DE1667502A1 - Synthetic clay-like mineral and process for its production - Google Patents

Description

* ^YourSign Our sign Date 1 2. $ ΘΡ. 1967

Attorney file 16 555 β

Be / Be

The Puller ^ Earth Union limited Patteson Court, Nutfield Road, Redhill, Surrey, England

"Synthetic, clay-like mineral and process for its production"

Most clay minerals, as they occur in nature, are in an impure state and require complete purification is difficult and expensive for some, and in some cases impossible. There are also cases where the Supply with a clay material of a special chemical composition, either pure or impure, unacceptable

Case F 40 / F41 / F42, / F43 / 21110 -2-

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is sufficient. It is therefore desirable that synthetic, can produce clay-like minerals in an essentially pure form.

There is a special interest in the production of synthetic, clay-like minerals with rheological properties similar to or better than those of hectorite However, since natural hectorite has valuable properties, large amounts of hectorite are not available stand. In every lall there is natural hectorite with impurities mixed, at least some of which are extremely difficult to remove.

There are only two methods of synthesizing hectorite-type clay minerals known, capable of delivering more than a few milligrams of the product under conditions which are possible on an industrial scale. One method is by Granquist and Pollack in "Clays and Clay Minerals ", Natl. Acad. Soi., Natl. Res. Council Publ. 8. 150-169, (1960) and the other by Strese and Hofmann in "Z. Anorg.Chem." 247, 65-95, 1941. It is not possible by any of these processes to obtain products that are completely pure. So contains the product of the Streseund-Hofmann process a high proportion of amorphous silica or silicate and some crystalline silica or quartz. Removal of the amorphous substance is impossible, and any product obtained by this process

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necessarily contains so high an amount of impurity that the rheological properties of aqueous Dispersions of the product are adversely affected. That according to the procedure described by Granquist and Pollack product obtained contains some magnesium hydroxide. Its removal is difficult and probable impossible to remove it altogether. It is known that the presence of even small amounts of magnesium hydroxide harms the theological properties of aqueous dispersions of clay minerals.

Many clay-like minerals contain fluoride, but do however, when they are cleaned there is always a risk of some fluoride from the mineral during certain uses can be extracted. That is, for example in pharmaceutical and cosmetic preparations, of big disadvantage. The present invention therefore has particular value because it easily facilitates the production of fluoride-free, clay-like minerals and, moreover, those swelling clays that are free of fluoride.

The synthetic swelling clays of the present invention have swelling properties that are even greater than those of our earlier invention. This is surprising in so far as it is in the procedure of our earlier Invention critical was fluoride-containing materials to use, whereby it is critical to have this over a

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agreed to use minimal amount beyond. However, it has now been found a method whereby fluoride-containing Materials are not required, the clay products have excellent properties and, accordingly, natural can be used in the cosmetic and pharmaceutical fields.

According to the present invention, a clay-like mineral is synthesized by precipitating from a solution which contains all of the cations and anions whose presence in the mineral is desired and which is maintained at a pH of at least 8, then the precipitated product without washing off soluble salts is heated under pressure. The pressure, temperature and duration of the heating must be sufficient to cause crystal formation, but not so great that the crystals become larger than desired. Preferably the pH should not exceed 12.5 and is desirably from 8.5 to 9>5> most preferably about 9 · A major difference between this process when used to make materials similar to hectorite and the known processes described above, is that in the process of the invention all of the materials present in the clay-like mineral must be present during the co-precipitation steps.

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A very large variety of synthetic, clay-like minerals can be produced using the method according to the invention. One class of natural clay minerals are the smectites, including montmorillonite, beidellite, nontronite, sauconite, saponite, and hectorite. The elementary structure of these "minerals" is based on the fact that the two end links of the series, which are not themselves clay minerals, are M pyrophyllite, Si ₈ Al ₄ O ₂₀ (OH) ₄ and talc, Si ₈ Mg ₆ O ₂₀ (OH) _4. In In the clay mineral structures, at least some of the silicon, aluminum or magnesium and hydroxyl ions are replaced by other ions As a result of the substitution of the first two types, the structure shown can acquire a negative charge which is neutralized by associated, exchangeable cations, often alkali metal cations It is therefore possible to replace silicon with aluminum, aluminum with iron (II) or magnesium, magnesium with lithium and hydroxyl with eluoride. Sometimes some of the silicon is replaced by aluminum Clay-like minerals have X-ray diffraction patterns similar to those of some after Preparations produced in accordance with the invention are similar if the solution from which the co-precipitation takes place contains essentially atoichiometric amounts of silicon, magnesium and possibly lithium and aluminum or some other

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ren in the preparation desired ion, along with sufficient Alkali metal compound, generally the carbonate or hydroxide, is introduced to the solution continuously at the desired alkaline pH. The procedure is of particular value as it is now possible to have one to produce a new class of synthetic clay-like minerals with X-ray diffraction patterns similar to those are similar to natural hectorites. However, aqueous dispersions of the new, clay-like minerals have rheological properties Properties that are better than those of the natural Tones of similar X-ray diffraction patterns.

An essential property of a usable source clay is characterized by the Bingham result value (Bingham Yield Value) exhibited by an aqueous dispersion of clay. The term "Bingham Score" (also known as Bingham Yield Stress (Bingham Yield Stress), this designation optionally to identify the same property is used) is in standard works of rheology, such as "Rheology Theory and Applications", edited by F.R. Eirich (Academic Press), Volume 1 (1956), Page 658; "Colloidal Dispersions", L.K. Fischer (N.Y. Bureau of Standards), 2nd Edition 1953, pages 150 to 170 and "The Chemistry and Physics of Clays and Other Ceramic Materials "3rd edition, page 463 by A.B. Searle and R.W. Grimshaw, desisted. The designation can be used as shear force, or voltage are explained before the

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Shear rate has a linear relationship to the shear force should be exceeded, the former is proportional to the difference between the shear force and the Bingham result value.

