Organophilic clay gellant having enhanced dispersibility

This invention relates to organophilic organic-clay complexes which are dispersible in organic liquids to form a gel therein. Depending on the composition of the gel, such gels may be useful as lubricating greases, oil base muds, oil base packer fluids, paint-varnish-lacquer removers, paints, foundry molding sand binders and the like.
It is well known that organic compounds which contain a cation will react under favorable conditions by ion-exchange with clays which contain a negative layer-lattice and exchangeable cations to form organophilic organic-clay products. If the organic cation contains at least one alkyl group containing at least 10 carbon atoms, then such organoclays have the property of swelling in certain organic liquids. See for Example U.S. Pat. No. 2,531,427 and U.S. Pat. No. 2,966,506, both incorporated herein by reference, and the book "Clay Mineralogy", 2nd Edition, 1968 by Ralph E. Grim (McGraw-Hill Book Co., Inc.), particularly Chapter 10, Clay-Mineral-Organic Reactions; pp. 356-368-Ionic Reactions, Smectite; and pp. 392-401-Organophilic Clay-Mineral Complexes.
Since the commercial introduction of these organo-clays in the early 1950's (trademarked BENTONE, a product of NL Industries, Inc.), it has become well known to gain the maximum gelling (thickening) efficiency from these organoclays by adding a low molecular weight polar organic material to the composition. Such polar organic materials have been variously called dispersants, dispersion aids, solvating agents, dispersion agents and the like. See for example the following U.S. Pat. Nos.: O'Halloran U.S. Pat. No. 2,677,661; McCarthy et al. U.S. Pat. No. 2,704,276; Stratton U.S. Pat. No. 2,833,720; Stratton U.S. Pat. No. 2,979,229; Stansfield et al. U.S. Pat. No. 3,294,683.
It is disclosed in U.S. Pat. No. 3,753,906 that water is a dispersant when used in a heated grease preparation process. U.S. Pat. No. 3,654,171, however, discloses that water is not a dispersant in grease preparation processes conducted at a temperature ranging from ambient to about 220.degree. F. (104.44.degree. C.). These polar materials may also affect properties other than the viscosity or gel strength of the organic gels, such as mechanical stability, thixotropy, and storage stability.
The most efficient and accepted polar materials for use as dispersants have been found to be low molecular weight alcohols and ketones, particularly methanol and acetone. These dispersants, however, have very low flash points and require the use of flameproof apparatus. Higher boiling, high flash point dispersants may be used but these are less efficient and often produce gels having poor secondary properties such as mechanical stability or storage stability.
U.S. Pat. No. 3,537,994 to R. House discloses the use of organophilic clays prepared from methyl benzyl dihexadecyl ammonium compounds as gellants for lubricating greases. All of the examples in this patent disclose the use of a polar organic dispersant for the organophilic clay in the preparation of the greases.
Accordingly, there is a need for an organophilic clay gellant which is easy to disperse in organic systems and which requires no dispersant, other than perhaps minor quantities of water, for gelling organic systems.
An organophilic clay gellant having enhanced dispersibility in organic systems has been unexpectedly discovered comprising the reaction product of a methyl trialkyl ammonium compound and a benzyl trialkyl ammonium compound, wherein the alkyl groups have from 14 to 20 carbon atoms and a smectite-type clay having a cation exchange capacity of at least 75 milliequivalents per 100 grams of said clay, and wherein the amount of said ammonium compound is from 100 to 120 milliequivalents per 100 grams of said clay, 100% active clay basis. Preferably the compound contains 20 to 35% alkyl groups having 16 carbon atoms and 60% to 75% alkyl groups having 18 carbon atoms. A similar reaction product containing methyl benzyl dialkyl ammonium compound is defined in U.S. Pat. No. 4,105,578 patented Aug. 8, 1978.
The clays used to prepare the organoclay thickeners of this invention are smectite-type clays which have a cation exchange capacity of at least 75 milliequivalents per 100 grams of clay. Particularly desirable types of clay are the naturally occurring Wyoming variety of swelling bentonite and like clays, and hectorite a swelling magnesium-lithium silicate clay.
The clays, especially the bentonite type clays, are preferably converted to the sodium form if they are not already in this form. This can conveniently be done by preparing an aqueous clay slurry and passing the slurry through a bed of cation exchange resin in the sodium form. Alternatively the clay can be mixed with water and a soluble sodium compound such as sodium carbonate, sodium hydroxide, etc., and shearing the mixture such as with a pugmill or extruder.
