quantities of an oxygenated org~nic com~ound. The i2 amount of the overtreated clay when used as a gellant in 13 these systems will be in 2n amount sufficient to att~in the .
14 desired thixotropic characteristics for the particular com-p,osition being prepared.
16 ' In many instances, the amount of the overtre~.ted 17 cl~y of the present, invention will be in the range from about 18 0.2 to 10% by weight of the entire composition, preferably 1~ the overtreated clay will ~e present in an amount ranging from about 0.5 to about 3 weight percent. The balance of the 21 com?osition will be comprised of the oxygenated organic com-22 pound, preferably an o~ygenated organic resin and more prefer-23 ably an alkyd type polyester or an unsaturated polyester.
24 In the latter case the composition ~ill typically contain 2 solvent for the oxygenated organic resin in an amount to suf-26 ficiently disperse or dissolve the resin.

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing a quaternary higher dialkyl dimethyl ammonium clay composition of layer and chain type structure comprising reacting in a reaction media comprising a water miscible polar organic solvent and water having dispersed therein mineral clays of layer and chain type structure with a quaternary higher dialkyl dimethyl am-monium salt dissolved in said reaction media, wherein the concentration of ammonium ions of said ammonium salt ranges from about 12 to 25% above the ion exchange capacity of the clay as expressed in milliequivalents per 100 g. dry clay and as determined by the amount of ammonium acetate which reacts with the clay when an excess of ammonium acetate is used as a reactant.

2. The process of claim 1 wherein the concentra-tion of the ammonium ions ranges from about 15 to about 20%
above the ion exchange capacity of the clay.

3. The process of claim 1 wherein the said higher dialkyl substituent of the quaternary higher dialkyl dimethyl ammonium salt is C8 to C35 alkyl.

4. The process of claim 1 wherein the said higher dialkyl substituent of the quaternary higher di-alkyl substituent of the quaternary higher dialkyl dimethyl ammonium salt is C16 to C18 alkyl.

5. The process of claim 1 wherein the polar or-ganic solvent is a member selected from the group consist-ing of C11 to C12 alcohols, ketones, ethers, nitriles, sul-fones, carboxylic acids, carboxylic esters and amides.

6. The process of claim 1 wherein the polar organic solvent is isopropanol.

7. The process of claim 1 wherein the solvent to water ratio ranges from about 1:20 to about 2:1.

8. A process for preparing a quaternary higher dialkyl dimethyl ammonium clay composition of layer and chain type structure comprising reacting in a reaction media comprising isopropanol and water having dispersed therein a Wyomining montmorillonite clay with a dihydrogen-ated ditallow dimethyl ammonium chloride dissolved in said reaction media, wherein the concentration of ammonium ions of said ammonium salt ranges from about 15 to 20% above the ion exchange capacity of the clay as expressed in milliequivalents per 100 g. dry clay and as determined by the amount of ammonium acetate which reacts with the clay when an excess of ammonium acetate is used as a reac-tant.

9. A thixotropic composition comprising a major amount of an oxygenated organic compound and a quater-nary higher dialkyl dimethyl ammonium clay gellant of layer and chain type structure containing ammonium ions in a con-centration ranging from about 12 to about 25% above the ion exchange capacity of the clay as expressed in milli-equivalents per 100 g. dry clay and as determined by the amount of ammonium acetate which reacts with the clay when an excess of ammonium acetate is used as a reactant, said clay gellant being present in amounts sufficient to attain the desired thixotropic characteristics.

10 . The thixotropic composition of claim 9 where-in the oxygenated compound is an alkyd type polyester.

11. The thixotropic composition of claim 9 where-in the oxygenated compound is an unsaturated polyester.

12. A thixotropic composition comprising a major amount of an oxygenated organic compound and a quaternary dihydrogenated ditallow dimethyl ammonium montmorillonite clay gellant containing ammonium ions in a concentration ranging from about 15 to 20% above the ion exchange capacity of the clay as expressed in milliequivalents per 100 g. dry clay and as determined by the amount of ammonium acetate which reacts with the clay when an excess of ammonium acetate is used as a reactant, said clay gellant being pres-ent in amounts sufficient to attain the desired thixotropic characteristics.

13. The thixotropic composition of claim 12 wherein the clay is a three layered type.