The Bingham result value is first determined by obtaining a flow curve in the ratio of shear force to shear rate and then extrapolating the straight line intersection of the curve to the sighting force axis. The mean is the Bingham score. It can be easily determined by any viscometer suitable for measuring a range of shear rates and shear forces. In the present description, a "Fann rotational viscometer" was used for the measurement, as described in the book "Oil Well Drilling Technology ¹¹ by AW McCray and PW Cole, union of Oklahoma Press, pages 94 to 96 (1958) When measuring with this instrument, use the results in units of dynes / cm.

The preferred, new, synthetic, clay-like minerals have the general formula:

(i2-2a-b-c) "

. M (i2-2a-bc) ⁺

where (1.) M is a sodium, a lithium, or an equivalent of an organic cation

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(2.) a, b and c have a value that either

a <6, b> O, c> 0

and b + o <2, + (a + b + c-6) <2

or a <6, b = 0, + c < 2

and + (a + c-6) <2,
(3) a cation exchange capacity of about 50

to 120 meq / 100 g and (4.) M is Na ⁺ or Li ⁺ , with a Bingham result of approximately 50 to 250 dynes / cm given as a 2-fold dispersion in tap water.

The ratios given above between a, b and c indicate in a greatly abbreviated manner that in all cases the The number of magnesium ions per cell unit of crystal is less than six and that is the total number of ions in the octahedral lattice does not differ from 6 by more than 2. When lithium is present, the total number of hydrogen ions is including those normally present as hydroxyl, greater than or equal to four and the total the octahedral ions, other than magnesium, are less than two. If lithium is absent, the total number can be the hydrogen ions change from four to no more differ as two.

The Bingham result values given above relate to on values in tap water. However, in this case, the Bingham score depends on the synthetic clay dispersions

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-M-

depends to a large extent on the concentration and type of electrolytes present in the water. The general effect is that the addition of electrolyte to a dispersion of synthetic clay made in distilled water or tap water first increases the Bingham score, then decreases it. The maximum value obtained at an optimal electrolyte concentration is M several times higher than the value that prevails for dispersions made with local tap water. This effect is explained below.

In addition to being free of fluorides, the novel materials of the invention are essentially pure, being essentially free of magnesium hydroxide, amorphous silica or silicate and other impurities. Essentially pure is to be understood as meaning that the clays are either completely free of impurities or contain only such small amounts that the rheological properties of aqueous dispersions of materials are not seriously affected, the preferred materials of the structural formula given above also having a Bingham- Results in a 2% dispersion in water of at least 40 or 50 and preferably at least 75 dyne / aw . The materials can contain a maximum of 5 to 10 wt. ';' Have impurities, but the impurities and their amounts will always be such that the radiation analysis does not show their presence.

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Therefore, impurities in excess of trace amounts become present be amorphous.

In this description, the Bingham score is the Value obtained with a dispersion consisting of dispersing 2 g of material in 100 ml of hot water and Allowing the dispersion to cool is obtained.

Bingham Yield Values of at least 40 or 50 and generally of at least 75 dyne / cm, compare with values of less than about 15 dyne / cm for products, made by the Granquist and Pollack process, even if, as shown by X-ray analysis, the magnesium hydroxide initially present in the product has apparently been completely removed and opposite Products based on the Strese and Hofmann process and compared to naturally occurring hectorite. The crystal nature determined by X-ray analysis of the new materials is similar to that of natural hectorite, and it is not possible through readily available, experimental procedure to determine exactly which the The properties of the microstructure and chemical composition of the new materials make them such high Bingham results are obtained when dispersed in water. However, it can be done by choosing appropriate proportions the components in the solution from which the clays are precipitated and therefore the proportions of the atoms in

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the materials and process conditions more synthetic Materials can easily be obtained from their Bingham result values are even greater than 75 dyne / cm. Synthetic materials with Bingham scores greater than 100 and often more than 150 and sometimes even more than 250 dyne / cm can be obtained, especially with lithium containing materials. These values refer to 2% dispersions in tap water. The values can be like indicated above. The preferred, new, clay-like minerals have a very high, specific one Surface area. Generally it is at least 100 square meters / g and often 350 square meters / g or more, although it is natural shouldn't be too high. These values are compared to a value of approximately 70 qm / g for naturally occurring Hectorite.

From the structural formula given above for the preferred new synthetic materials it is clear that in It is considered that more or less hydrogen atoms than the four required for the four hydroxyl groups can be present as opposed to the expectation that in one Fluoride-free hectorite molecule according to the conventional concept the smectite structure would be present. The occurrence of this possibility is due to the fact that many of the preferred materials have a cation exchange capacity which would be incompatible with the conventional formula, although the latter for naturally occurring hecto-

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rit or for the synthetic hectorites produced by the two known processes mentioned above is. The cation exchange capacity of the preferred, according to the invention For example, materials can be 64 milliequivalents per 100 grams and chemical analysis equivalent to

Si ₀ Mg ₁ -., "" Hx.0 _o a Wa _{n Ao} ~ , where χ by analysis is not 8 pobu ^ 4 U, 4o ^

can be easily determined. The cation exchange capacity can only be made consistent with the preparation, if one assumes that χ = 4.723, that is ο = 0.723 according to the formula calculated above. The conventional formula requires a cation exchange capacity of 2 (6-5,397) = 1,206 equivalents per cell unit or approximately 160 milliequivalents per 100 g, which is much higher than the experimentally measured value. In general the new materials have cation exchange capacities in the range of 40 or 50 to 120 meq / 100 g, typically from 60 to 90, and this is particularly desirable.

A high proportion of the magnesium, lithium and silicon ions present in the solution, from which the materials are made are precipitated together, go into the formed materials, and accordingly brings about the adjustment of the relative Ratios of the amounts of these ions changes in the empirical formula of the material formed. The retained Ratio is even higher than in the applicant's method of an earlier invention and therefore forms

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an even greater economic use of the materials.