Smectite-type clays prepared synthetically by either a pneumatolytic or, preferably, a hydrothermal synthesis process can also be used to prepare these novel organic clay complexes. Representative of such clays are the following:
Montmorillonite
[(Al.sub.4-x Mg.sub.x) Si.sub.8 O.sub.20 (OH).sub.4-f F.sub.f ]x R.sup.+ where 0.55.ltoreq..times..ltoreq.1.10, f.ltoreq.4 and R is selected from the group consisting of Na, Li, NH.sub.4, and mixtures thereof;
Bentonite
[(Al.sub.4-x Mg.sub.x (Si.sub.8-y Al.sub.y)O.sub.20 (OH.sub.4-f F.sub.f ](x+y) R.sup.+ where 0<.times.<1.10, 0<y<1.10, 0.55.ltoreq.(x+y).ltoreq.1.10, f.ltoreq.4 and R is selected from the group consisting of Na, Li, NH.sub.4, and mixtures thereof;
Beidellite
[(Al.sub.4+y) (Si.sub.8-y Al.sub.y)O.sub.20 (OH).sub.4-f F.sub.f ]x R.sup.+ where 0.55.ltoreq..times..ltoreq.1.10, 0.ltoreq.y.ltoreq.0.44, f.ltoreq.4 and R is selected from the group consisting of Na, Li, NH.sub.4, and mixtures thereof;
Hectorite
[(Mg.sub.6-x Li.sub.x)Si.sub.8 O.sub.20 (OH).sub.4-f F.sub.f ]x R.sup.+ where 0.57.ltoreq..times..ltoreq.1.15, f.ltoreq.4 and R is selected from the group consisting of Na, Li, NH.sub.4, and mixtures thereof;
Saponite
[(Mg.sub.6-y Al.sub.y) (Si.sub.8-x-6 Al.sub.x+y)O.sub.20 (OH).sub.4-f F.sub.f ]x R.sup.+ where 0.58.ltoreq..times..ltoreq.1.18, 0.ltoreq.y.ltoreq.0.66, f.ltoreq.4 and R.sup.+ is selected from the group consisting of Na, Li, NH.sub.4, and mixtures thereof;
Stevensite
[(Mg.sub.6-x Al.sub.y)Si.sub.8 O.sub.20 (OH).sub.4-f F.sub.f ]2.times.R.sup.+ where 0.28.ltoreq..times..ltoreq.0.57, f=4 and R is selected from the group consisting of Na, Li, NH.sub.4, and mixtures thereof.
These clays may be synthesized hydrothermally by forming and aqueous reaction mixture in the form of a slurry containing mixed hydrous oxides or hydroxides of the desired metals with or without, as the case may be, sodium (or alternate exchangeable cation or mixture thereof) fluoride in the proportions defined by the above formulas and the preselected values of x, y and f for the particular synthetic smectite desired. The slurry is then placed in an autoclave and heated under autogenous pressure to a temperature within the range of approximately 100.degree. to 325.degree. C., preferably 275.degree. to 300.degree. C., for a sufficient period of time to form the desired product. Formulation times of 3 to 48 hours are typical at 300.degree. C., depending on the particular smectite being synthesized, and the optimum time can readily be determined by pilot trials. Representative hydrothermal processes for preparing synthetic smectites are described in the following U.S. Pat. Nos., incorporated herein by reference: Granquist U.S. Pat. No. 3,252,757; Neumann U.S. Pat. No. 3,586,478; Orelemann U.S. Pat. No. 3,666,407; Neumann U.S. Pat. No. 3,671,190; Hickson U.S. Pat. No. 3,844,978; Hickson U.S. Pat. No. 3,844,979; Granquist U.S. Pat. No. 3,852,405; Granquist U.S. Pat. No. 3,855,147.
The cation exchange capacity of the smectite-type clay can be determined by the well known ammonium acetate method.
The organic compounds useful in the practice of this invention are quaternary ammonium salts containing one methyl radical, or one benzyl radical, and a mixture of trialkyl radicals having from 14 to 20 carbon atoms, preferably, wherein 20 to 35% have 16 carbon atoms and 60 to 75% have 18 carbon atoms, 100% basis. The salt anion is preferably selected from the group consisting of chloride and bromide, and mixtures thereof, and is more preferably chloride, although other anions such as acetate, hydroxide, nitrite, etc., may be present in the quaternary ammonium salt to neutralize the quaternary ammonium cation. The methyl, or benzyl trialkyl ammonium salt may be represented by the formula: ##STR1## where R.sub.1 =CH.sub.3, or C.sub.6 H.sub.5 CH.sub.2 ; R.sub.2, R.sub.3 and R.sub.4 are alkyl groups containing 14 to 20 carbon atoms and mixtures thereof based on 100%; and where M.sup.- is preferably selected from the group consisting of Cl.sup.-, Br.sup.-, NO.sub.2.sup.-, OH.sup.-, C.sub.2 H.sub.3 O.sub.2.sup.-, and mixtures thereof.
The preferred quaternary amine for use in the practice of this invention is methyl or benzyl trihydrogenated tallow ammonium chloride. Commercially prepared hydrogenated tallow typically analyzes 2.0% C.sub.14, 0.5% C.sub.15, 29.0%, C.sub.16, 1.5% C.sub.17, 66.0%, C.sub.18 and 1.0% C.sub.20 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, as well as various animal oils and fats. The alkyl radicals may be petrochemically derived such as from alpha olefins.
Many processes are known which can be used to prepare methyl or benzyl trialkyl ammonium salts. Generally one skilled in the art would prepare a trialkyl tertiary amine, for example by the hydrogenation of nitriles, and thereafter form the quaternary amine halide by adding benzyl chloride or benzyl bromide to the amine; see Shapiro et al U.S. Pat. Nos. 2,775,617 and 3,136,819.
The organophilic clays of this invention can be prepared by admixing the clay, quaternary ammonium compound and water together, preferably at a temperature within the range from 100.degree. F. (38.degree. C.) to 180.degree. F. (77.degree. C.) for a period of time sufficient for the organic compound to coat the clay particles, followed by filtering, washing, drying and grinding. In using the organophilic clays in emulsions, the drying and grinding steps may be eliminated. When admixing the clay, quaternary ammonium compound and water together in such concentrations that a slurry is not formed, then the filtration and washing steps can be eliminated.