In making the preferred fluoride-free materials with satisfactory Bingham scores and For lithium content, it is preferred that the amounts in the solution should be such that from 0.4 or 0.6 to 1.45 Li, thium atoms are present per 8 silicon atoms and preferably from 0.6 to 1.2. Bingham result values greater than 100 can be obtained in this way. Bingham result values greater than 150 can be obtained with solutions containing from 0.7 to 1.45 lithium atoms per 8 silicon atoms. In the final product, it is preferred that the number of lithium atoms per unit cell (i.e. 8 silicon atoms) is about 0.6 to 1.05.

If the solution and the material to be precipitated therefrom are free of lithium, it is also preferred that less than 6 magnesium atoms per 8 silicon atoms should be present in the solution and the product. To be satisfactory Achieving Bingham scores is the magnesium deficiency preferably at least 0.1 atoms per unit cell, but generally is no more than about 1.5 atoms per cell Cell unit. Preferably the error is greater than about 0.2 and most satisfactory results will be obtained with Magnesium deficits of around 0.5 to 1 atom per cell unit

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with the preferred missing of around 0.7 obtained. It is therefore when b = ο, a preferably equals about 5.3.

Any suitable magnesium and lithium salts can be used to introduce these cations into the solution. Examples are magnesium chloride, magnesium sulfate, magnesium nitrate and lithium chloride, sulfate and nitrate. the The reaction solution must remain alkaline throughout the co-precipitation and it must contain sufficient alkali to around the anions which become free during the co-precipitation neutralize, for example to neutralize the sulfate ions released from magnesium sulfate. It is therefore preferably more than the stoichiometric amount of alkali for Neutralization of the anions released during the reaction as well as the anion of the clay molecule present necessary. The amount is preferably between the stoichiometric Amount and about three times the stoichiometric Amount, with the preferred amount being about 1% times.

The co-precipitation is preferably carried out by mixing a hot solution containing the magnesium salt and any Lithium salt included with a cold silicon-containing solution. This cold solution generally also contains the alkali. The silicon can be introduced in the form of any suitable silicate. The addition of one solution to the other can be sohneil

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or performed slowly, but it has been found that the addition is most satisfactory over a period of around 20 minutes.

The properties of the material obtained do not seem to vary greatly with the concentration of the reactants used and, accordingly, with the concentration of the precipitate formed to change. However, for experimental reasons, it is generally preferred to use the concentrations of To select reactants so that the concentration of Precipitation is no more than about 5%. About this Difficulties in filtering and washing occur at altitude Precipitation on.

The precipitate, after it is formed, before it is heated under pressure, can be boiled to make the subsequent one To facilitate processing of the precipitate. This particularly makes washing and filtering the precipitate easier. Boiling times of about 4 hours have been found to be satisfactory found.

The pressurized heating, carried out in a pressure vessel, should preferably be at a pressure of at least 100 psi (7.03 kg / cm) (170 ° C) when lithium is present at suitable pressures of about 150 to 700 psi (10 to 49 degrees Centigrade) kg / cm ² ) (186 to 263 ⁰ C). Pressures of 700 to 1000 psi (49.2 to 70.3 kg / cm) are advantageous when, as follows,

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Gend explained, an organic derivative is to be produced below. However, if this is not the case, good results can be obtained at pressures of 200 Ms 600 psi (14.1 to 42.2 kg / cm ² ) (198 to 254 ^° C). A suitable pressure is about 400 psi (28 kg / cm) (231 ^° C.). In the absence of lithium, the mentioned low pressures are not entirely satisfactory and in general the pressure should be at least 250 psi (17.6 kg / cm) (207 ^° C). A suitable pressure range in the absence of lithium is from 500 to 1000 psi (35 »2 to 70.3 kg / cm), with a preferred value of about 700 (49 kg / cm). However, there is no critical upper limit in all cases and pressures as high as 3000 psi (210.9 kg / cm) are suitable in some cases where it is intended to reduce the time required for the process. This then enables a continuous charging and mixing process to be carried out by appropriately designed and arranged means.

The processing in the pressure vessel leads to the crystallization of the clay-like mineral and if it is continued for too long, excessive crystallization occurs and the rheological properties of the aqueous dispersions of the product are negatively affected. Holding in the pressure vessel, especially at 400 pei (28.2 kg / cm), should be carried out for at least one hour, but 8 hours are generally sufficient. A preferred duration is included

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about four hours. However, it will if, like thea later is detailed below, an organic derivative is to be produced, sometimes preferred the autoclave treatment can even be carried out for 24 hours.

The product of autoclaving is generally a suspension. The solids are usually separated by filtration or centrifugation and washing, for example with water, to remove soluble by-products such as sodium sulfate from the co-precipitate. This wet product can then either be used as such, for example for chemical reaction, or it can be dried. Drying may take place for 16 hours for example, by heating at 11O ⁰ C.

In the following examples, Examples 1 and 2 explain, according to the invention, the production of new materials according to the invention which have X-ray diffraction patterns similar to those of hectorite and are fluoride-free, but contain lithium. Example 2 further illustrates the modification of the Bingham result value with electrolyte enlargement. Example 3 illustrates that increasing the lithium content up to 1 _tonne 75 atoms per unit crystal decreases the Bingham score, and Example 4 shows that lithium contents greater than 2 do not give a significant Bingham score. Examples 5 and 6 are examples of the preparation of both lithium

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as well as fluorine-free material. Example 7 explained a method with high D ^ uek and short time.

Examples 8 and 9 show that very poor results are obtained when the co-precipitation is not in Ge ~ in the presence of all anions and cations that should be present in the final tone. Example 8 is a Strese and Hofmann method as indicated above especially as it is described on pages 73 and 78 to 80 there. Example 9 is similar to Example 8 Similar procedure, but using the amounts described in Example 2.

In all examples, the cation exchange capacity was according to the method of R.C. Mackenzie, in J. Colloid Sci., 6, 216 (1951).