Preferably the clay is dispersed in water at a concentration from about 3% to 7%, the slurry optionally centrifuged to remove non-clay impurities which constitute about 10% to about 50% of the starting clay composition, the slurry agitated and heated to a temperature in the range from 104.degree. F. (60.degree. C.) to 170.degree. F. (77.degree. C.), the quaternary amine salt added in the desired milliequivalent ratio, preferably as a liquid in isopropanol or dispersed in water, and the agitation continued to effect the reaction.
The amount of the methyl or benzyl trialkyl ammonium salt added to the clay for purposes of this invention must be sufficient to impart to the organophilic clay the enhanced dispersion characteristics desired. The milliequivalent ratio is defined as the number of milliequivalents of the organic compound in the organo-clay per 100 grams of clay, 100% active clay basis. The organophilic clays of this invention must have a milliequivalent ratio from 100 to 120. At lower milliequivalent ratios the organophilic clays produced are not effective gellants even though they may be good gellants when dispersed in a conventional manner with polar organic dispersants. At higher milliequivalent ratios the organophilic clays are poor gellants. However, it will be recognized that the preferred milliequivalent ratio within the range from 100 to 120, will vary depending on the characteristics of the organic system to be gelled by the organophilic clay.

The following examples illustrate the composition of this invention and thebenefits afforded through the utilization thereof but are not to be construed as limiting the invention except as discussed herein.
The smectite-type clays used are hectorite and Wyoming bentonite. The hectorite clay was slurried in water and centrifuged to remove essentiallyall of the non-clay impurities. The Wyoming bentonite clay was slurried in water, centrifuged to remove essentially all of the non-clay impurities, and ion-exchanged to the sodium form by passing the slurry through a bed of cation exchange resin in the sodium form.
The conventionally refined oil and the solvent refined oils having the following properties were used in Example 1.
______________________________________ Conventionally Solvent Refined Refined______________________________________Gravity, .degree.API at 60.degree. F. 20 30.4Viscosity, SUS at 100.degree. F. 500 400Viscosity, SUS at 210.degree. F. 53 58Viscosity Index 12 98Index of Refraction 1.5085 1.4811Flash Point .degree.F. 390 460Pour Point, .degree.F. -5 5______________________________________
EXAMPLE 1
The organophilic clays listed in Table I were prepared by heating the clay slurry to a temperature within the range from 150.degree. F. (66.degree. C.) to 170.degree. F. (77.degree. C.), adding while stirring the clay slurry the indicated amount of the indicated quaternary ammonium chloride which had been previously melted for convenience in handling, and continuing the stirring for approximately 45 minutes, followed by filtering, washing, drying at 140.degree. F. (60.degree. C.), and grinding.
These organophilic clays were evaluated in the conventionally refined oil in the ease of dispersion test which drammatically indicates the improved ease of dispersion of these thickeners as compared to similar organophilicclay thickeners. The data in Table I indicates the ease of dispersion of organophilic clays prepared from methyl or benzyl trihydrogenated tallow ammonium chloride and the smectite-type clays when the amount of this quaternary ammonium compound was in the range of 100 to 120 milliequivalents per 100 grams of clay. The data also illustrates the dispersion characteristics of the inventive organophilic clays as comparedwith other organophilic clays prepared from somewhat similar but different quaternary ammonium compounds when used in this oil system.
The test is conducted by mixing the organophilic clay with a conventionallyrefined low VI oil at a concentration of 4.5% by weight for 0.5 minutes using a Fisher Scientific Co. DYNA-MIX.TM.0 mixer operating at 1800 rpm. The viscosity of the oil-gellant mixture is then obtained. Longer mixing times may be undertaken. Thereafter 0.12% water is added to the mixture and the mixing is continued. The viscosity of the mixture is periodically determined, generally after 6-9 minutes. A Brookfield RVT Viscometer is used to obtain the viscosity although any suitable viscometer can be used.
The following examples illustrate the ease of incorporation of the organoclays of the present invention to different paint systems to obtain an improved thickening effect. The ingredients and amounts thereof, used to prepare each composition of Examples 2 thru 12 are summarized in chart form at Tables II, IX and XI. Instructions for mixing the ingredients of the paints of Examples 2 thru 12 are provided at their respective tables.
EXAMPLE 2
Procedure for Low Shear Post Addition of Benzyl Trihydrogenated Tallow Ammonium Bentonite into a Finished Alkyd Enamel Paint (Aliphatic Solvent Type)
The benzyl trihydrogenated tallow ammonium bentonite having an M.E. ratio of 114.1 was post-added under low shear contions into a finished alkyd airdry gloss enamel paint without a polar solvent activator. For comparison, adimethyl dihydrogenated tallow ammonium bentonite having a M.E. of 95 was also post-added to the enamel at the same shear condition as the test bentonite; however, in this case a mixture of 95% methanol and 5% water was used as a polar solvent activator for the organoclay.
Specifically, 600 grams of a previously prepared alkyd enamel paint (see Table II), not containing a rheological additive, was weighed into a derimmed circular quart can which measures 4 inches in diameter and 45/8 inches in height. The paint is agitated using a 1 HP Premier dispersator equipped with a 13/4 inch diameter saw toothed Cowles blade. The blade waspositioned in the paint at the center of the quart can at a height such that the bottom of the blade is 1/2 inch above the bottom surface of the can. The shaft speed is held constant at 3,000 rpm. 5.1 grams of the benzyl trihydrogenated tallow ammonium bentonite is slowly shifted into the swirling paint. In the case of the dimethyl dihydrogenated tallow bentonite, 1.7 grams (2.1 cc) of a mixture of 95% methanol and 5% water isalso added to the paint exactly one minute after the addition of the organoclay is completed. This polar solvent activator is injected into thepaint using a 5 cc glass syringe.