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example 1

130.7 g of magnesium sulfate heptahydrate and 2.97 S lithium chloride were dissolved in 900 ml of water in a flask of approximately 5 liters capacity and heated to the boiling point. In a separate kettle, 38.6 g of sodium carbonate were dissolved in 900 ml of water and 166 g of sodium silicate solution containing 29 g of SiO ₂ and 8.8 g of NaO per 100 g were added thereto. The second solution was added to the first and it was observed that a white precipitate was formed. The mixture was brought to the boil under reflux with efficient continued stirring. After boiling for two hours, the contents of the flask were placed in a pressure kettle equipped with a stirrer, heated to 250 g and a corresponding pressure of 562 psig (4-0.3 kg / cm) in 1/2-1 hour and at that temperature Maintained for 4 hours with continuous stirring. The mixture was then ^{allowed to cool to below 100 °} C., it was removed from the pressure vessel, the solids present were filtered, washed with tap water by filtration until the filtrate showed no noticeable sulfate reaction when it was tested with barium chloride solution. The filter cake was ground in the heating furnace at 110 ⁰ O 16 hours and to a powder.

The product contained M = Na ⁺ , a = 5.29, b = 0.47, c * 0.4-9.

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When 2 g of the powder was dispersed in 100 ml of hot tap water (containing 39 ppm Ca ⁺⁺ and 4 ppm Mg ⁺⁺ ), it was found that a white transparent gel was obtained after cooling. When using an inverted viscometer (Fann VG model), the following rheological parameters were measured for this dispersion:

Plastic viscosity 13 centipoises

ρ Bingham result value 72 dyne / cm

The cation exchange capacity was 0.59 milliequivalents per gram Powder diffraction X-ray analysis showed that the structure corresponded to that of natural hectorite and that no other crystalline Material could be determined. The differential thermal analysis showed a natural hectorite similar diagram showing only endothermic peaks in the range of 600-800 ° G.

Example 2

The same procedure as in Example 1 was followed, except that the amount of certain ingredients was changed. So here were 122.0 g of magnesium sulfate hexahydrate and 4.4-5 g Lithium chloride used.

The product had M = Na ⁺ , a = 5.03, b = 0.63, c = 0.78.

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The cation exchange capacity was 0.67 raeq / g. the
X-ray analysis showed the same picture as hectorite and the distinctive thermal analysis only showed
endothermic peaks in the range of 600 - 800 ⁰ C.

The dispersion of 2 g of the product in 100 ml of hot tap water after cooling gave a mostly clear thixotropic gel with a plastic viscosity of 18 centipoise and a Bingham Yield Value of 210 dyne / cm.

The Bingham Score (BYV) for this dispersion was
again measured after adding various amounts of sodium sulphate in the form of a concentrated solution. It
the following results were obtained:

Admitted Na ^ üO ^ amount in

milliequivalents per liter of Bingham result value dispersion, this being 2% (dyne / cm)

contains synthetic clay

10 Example '6 400 20th 520 30th 550 40 565 60 520 100 400 150 180

The procedure of Example 1 is used again, however

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was the amount of magnesium sulfate heptahydrate used 105.0 g and lithium chloride 7.42 g.

The product had M = Na ⁺ , a = 4.63, b = 0.82, ο ie b + c = 2.24.

A dispersion of 2 g of product in 100 ml of hot water gave a white, cloudy thixotropic gel after cooling a plastic viscosity of $ 1 centipoise and a Bingham score of 38 dyne / cm. The cation exchange capacity was 0.65 niq / g. The X-ray analysis gave the diffraction pattern of hectorite, but the diffraction lines were not as diffuse as those of the products of the examples 1 and 2. The differential thermal analysis showed endothermic and exothermic peaks in the 600 - 800 ° C range, the exothermic peak being sharp and relatively narrow compared to the endothermic peak.

Example 4

The same procedure was used as in Example 1, but the amount of magnesium sulfate heptahydrate was 96.1 g and Lithium chloride 8.90 g.

The product had M = Na ⁺ , a = 4.42, b = 0.92, c = 1.71 ie b + c = 2.6'3.

When 2 g of the product has been dispersed in hot water,

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it was found that the I-'eststoffe immediately after Stop stirring and no thixotropic gel could be obtained.

The cation exchange capacity was 0.69 meq / g. The Höntgenstrahl analysis produced a very diffuse hectorite-like diffraction pattern with a high degree of scattering, whereby the weakly crystallized or amorphous material is shown. The differential thermal analysis showed between 600 and 800 ° C are both exothermic and endothermic peaks, the two species being of similar size.

The amounts of chemicals used in Examples 1-4, were calculated with regard to the supply of silicon, magnesium and lithium in the following atomic ratios:

example Si Mg Li Bingham Score 1 8th 5.3 0.70 72 2 8th 4.95 1.05 210 5 8th 4.25 1.75 38 4th 8th 3.90 2.10 0

At the same time, the amount of sodium carbonate became the following given formula is calculated:

W = 0.882 ρ ( 1.5r «- D

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where W is the amount in grams of NapCO-z used per 100 g of sodium silicate is required when the Si02 tration in the sodium silicate p $ (w / w) and the molar ratio from biOp to NaOH r isto

Example 5

The same procedure is followed as in Example 1, but the amount of magnesium sulfate heptahydrate was 139.5 g and es no lithium chloride was used and the amount of sodium carbonate was 42.5 6

The product had M = Na ⁺ , a = 5.09, b = 0, c = 1.38.

A dispersion of 2 g of the product in 100 ml of hot water gave, after cooling, a mostly clear, colorless thixo-

tropic gel with a plastic viscosity of 12 centίο poise and a Bingham value of 95 dyne / cm. The cation exchange capacity was 0.55 meq / g. The X-ray analysis showed the typical hectorite picture. The differential thermal analysis showed large exothermic and endothermic peaks in the range of 600 - 800 ^° C.

The products used in this example were made in terms of the addition of silicon and magnesium in atomic ratio from 8: 5.65 calculated. The sodium carbonate added was carried out in accordance with the procedure given in Example 4 above

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Formula plus 1O # excess calculated.