The paint plus organoclay plus, in the case of the comparator organophilic clay, activator is allowed to mix at a shaft speed of 3,000 rpm for a total of 5 minutes. At this time, without stopping the dispersator, a small aliquot of paint is withdrawn from the quart can using a tapered 5 inch stainless steel spatula. This aliquot is used to measure the finenessof dispersion of the paint. This measurement is made using a Hegman fineness of grind gauge calibrated in a scale that ranges from 0 to 8 is equal to a film thickness of zero mils. The grind gauge is a stainless steel block into which a channel of varying depth has been cut out. The paint to be tested is placed into the channel at the deepest end (zero Hegman) and cast down the full length of the channel. The fineness of the grind of the paint is determined on the paint along the channel depth at which the pigment particles are first visible above the surface of the paint film. This measurement is taken after 5, 7, 9, 11, 13 and 15 minutesmixing time. The paints are then transferred to a tin can and allowed to equilibrate overnight at 25.degree. C. before being tested for viscosity and sag.
In addition, the dimethyl dihydrogenated tallow ammonium bentonite was alsoincorporated into the alkyde gloss enamel using a high shear dispersing procedure which is the normally used procedure for incorporation of these organoclay type thickeners into pigmented coatings. Again the above mentioned polar solvent activator was added to impart the full thickening action of the organoclay to the paint.
In this procedure the dimethyl dihydrogenated tallow ammonium bentonite is added to the millbase of the paint, as indicated on Table II, and dispersed at the shaft speed of 5,400 rpm for a total of 15 minutes.
Viscosity, dispersion and sag measurements for these enamel compositions are given in Table III. The ease of dispersion test is made using a Brookfield RVT model viscometer equipped with a #4 spindle at a spindle speed of 10 rpm. The sag measurements were made with a Leneta anti-sag blade calibrated from 3 to 12 mils. The sag drawdowns were cast into Leneta 7B charts with the aid of a mechanical drive film applicator equipped with a perforated vacuum plate. The completed drawdowns are placed in a vertical position with the paint stripes horizontal, the thinnest (3 mils) stripe at the top. The sag is read, after the paint filmhas dried, as the thickest paint stripe which does not sag sufficiently to cross into the next stripe of paint below it. Sag units are in mils (0.001inch).
The table shows that the benzyl trihydrogenated tallow ammonium bentonite post-added to the paint at moderately low shear imparts the same viscosityand sag to the paint and is dispersed to the same fineness as the conventionally employed dimethyl dihydrogenated tallow ammonium bentonite when incorporated into the paint at a significantly higher shear condition. In addition, the dimethyl dihydrogenated tallow ammonium bentonite when incorporated into the paint at the lower shear condition isshown to be decidedly inferior in dispersibility, viscosity build and sag resistance properties compared to the benzyl trihydrogenated tallow ammonium bentonite material incorporated into the paint at the same shear.Thus, the benzyl trihydrogenated tallow ammonium bentonite is a distinct improvement over the conventionally employed organoclay in terms of ease of dispersion, viscosity development and sag control properties.
EXAMPLE 3
Procedure for the Low Shear Post Addition of Methyl Trihydrogenated Tallow Ammonium Bentonite into a Finished Alkyd Enamel Paint (Aliphatic Solvent Type)
The procedures of Example 2 were used in this example except that the organoclay thickener used was the methyl trihydrogenated tallow ammonium bentonite having an M.E. ratio of 116 instead of the benzyl trihydrogenated tallow ammonium bentonite. All other ingredients and amounts were exactly the same as those given in Table II.
The results in the table show that the methyl trihydrogenated tallow ammonium bentonite post-added to the paint at moderately low shear impartssuperior viscosity and sag to the paint and is dispersed to almost the samelevel as the conventionally employed dimethyl dihydrogenated tallow ammonium bentonite when incorporated into the paint at a signficantly higher shear condition. Also, the dimethyl dihydrogenated tallow ammonium bentonite when incorporated into the paint at lower shear condition is shown to be decidedly inferior in dispersibility, viscosity build and sag resistance properties compared to the methyl trihydrogenated tallow ammonium bentonite material incorporated into the paint at the same shear.
The methyl trihydrogenated tallow ammonium bentonite is, therefore, a distinct improvement over the conventionally employed organoclay in terms of ease of dispersion, viscosity development and sag control properties.
EXAMPLE 4
Procedure for Low Shear Post Addition of Benzyl Trioleyl Ammonium Bentoniteinto a Finished Alkyd Enamel Paint (Aliphatic Solvent Type)
The procedures of Example 2 were used in this example except that the organoclay thickener used was the benzyl trioleyl ammonium bentonite having an M.E. ratio of 109.6 instead of benzyl trihydrogenated tallow ammonium bentonite. All other ingredients and amounts were exactly the same as those given in Table II.
The results in Table V show that the benzyl trioleyl ammonium bentonite, post-added to the paint at moderately low shear, imparts similar viscosityand sag to the paint as the conventionally employed dimethyl dihydrogenatedtallow ammonium bentonite when incorporated into the paint at a significantly higher shear condition. The dimethyl dihydrogenated tallow ammonium bentonite, when incorporated under the low shear condition, gave significantly poorer viscosity build and sag resistance compared to the benzyl trioleyl ammonium bentonite incorporated at the same shear.