Example 6

125 »7 g of magnesium sulfate heptahydrate were dissolved in 6JO ml of water dissolved and heated to boiling point. In a separate pressure vessel, 38.7 g of sodium carbonate in 630 ml The water was dissolved and 166 g of sodium silicate, this type used in the other examples, were added over a period of time of 30 minutes added. The mixture became two Held under reflux for hours, then at 286 G (corresponding to heated to a pressure of 1000 psi (70 kg / cm), held at that temperature for 4 hours with stirring. the subsequent treatment was the same as in all of the previous examples.

The product consisted of h = Na ⁺ , a = 5.38, b = 0, c = 0.78. The rheological parameters of the product were

ßingham result value 152 dyne / cm

Plastic viscosity 13 centipoise

Cation exchange capacity 0.63 niq / g

After adding the same concentrated Na ₂ SO ₂ , solution to increase the electrolyte content of the solution to 45 meq / 1, the Bingham result rose to a maximum of 382

dyne / cm.

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Example 7

In this example, the same procedure was initially followed as in Example 2, except that that for preparation was of the two solutions used 630 ml of water instead of 900 ml. The oil clamp containing the precipitate was heated as quickly as possible to 336 C corresponding to 2000 psi (14-0 kg / cm) (total heating time from Boiling point 2 3/4 hours) immediately cooled down as quickly as possible by letting the pressure vessel stand in cold water. The product was then treated like the other preparations and had the following properties:

Bingham result value 40 dyne / cm Plastic viscosity 5 centipoise

The maximum Bingham result value was at optimal electrical

lyt concentration 475 dyne / cm. The cation exchange capacity was 0.70 meq / g.

Example 8

122 g of magnesium sulfate heptahydrate were in 4-50 ml of water dissolved and in another pressure vessel 166 g of sodium silicate solution of the type used in Examples 1-5 mixed with 4-50 ml of water. The second solution was added to the first and the resulting precipitate passed through filter until it was free of sulfate.

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It was then dried for 16 hours at 110 ° C., ground and then mixed with 600 ml of 2N sodium hydroxide solution. The resulting mixture was placed in a pressure vessel and ^{heated at 240 °} C. for 56 hours. After cooling, the solids were washed by filtration until the filtrate was mostly free of alkali; finally, the product was dried at 110 ° C. and ground.

When 2 grams of the product was dispersed in hot water, it was found that most of the material set immediately, while the remainder formed a white, cloudy, weak gel on cooling with a plastic viscosity of 6 centipoise and a Bingham score of 14 dyne / cm. The cation exchange capacity was 0.55 m. The contra-ray analysis gave a complex picture showing faint and diffuse lines from hectorite and much stronger and sharper lines from at least one other crystalline substance, mainly quartz. The differential thermal analysis showed only small exothermic and endothermic bpitzen between 600 ⁰ C and 800 ⁰ C.

The amount of the products used in this preparation corresponded to an Si / Mg atomic ratio of 1.6. The amount Sodium hydroxide is considerably higher than the equivalent amount of sodium carbonate given after that given in Example 4 Formula was calculated.

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Example 9

In this experiment, the same amounts and types of products as in Example 2 were used, while the Procedure was the same as in Example 8. There were therefore the magnesium sulfate and sodium silicate solutions under Formation of a precipitate mixed, which is then washed, dried and redissolved in 600 ml of solution containing sodium carbonate and lithium chloride was dispersed. After treatment in the pressure vessel, washing, drying and grinding as in example 8, the product was tested and gave results very similar to those of example 8.

Plastic viscosity at

2 # concentration 10 centipoise

Bingham score at ₂

2 # concentration 14-dyne / cm

Cation exchange capacity 0.69 meq / g

X-ray analysis of weak hectorite,

strong quartz like) diffraction pattern

DTA! ^ Example 8

All of the synthetic clay-like minerals specified above have an inorganic cation M, however, useful derivatives in which the cation is organic can be made. It can therefore the inorganic materials into new synthetic clay mineral organophiles Products are converted into which

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at least some of the exchangeable cations from one or several organic cations that provide these products with an organophilic structure. These new organophilic products can be implemented by one of new synthetic clay minerals either before washing or after washing or after drying in a liquid, preferably aqueous, medium with an organic compound or a salt thereof which creates an organic cation in the medium which is used to bring about a cation exchange reaction is capable of using the synthetic clay. Preferably at least a major part of the interchangeable Cations in the organophilic product are the designated organic cations.

Examples of organic compounds or salts thereof from which such cations may originate can be found in the the following classes: organic ammonium, organic phosphonium, organic stibonium, organic Arsonium, organic oxonium, organic sulphonium.

In general, the cations are essential as far as they relate to the present invention, based on nitrogen, i.e. the organic ammonium salts, By way of example, this class of inventions includes salts (including quaternary salts) of primary,

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secondary and tertiary amines, including mono-, di-, tri- and polyamines, as well as aliphatic, aromatic, cyclic and heterocyclic amines and substituted derivatives thereof. Other mono- or polyvalent compounds, which are of particular value in the practice of the present invention are the so-called "Ethomeens" (Armor & Company Ethomeen is the trade name). These compounds are to be regarded as tertiary amines, the have a single alkyl group and two polyoxyethylene groups linked to the nitrogen atom. In a similar way The so-called "Ethoduomeens" (Armor & Company) worth it too.

Preferably the organic residue present has at least 10 _; desirably at least 12 and advantageously at least 18 carbon atoms. The compounds can have up to 30, 40, or even 50 and more carbon atoms, depending on the availability of such materials.

Specific examples of suitable organic ammonium cations are dimethyldioctadecylammonium, trimethyloctadecylammonium, Dodecylammonium, hexadecylammonium, octadecylammonium, dioctadecylmorpholinium, l-propyl ^ -octadecylimidazolinium and Bis (-2-hydroxyethyl) octadecylammonium. These can be used individually or together to produce an organosilicate with the desired properties can be used.

109825/1571.

When a substantially complete cation exchange if desired, it is preferred from 0.9 to 1.4 equivalents to use organic cation, although it has been found to be very beneficial in some cases, 1.7 to 1.8, even up to 2.2 equivalents to be used. However, if the sound is heard at higher pressures, for example at 700 to 1000 psi (49-70 kg / cm) was synthesized, the ranges given above are respectively 0.6 to 1.4 and 1.0 to 2.2 equivalents.