EXAMPLE 5
Procedure for the Low Shear Post Addition of Methyl Trioleyl Ammonium Bentonite into a Finished Alkyd Enamel Paint (Aliphatic Solvent Type)
The procedures used in Example 2 were used in this example except that the methyl trioleyl ammonium bentonite having and ME ratio of 108.6 was used instead of the benzyl trihydrogenated tallow ammonium bentonite. All otheringredients and amounts were exactly the same as those listed in Table II.
The results in Table VI show an improvement for the methyl trioleyl ammonium bentonite in viscosity build over the dimethyl dihydrogenated tallow ammonium bentonite, when post-added to the test paint, at shear conditions that are lower than normally used to incorporate the conventional organophilic clay into the paint system. Thus the methyl trioleyl ammonium bentonite is an improvement over the conventional employed organoclay in viscosity build at the low shear condition.
EXAMPLE 6
Procedure for Low Shear Post Addition of Benzyl Tristearyl Ammonium Bentonite into a Finished Alkyd Enamel Paint (Aromatic Solvent Type)
The proceedings used in Example 2 were used in this example except that thebenzyl tristearyl ammonium bentonite having an ME ratio of 112.8 was used instead of the benzyl trihydrogenated tallow ammonium bentonite. All otheringredients and amounts were exactly the same as those listed in Table II.
The results in Table VII show that the benzyl tristearyl ammonium bentonite, post-added to the paint at moderately low shear, imparts superior viscosity, and sag resistance to the paint as compared to the conventionally employed dimethyl dihydrogenated tallow ammonium bentonite when incorporated into the paint at a much higher shear rate. In addition,the dimethyl dihydrogenated tallow ammonium bentonite, when incorporated into the paint at the low shear condition, is definitely inferior in dispersibility, viscosity build and sag resistance properties compared to the benzyl tristearyl ammonium bentonite incorporated into the paint at the same shear. These data show the benzyl tristearyl ammonium bentonite to be a distinct improvement over the conventionally employed organoclay in both viscosity build and sag resistance properties.
EXAMPLE 7
Procedure for Low Shear Post Addition of Methyl Tristearyl Ammonium Bentonite into a Finished Alkyd Enamel Paint (Aromatic Solvent Type)
The procedures used in Example 2 were used in this example except that methyl tristearyl ammonium bentonite having an ME ratio of 114.3 was used instead of the benzyl trihydrogenated tallow ammonium bentonite All other ingredients and amounts were exactly the same as those listed in Table II.
The results in Table VIII show a significant improvement for the methyl tristearyl ammonium bentonite in viscosity build over the dimethyl dihydrogenated tallow ammonium bentonite, when post-added to the test paint, at shear conditions lower than those normally used to incorporate the conventional organophilic clay into the paint system. This higher viscosity build shows that the methyl tristearyl ammonium bentonite is an improvement over the conventional organoclay at the lower shear conditions.
EXAMPLE 8
Procedures for Low Shear Post Addition of Methyl Trihydrogenated Tallow Ammonium Bentonite into a Finished Alkyd Baking Enamel (Aromatic Solvent Type)
The procedures of Example 2 were used in this example except that the alkydbaking enamel described below in Table IX was the test system instead of the alkyd air dry enamel and the comparative organoclay used was dimethyl dihydrogenated tallow ammonium hectorite instead of the dimethyl dihydrogenated tallow ammonium bentonite. In addition, the exact weights of the alkyd bake enamel, organoclays and in the case of the comparative thickener, polar solvent activator, were different from those used in Example 2. Specifically, in this example 626 grams of the test alkyd was used for the post-addition of 5.6 grams of the organophilic clays and 1.8 grams (2.3 cc) of the polar solvent activator.
The results listed on Table X indicate that the methyl trihydrogenated tallow ammonium bentonite represents a definite improvement over the conventionally employed dimethyl dihydrogenated tallow ammonium hectorite showing superior ease of dispersion, viscosity build and sag control properties when post-added to the test paint at shear conditions that are lower than normally used to commercially incorporate the comparator organophilic clay into the paint system.
EXAMPLE 9
Procedure for Low Shear Post Addition of Benzyl Trioleyl Ammonium Bentoniteinto an Alkyd Solution in Xylene
The benzyl trioleyl ammonium bentonite was post-added under low shear conditions into a short oil alkyd resin dissolved in xylene. For comparison, a dimethyl dihydrogenated tallow ammonium hectorite was also post-added to the resin solution at the same shear conditions as the test organophilic clay; however, in this case a mixture of 95% methanol and 5% water was used as a polar solvent activator for the organoclay.
Specifically, 392 grams of resin solution (see Table XI), not containing a rheological additive, was weighted into a derimmed circular quart can which measures 4 inches in diameter and 45/8 inches in height. The paint is agitated using a 1 HP Premier dispersator equipped with a 13/4 inch diameter saw toothed Cowles blade. The blade was positioned in the resin at the center of the quart can at a height such that the bottom of the blade is 1/2 inch above the bottom surface of the can. The shaft speed is held constant at 3000 rpm. 8.0 grams of the benzyl trioleyl ammonium bentonite is slowly shifted into the swirling resin. In the case of the dimethyl dihydrogenated tallow hectorite, 2.6 grams (3.2 cc) of a mixture of 95% methanol and 5% water is also added to the resin exactly on minute after the addition of the organoclay is completed. This polar solvent activator is injected into the paint using a 5 cc glass syringe.
The fineness of grind, viscosity and sag resistance of the resin organoclaymixture is measured exactly as described in Example 1 except that the viscosity is measured using spindle number 6 instead of spindle number 4 and the anti-sag blade used to measure the sag index is calibrated from 14to 60 mils instead from 3 to 12 mils.
Viscosity, dispersion and sag measurements for these resin/organoclay mixtures are given in Table XII. These results indicate the improvement inviscosity build and sag resistance that is obtained when the test resin is thickened with the stir-in additive, benzyl trioleyl ammonium bentonite, compared to that obtained when the conventional organoclay is used.
EXAMPLE 10
The procedure of Example 9 was repeated except that the stir-in experimental organophilic clay utilized was methyl trioleyl ammonium bentonite instead of benzyl trioleyl ammonium bentonite.
The data listed on Table XIII indicates that the methyl trioleyl ammonium bentonite is a definite improvement over the conventionally employed organoclay in terms of imparting viscosity build and sag control to the subject test resin solution.
EXAMPLE 11
The procedure of Example 9 was repeated except that the stir-in organophilic utilized was benzyl tristearyl ammonium bentonite instead of benzyl trioleyl ammonium bentonite.
Table XIV shows that the benzyl tristearyl ammonium bentonite represents a distinct improvement over the conventionally employed organophilic clay interms of imparting greater viscosity build and sag control to the resin test solution.
EXAMPLE 12
The procedure of Example 9 was repeated except the organophilic clay was methyl tristearyl ammonium bentonite instead of benzyl trioleyl ammonium bentonite.
Table XV indicates the superior viscosity build and sag control of the resin solution thickened with the methyl tristearyl ammonium bentonite compared to that containing the conventionally employed organoclay, dimethyl dihydrogenated tallow ammonium hectorite.
TABLES I-XV
TABLE I__________________________________________________________________________ 4.5% Organophilic ClayOrganophilic Clay 10 rpm Brookfield Viscosity, cp. ME 0% Water 0.12% WaterQuaternary Ammonium Chloride Clay Ratio 0.5 Minutes 6 Minutes 9 Minutes__________________________________________________________________________Methyl benzyl dihydrogenated tallow Hectorite 87.5 480 --(2) 1,000Methyl benzyl dihydrogenated tallow Hectorite 92.4 480 -- 2,000Methyl benzyl dihydrogenated tallow Hectorite 97.2 560 -- 9,000Methyl benzyl dihydrogenated tallow Hectorite 99.1 560 -- 11,200Methyl benzyl dihydrogenated tallow Hectorite 99.7 -- 11,200 --Methyl benzyl dihydrogenated tallow Hectorite 103.8 7,000 48,400 58,400Methyl benzyl dihydrogenated tallow Hectorite 104.3 -- 35.200 50,000Methyl benzyl dihydrogenated tallow Hectorite 106.5 6,720 48,000 --Methyl benzyl dihydrogenated tallow Hectorite 108.0 2,040 49,600 64,400Methyl benzyl dihydrogenated tallow Hectorite 110.5 1,040 33,000 46,800Methyl benzyl dihydrogenated tallow Hectorite 112.9 890 44,000 67,600Methyl benzyl dihydrogenated tallow Hectorite 115.0 3,400 33,600 34,800Methyl benzyl dihydrogenated tallow Hectorite 117.9 -- 21,000 --Methyl benzyl dihydrogenated tallow Hectorite 124.9 -- 13,000 --Methyl benzyl dihydrogenated tallow Bentonite 91.5 400 400 --Methyl benzyl dihydrogenated tallow Bentonite 96.9 -- 3,200 --Methyl benzyl dihydrogenated tallow Bentonite 102.6 2,880 36,800 44,000Methyl benzyl dihydrogenated tallow Bentonite 106.0 9,280 51,200 50,000Methyl benzyl dihydrogenated tallow Bentonite 111.0 20,000 30,400 25,000Methyl benzyl dihydrogenated tallow Bentonite 114.4 -- 15,500 --Methyl benzyl dihydrogenated tallow Bentonite 120.2 -- 14,600 --Methyl benzyl dihydrogenated tallow Bentonite 123.6 -- 6,800 --Methyl Trihydrogenated tallow Hectorite 95.8 -- 4,800 --Methyl Trihydrogenated tallow Hectorite 101.9 -- 4,400 --Methyl Trihydrogenated tallow Hectorite 108.5 640 3,320 --Methyl Trihydrogenated tallow Hectorite 118.5 -- 7,400 --Benzyl Trihydrogenated tallow Hectorite 95.5 -- 5,000 --Benzyl Trihydrogenated tallow Hectorite 101.4 -- 4,800 --Benzyl Trihydrogenated tallow Hectorite 107.9 1,480 4,000 --Benzyl Trihydrogenated tallow Hectorite 119.9 -- 5,600 --Dimethyl dihydrogenated tallow Hectorite 95.2 -- 3,400 --Dimethyl dihydrogenated tallow Hectorite 102.9 480 3,400 --Dimethyl dihydrogenated tallow Hectorite 108.8 480 12,500 --Dimethyl dihydrogenated tallow Hectorite 117.0 440 400 --Dimethyl benzyl hydrogenated tallow Hectorite 117 -- -- 560Dimethyl benzyl hydrogenated tallow Bentonite 96.6 -- 400 --Dimethyl benzyl hydrogenated tallow Bentonite 101.9 -- 200 --Dimethyl benzyl hydrogenated tallow Bentonite 111.1 -- 400 --Dimethyl benzyl hydrogenated tallow Bentonite 120.5 -- 400 --Methyl benzyl dihydrogenated tallow (1) 111.0 8,800 41,600 41,800__________________________________________________________________________(1) 1:1 weight ratio of hectorite and bentonite(2) -- indicates the data was not obtained