The product can go through the usual stages of dewatering and drying and finally, if desired, milled. Usually the product is washed in the same way.

The processes described can be dried as starting material use synthetic clay. However, if preferred, the reaction is in an aqueous medium To carry out, it is obviously beneficial to make an aqueous slurry or cake-like mass without heat treatment to use.

Certain cation-modified clays according to the invention have oleophilic and gel-forming properties, which they for example very useful for the production of lubricating greases

- 32 -

109825 / 1S71

make cash. Others have the ability to form organosols.

The following examples 10 to 14 show examples of the preparation of organic derivatives of the new invention Materials.

Example 10
11.25 gal (51 liters) of water were added to a pressure vessel for

Boiling point heated and 21.8 lb (9.89 kg) magnesium sulfate heptahydrate and 0.8 lb (0.363 kg) lithium chloride dissolved in the water. A separate solution was prepared comprising 11.25 gallons (51 liters) of water with 29.6 lb (13.5 kg) sodium silicate, of the type used in all of the other examples, and 10.4 lb (4.72 kg) anhydrous sodium carbonate contained. The second solution was gradually added to the first solution in the pressure vessel over a period of one hour. The mixture was then heated at atmospheric pressure with continuous stirring for two hours, then the pressure kettle was sealed and heated to 207 ° C (250 psi pressure) (17.6 kg / cm ² ) in 41/2 hours same 'temperature and pressure were maintained for 8 hours, then adjusted the heating and allow the mixture to cool to below 100 ⁰ C. It was then the autoclave

taken.

- 33 -1 09825/1671

1000 g of the unwashed sludge from the pressure vessel, which contained 60 g of synthetic clay, was mixed with 2 liters of hot water. A solution of 50.8 g (1.1 equivalents) _r this under the trade designation on the market brought material Arquad 2HT - 75 $ T, (this material is dimethyl dioctadecyl ammonium chloride in 75 $ strength by weight concentration in isopropanol) in 1.5 1 hot water was added thereto with vigorous stirring. The mixture was heated to the boiling point when the dispersed solids were observed to flocculate and settle on standing. The precipitate was filtered under vacuum, washed with hot water until the filtrate was essentially chloride-free and un ^. dried at 80 ° C for 2 hours. A soft, powdery product was obtained which could easily be ground into a fine powder suitable for use in making a fat.

Example 11

The same procedure is used as in Example 10, with the difference that the procedure is carried out in the pressure vessel Continued for 24 hours. The resulting soft, powdery product was even more suitable for making a fat.

- 34 -

109825/1571

Example 12

The same procedure was used as in Example 10 except that the slurry was washed from the pressure vessel by filtration until the filtrate was essentially free of sulfate. The filter cake was ^{dried at 120 °} C. for 8 hours and the finely ground 60 g of dried solids were dispersed in 3 l of hot water by mixing in for 15 minutes and mixed with a solution of 50.8 g of Arguad 2HT, after which that described in Example 10 was carried out Manufacturing continued.

Again a soft, powdery product was obtained which can easily be ground to a fine powder suitable for use in the manufacture of a fat.

Example 13

The same procedure is used as in Example 10 with except that 74 g (1.7 equivalents) of Arguad 2HT was used. In this case it was the resulting product suitable for the production of an organosol.

Example 14

The product obtained in Example 6 became an organophilic Form converted by dispersing 15 g dry

- 35 -109825/1571

nem clay in 150 ml of hot water, while adding a solution of 11.6 g of Arguad 2HT in 375 ml of hot water and by continuing the preparation as described in Example 10.

The product was dispersed in a low viscosity lubricating oil and it was found that at 8-10% Concentration of stiff greases were obtained, which are similar in consistency to conventional lubricating greases.

In general, fats can be mixed with the organic ammonium clay derivatives in a suitable, finely divided form a wetting agent and a fatty base oil. Mixing is preferably used as a milling process carried out and advantageously in two stages, the first with part of the desired amount of fatty base oil, the second is done with the rest. Lastly, the fat can be used for easier removal of trapped air bubbles centrifuged.

The fats generally comprise a major amount of fatty base oil and a minor amount, suitably 2-29 Weight percent (more suitably 5 - 13 ^ and preferably 10 $) organic clay derivative.

The following examples 15 and 16 explain the manufacture

- 56 -

109825/1571

position of certain organic clay derivatives and the use of such materials in the. Manufacture of fats.

Example 15

174 g of light spindle oil (Carnea 21 grade) were mixed with 4 g of methyl alcohol and 29 g of powder, as previously prepared according to Example 10, were added to this. The mixture was stirred with a high-performance mixer for 3 minutes, then allowed to run through a colloid mill, the cutting surfaces of this mill being set at a distance of 0.05 πιπί. After passing through the mill, 150 g of the resulting fat having a solids content of $ 14 was mixed with 60 g of the same type of light spindle oil as previously used to reduce the solids content to $ 10, and the mixture was then passed through the colloid mill again to run. The resulting fat was then centrifuged to facilitate removal of trapped air bubbles. The consistency of the fat was checked by a Gellenkamp miniature penetrometer using a cone with a fixed angle of 90 ° and a total weight of 15 »3 g. A value of 30 (one tenth of a millimeter unit) was obtained.

Example 16
For the production of organosols according to the invention, the orga-

109825/1571

African ammonium compound which is used for reaction with the synthetic swelling clay, preferably a chain of at least 18 ⁰ O atoms and is (preferably not more than 2.2) in an amount of at least 1.5 equivalents, and suitably between 1.7 and 1.8 used. However, if the synthetic clay was made at higher pressures, namely 700 to 1000 psi (49-70 kg / cm ² ), the amount of ammonium compound used can be as little as 1.0 equivalent.

As a result, the product has essentially all of its exchangeable cations as organic cations. The core of the cations contained in the reaction (ie ^> Q% or more) are retained by the clay. The anion from the organic compound is not retained.