TABLE II__________________________________________________________________________ADD IN THE FOLLOWING ORDER WITH MIXING EXPERI- CONTROL MENTAL NORMAL LOW SHEAR BLANK PROCESSING PROCESSING (NO (HIGH (POST THICKENER) SHEAR) ADDITION)INGREDIENTS GENERIC NAME MANUFACTURER POUNDS POUNDS POUNDS__________________________________________________________________________MILLBASEAroplaz 1266M70 Long Oil Soya Alkyd Spencer Kellog 66.1 66.1 66.1 Resin Solution Div. of Textron, Inc. (70% N.V.)Mineral Spirits 663 Aliphatic Union Oil Company 66.7 66.7 66.7 Hydrocarbon of CaliforniaRheological Dimethyl di- NL Industries, Inc. -- 10 --Additive hydrogenated tallow ammonium bentoniteMethanol/Water, 95/5 -- -- -- 3.3 --TITANOX 2020 Titanium Dioxide Rutile NL Industries, Inc. 240.1 240.1 240.1Atomite Calcium Carbonate Thompson, Weinmann & Co. 191.3 191.3 191.3 Natural GroundGRIND AT HIGH SPEED - 5400 RPM FOR 15 MINUTESLET DOWN - ADD IN ORDER LISTED WITH MIXING AT 2,000 RPMAroplaz 1266 M70 Long Oil Soya Alkyd Spencer Kellogg 241.4 241.4 241.4 Resin Solution Div. of Textron, Inc. (70% N.V.)Aroflat 3113P30 Thixotropic Alkyd Spencer Kellogg 191.3 191.3 191.3Mineral Spirits 663 Aliphatic Union Oil Company 46.8 46.8 46.8 Hydrocarbon of CaliforniaPaint Drier 6% Cobalt Naphthenate Tenneco Chemical, Inc. 1.8 1.8 1.8Paint Drier 4% Calcium Naphthenate Tenneco Chemical, Inc. 8.6 8.6 8.6Exkin #2 Oxime Antiskin Agent Tenneco Chemical, Inc. 1.0 1.0 1.0MIX AT 3000 RPMStir-In Thickener Benzyl Trihydrogenated Experimental -- -- 10.0 Tallow Ammonium Bentonite TOTALS 1055.1 1068.4 1065.1__________________________________________________________________________
TABLE III__________________________________________________________________________ SHEAR VISCOSITYORGANOPHILIC CLAY CONDITION DISPERSION CPS SAG__________________________________________________________________________Benzyl trihydrogenated Cowles @ 6.0 1300 6tallow ammonium bentonite 3000 rpmDimethyl di- Cowles @ 0.0 480 3hydrogenated tallow 3000 rpmammonium bentoniteDimethyl di- Cowles @ 6.0 1280 6hydrogenated tallow 5400 rpmammonium bentonite (normal pro- cessing)Blank Paint Cowles @ 6.0 350 2(no organophilic clay) 5400 rpm__________________________________________________________________________
TABLE IV__________________________________________________________________________ SHEAR VISCOSITYORGANOPHILIC CLAY CONDITION DISPERSION CPS SAG__________________________________________________________________________Methyl trihydrogenated Cowles @ 5.0 1650 7tallow ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 480 3tallow ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 6.0 1280 6tallow ammonium bentonite 5400 rpm (normal pro- cessing)Blank Paint Cowles @ 6.0 350 2(no organophilic clay) 5400 rpm__________________________________________________________________________
TABLE V__________________________________________________________________________ SHEAR VISCOSITYORGANOPHILIC CLAY CONDITION DISPERSION CPS SAG__________________________________________________________________________Benzyl trioleyl ammonium Cowles @ 0.0 1400 5bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 480 3tallow ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 6.0 1280 6tallow ammonium bentonite 5400 rpm (normal pro- cessing)Blank Paint Cowles @ 6.0 350 2(no organophilic clay) 5400 rpm__________________________________________________________________________
TABLE VI__________________________________________________________________________ SHEAR VISCOSITYORGANOPHILIC CLAY CONDITION DISPERSION CPS SAG__________________________________________________________________________Methyl trioleyl Cowles @ 0.0 720 3ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 480 3tallow ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 6.0 1280 6tallow ammonium bentonite 5400 rpmBlank Paint Cowles @ 6.0 350 2(no organophilic clay) 5400 rpm__________________________________________________________________________
TABLE VII__________________________________________________________________________ SHEAR VISCOSITYORGANOPHILIC CLAY CONDITION DISPERSION CPS SAG__________________________________________________________________________Benzyl tristearyl Cowles @ 1.5 1800 7ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 480 3tallow ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 1280 6tallow ammonium bentonite 5400 rpmBlank Paint Cowles @ 6.0 350 2(no organophilic clay) 5400 rpm__________________________________________________________________________
TABLE VIII__________________________________________________________________________ SHEAR VISCOSITYORGANOPHILIC CLAY CONDITION DISPERSION CPS SAG__________________________________________________________________________Methyl tristearyl Cowles @ 0.0 1120 4ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 480 3tallow ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 6.0 1280 6tallow ammonium bentonite 5400 rpmBlank Paint Cowles @ 6.0 350 2(no organophilic clay) 5400 rpm__________________________________________________________________________
TABLE IX__________________________________________________________________________CHANGE TO ONE QUART PEBBLE MILL LOW SHEAR BLANK REGULAR PROCESSING (NO PROCESSING (POST THICKENER) (HIGH SHEAR) ADDITION)INGREDIENTS GENERIC NAME MANUFACTURER POUNDS POUNDS POUNDS__________________________________________________________________________MILLBASE - ADD IN THE FOLLOWING ORDERDuraplex 12-808 Short oil unmodified alkyd Reichhold Chemical, Inc. 215 215 215 (60% N.V.)Xylene -- Shell Chemical Co 146 146 146Rheological Dimethyl dihydrogenated NL Industries, Inc. -- 10 --Additive tallow ammonium hectoriteMethanol/Water, 95/5 -- -- -- 3.3 --TITANOX 2020 Rutile Titanium Dioxide NL Industries, Inc. 355 355 355PEBBLE MILL FOR 16 HOURSLET DOWN - ADD TO PEBBLE MILL IN ORDER SHOWNDuraplex 12-808 Short oil unmodified Reichhold Chemical, Inc. 198 198 198 alkyd (60% N.V.)Uformite 27-809 Melamine formaldehyde Reichhold Chemical, Inc. 177 177 177 Resin (50% N.V.)MIX FOR 1/2 HOUR IN PEBBLE MILL BEFORE CANNING OFFStir-in Thickener Methyl trihydrogenated experimental -- -- 10 tallow ammonium bentoniteMIX INTO FINISHED BLANK PAINT USING COWLES AT 3000 RPM TOTALS 736 749.3 746__________________________________________________________________________
TABLE X__________________________________________________________________________ SHEAR DISPERSION VISCOSITY SAGORGANOPHILIC CLAY CONDITION 15 MIN. CPS MILS__________________________________________________________________________Methyl trihydrogenated Cowles @ 4.0 NS 2550 16tallow ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 NS 480 5tallow ammonium hectorite 3000 rpmDimethyl dihydrogenated Cowles @ 5.5 NS 1500 9tallow ammonium hectorite 5400 rpm (normal pro- cessing)Blank Paint Cowles @ 5.5 NS 400 3(no organophilic clay) 5400 rpm (normal pro- cessing)__________________________________________________________________________
TABLE XI__________________________________________________________________________ CONVENTIONAL STIR-IN ORGANOCLAY ORGANOCLAYINGREDIENTS GENERIC NAME MANUFACTURER GRAMS__________________________________________________________________________Duraplex 12-808 Short oil Reichhold 392 392 unmodified Chemical, Inc. alkyd (60% N.V.)Rheological Dimethyl di- NL Industries 8 --Additive hydrogenated tallow ammonium hectoriteMethanol/ -- -- 2.6Water, 95/5Stir-In Benzyl tri- Experimental -- 8Thickener oleyl ammonium bentoniteMix into Resin Solution using Cowles at 3000 rpm.TOTALS 402.6 400.0__________________________________________________________________________
TABLE XII__________________________________________________________________________ SHEAR DISPERSION VISCOSITY SAGORGANOPHILIC CLAY CONDITION 15 MIN. CPS MILS__________________________________________________________________________Benzyl trioleyl ammonium Cowles @ 0.0 NS 31000 30bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 NS 9620 16tallow ammonium hectorite 3000 rpmBlank Paint -- 8.0 NS 5760 12(no organophilic clay)__________________________________________________________________________
TABLE XIII__________________________________________________________________________ SHEAR VISCOSITY SAGORGANOPHILIC CLAY CONDITION DISPERSION CPS MILS__________________________________________________________________________Methyl trioleyl ammonium Cowles @ 0.0 NS 19300 25bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 NS 9620 16tallow ammonium hectorite 3000 rpmBlank Paint -- 8.0 NS 5760 12(no organophilic clay)__________________________________________________________________________
TABLE XIV__________________________________________________________________________ SHEAR DISPERSION VISCOSITY SAGORGANOPHILIC CLAY CONDITION 15 MIN. CPS MILS__________________________________________________________________________Benzyl tristearyl ammonium Cowles @ 0.0 NS 30000 30bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 NS 9620 16tallow ammonium hectorite 3000 rpmBlank Paint Cowles @ 8.0 NS 5760 12(no organophilic clay) 3000 rpm__________________________________________________________________________
TABLE XV__________________________________________________________________________ SHEAR VISCOSITYORGANOPHILIC CLAY CONDITION DISPERSION CPS SAG__________________________________________________________________________Methyl tristearyl Cowles @ 0.0 20000 20ammonium bentonite 3000 rpmDimethyl dihydrogenated Cowles @ 0.0 9620 16tallow ammonium hectorite 3000 rpmBlank Paint Cowles @ 8.0 NS 5760 12(no organophilic clay) 3000 rpm__________________________________________________________________________
The invention being thus described, it will be obvious that the same may bevaried in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention and all such modifications are intended to be included within the scope of the following claims:

Number	Name	Date
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2531440	Jordan	Nov 1950
2548679	Olin	Apr 1951
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3136819	Shapiro et al.	Jun 1964
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4287086	Finlayson et al.	Sep 1981
4317737	Oswald et al.	Mar 1982

Number	Date	Country
1106281	Mar 1968	GBX
1592271	Jul 1981	GBX

Organophilic clay gellant having enhanced dispersibility

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