It seems that the multilayered deposition of the organic Material takes place on the bilicium layer of the synthetic clay structure.

Such organic products are used to form organosols with liquid aliphatic and aromatic hydrocarbons, especially petroleum ether, white spirit, benzene, l'oluene and xylene are suitable. They are organosols with a Dispersion phase of essentially inorganic content.

- 38 -

109825/1871

When the organosol is mixed with water or an aqueous solution and shaken, it forms an aqueous one Emulsion in which the organic liquid generally forms the outer phase.

As an example, an organic clay derivative was used according to Example 10 above, but using 7 ^ S (1> 7 Equivalents) amine produced.

The product was moistened with methyl alcohol and dispersed in toluene at a concentration of 8. A clear, low viscosity sol was formed. The sol was ^{stable between 0} ° C and 100 ° C. When part of this sol was mixed with half its volume of water and shaken for one minute, a stiff emulsion was obtained, the outer phase of which was toluene.

Natural hectorite does not form brine or water-organic solvent emulsions.

The inorganic swelling clays of the invention, i.e., those wherein M is Na or Li, can be used as such however, the handling of introduction into various media can be accomplished using a peptizer be relieved.

- 59 -

109825/1571

Thus, according to a further embodiment of this invention, the inorganic ΐοηβ of the general formula, when M is Na or Li, in a preparation with up to 25> 6 (based on the weight of the material) of one or more peptizers selected from alkali metal salts with polyvalent anions. The cation M of the material is preferably Na ⁺ or Li ⁺ . Optionally, organic materials can be used as peptizers, for example quebracho or lignosulfonate.

Preferably the amount of peptizer present is from $ 3 to Λ2% (based on the weight of the clay), suitably from 5 to 10% and most preferably from $ 5 to & p. These amounts are particularly useful when the peptizer is tetrasodium pyrophosphate.

Other peptizers that can be used are "Calgon" (trade name) and sodium tripolyphosphate too to name. In general, the most suitable peptizers are sodium salts with polyvalent anions, the anions are capable of forming either complex or insoluble salts with magnesium.

These preparations can be suitably prepared by dry mixing the synthetic, clay-like '■

- 40 -

109825/1571

Mineral and peptizer. The particle size of the resulting mixture is not critical, but primary depending on the use for which the mixture is intended.

In some cases it may be desirable that the preparations contain small amounts of one or more additives the nature of these additives being determined by the use for which the end connection is intended.

Certain formulations, for example those in which the cation M is Na ⁺ or Li ⁺ , have the unexpected property of having the ability to form substantially transparent golloid dispersions in the form of oils when mixed with water. Aqueous idols, whether made from these preparations themselves or directly from ingredients thereof, constitute a further subject of the present invention and can have a total solids content (synthetic material + peptizer) of up to about 10 $, although normally from 2 to &} ί > a suitable solid content is present. ! Such brines cannot be obtained from naturally occurring, swellable clays. In practice, the sols provide an easy method of introducing the synthetic swellable clay into the medium in which the clay is desired.

- 41 -

109825/1571

Although dilute, aqueous dispersions of the type just described, no thixotropic or noticeable Bingham result value can have these two properties developed by mixing them with specific compounds will. Such a property makes the preparation and / or oils of this invention particularly useful in emulsion paint media, such as a polyvinyl acetate paint medium, suitable.

It has actually been found in this regard that the preparations are very effective gelling agents, such as so are the lithium-containing clays when used without a peptizer.

Another application of the synthetic clays and mixtures thereof with a peptizer is in binding of foundry sand types.

Examples of sodium forming clays alone and with 6 ^l / a tetrasodium pyrophosphate were taken. 5 parts of each sample were mixed with 100 parts of quartz sand and 3.5 parts of water and milled for 5 minutes.

i / in commercially available quality of a natural, swelling Tones was edited in the same way.

- 42 -

109825/1571

The two synthetic clay-containing sand mixes were found to have freshly made (green) strengths that were $ 50 better than the natural clay sand mix. The properties as refractory material (measured according to their melting temperatures in electric fireclay furnaces) were essentially the same for all samples at approximately 1300 ^° C.

Another very important object of the invention is the further application of the mixtures of inorganic, swellable clay and the peptizer just described. With such mixtures or the separate ones Components can be obtained very useful mortar or filler preparations.

According to this embodiment of the invention comprises a mortar preparation in the mixture

(a) cement

(b) "Fly ash and / or other filler

(c) Up to a total weight of $ 5 (of the total weight of (a) + (b)) one or more synthetic, inorganic clay materials such as those in British Patent No. 1 05 ^ 473 and / or in the simultaneously pending Application 40683/66 are described, and

(d) up to a total weight of $ 5 (based on the

109825/1571

weight of (c)) one or more peptizers selected from alkali metal salts with polyvalent anions.

A suitable ratio of cement to filler is in the range 1: 4 to 1: 1, desirably in the range 1: 3 to 1: 2 and preferably about 1: 2.5

Desirably, the synthetic clay material is in the mixture at up to about 1 percent by weight of the total weight from (a) + (b), suitably from 0.1 to 0.5

Weight percent available.

The total amount of peptizer used is suitably in the range of 1-4% by weight of (c); about $ 2 is a beneficial amount.

öolche preparations are useful / asserbarrie- in tunneling through soft ground, for sealing embankments, for closing oteinsprüngen and wells and for production of partition walls and other continuous V

The significant properties of the filler (building material) preparations, Especially those when used in tunnel construction are (1) light freshening with water or another

- 44 -

109825/1571

suitable liquid medium to form a pumpable slurry, (2) initial settling in about an hour (3) plastic condition up to 12 to 16 hours. (4) Final grades in 12 to 24 hours. (5) Final strength from 200 to 800 lb / sq. inch (14.1 to 56.2 kg / cm). (6) Minor or no shrinkage during settling. (7) Little or no water excretion during settling. (8) No separation of pesticides in the cast cement and (9) fine pore structure.

In general, similar requirements apply when, instead of using it as a mortar, the formulation to form a pre-cast tunnel lining segment is used. In this case, however, the final settling time (for the ability to remove from the mold) must be shorter and the final strength will be higher.

The building materials used in tunnel construction are essentially aqueous mixtures of cement, filler and swelling clay. However, in all known cases, the swelling clay must be pregelatinized before it can be used, and this means a separate step in the production of aqueous mortar or building material. In the ideal case, a dry mixture of all components is desired, for which only water is necessary in order to form the aqueous structure.

-45-

109825/1571

add substance.

It is therefore a very important object of the present invention that such a Trodken mixture now is possible.

A particularly favorable mortar, building or filler preparation according to the invention contains (in parts by weight) 70 parts of fly ash, 30 parts of cement, 0.12 parts of synthetic clay material and 2% TSPP based on the weight of the synthetic clay.

Fly ash is pulverized fuel ash from a power plant (ß.ü.b. 3892; 1965).

To produce an aqueous mortar or building material from the dry mixture, approximately 35 to 55 parts by weight / liter may be required. In the case of the special preparation specified in the previous paragraph, 40 up to 4-5 parts are suitable, depending on the fineness of the filler, especially if it is fly ash.

The following example explains this embodiment the invention.

Example 17 The table below makes the nine above

109825/1571

given properties are shown.

Various designations have been used in the results given below, and these designations
have the following meanings:

consistency

A The freshly mixed Möi'te ^ or. Building material is thick with stirrable with a glass rod, but not pourable.

B Can be poured straight out of the cup as a continuous mass.

C Thin paste.

dehydration

The forms were placed on absorbent paper
and a liquid discharged during the initial settling period was seen as a water stain around the base.

A - None

B - tracks

C - something

D - a lot

Removability from the form

After 1 hour an attempt was made to take the sample off

109826/1571 "

to remove the shape. Yes means that the sample does not seem to deform or suddenly falls off. Just that it is slightly deformed, but could only be made safe by leaning against a carrier. Further explanations are clear.

Penetration or softening depth

This was measured on the surface of the sample after one hour, leaving a plastic cone weighing

15 »4- g and with a 45 ° angle

was used. The strength obtained was as follows

calculated:

1750
S = 2 lb / sq inch

where ρ is the penetration depth in 1/10 mm units, as read, was.

Loss of shape

The deformation during the sitting period was determined as follows:

A = no noticeable change

B = very little deformation

G = fairly noticeable deformation

D = considerable deformation

Ε = no shape (cannot be removed after 1 hour).

- 48 -

109825/1571

texture

The samples were cut off at both ends to

Position of "3" (76 mm) large cylinders for strength measurements with a triaxial strength tester. to At the same time, the fineness of the pore structure was tested.

A = very good, uniformly fine pores

B = good

C = pretty

D = (some very large pores)

E = no sample (cannot be removed after 1 hour)

In the tests given in the table, the Dry mortar or building material preparations first formed and then gradually became water with constant stirring added until the desired consistency was obtained. The resulting aqueous building materials were converted into fillitrian Sample molds 1 1/2 "(38 mm) in diameter were filled, which were separated by thin rubber partitions.

The tables below show the "Effect of the addition of synthetic clay with or without TSPP on the properties of Portland cement / fly ash with different initial consistencies.

Table I contains information on the behavior of a particular type of synthetic clay (Type 2). The table Il

1 0 9 8 2 G / 1 5 7 1 - 49 -

_ 4-9 -

shows the effect of using different types of synthetic clay (Type I) and two with trademarks protected natural hectorite, which comes under the trade names "BEN-A-GEL" and "BEN-A-GKL EW" to be brought to the Harkt.

The free bar in the tables shows that no measurements m were made.

-50- 109825/1571

Synth. TSPP fo water Consi Tone ia re. re. stence Cement: Dry on on (5) Fly ash Weight synth. Dry (2) volume Weight (D (3) (4)

Table I.

Penetration resistance

Plus distance after 1 hour loss
igk.- ability lb / sq..in on
Loss after 1 hour (kg / cm) shape

(7)

/ c
8th)

(9)

Shear strength

lb / s q .. 3, n.

(kg / cm ")

Texture change

Structure 1 day 7 days such (10) (11) (12)

O CO OO

50: 50 0.12 2 45 C. C. no 2.4 (0.17) E. E. 525 1725 l / y 40: 60 0.12 2 45 C. B. just 0.6 (0.04) B. B. (36.9) (120.8) O 210
(14.8) (9β] β) ^cement: ι 30: 70 0.12 2 45 C. A. just 1.0 (0.07) B. A. 0 1130 fly ash 25: 75 0.12 2 45 C. B. just 1.0 (0.07) B. A. (79.1) 0 546 20! 80 0.12 2 45 C. C. just 0.9 (0.06) B. A. (38.2) 1870 clay content 0 0 ^ m ^ consistency 10 y 90 0.12 2 45 G T) just 0.6 (0.04) D. (95.7) 30th . 70 0 0 40 A. A. no 0.9 (0.06) E. E. 923 30 « : 70 0 0 42.5 B. A. no 0.5 (0.03) E. E. (64.8) _, 30 - : 70 0 0 45 C. A. no 0.2 (0.01) E. E. 420 1700 _m 30th t 70 0.04 0 35 A. A. just 2.8 (0.20) B. C. (29.5) (119.2) S. 30th : 70 0.04 0 40 B. A. no 0.6 (0.04) E. E. 30th : 70 0.04 0 45 C. B. no E. E. 420 30th : 70 0.12 0 35 A. A. just 6.0 (0.42) G C. (29.5)
105 30th : 70 0.12 0 40 B. A. just 0.6 (0.04) C. A. (7.3) 63 30th : 70 0.12 0 49 C. B. just B. A. (4.4) 378 30th : 70 0.20 0 37.5 A. C. just 1.6 (0.11) D. B. (26.5) 30th : 70 0.20 0 40 B. C. not quite 1.9 (0.13) E. E. 30th : 70 0.20 0 45 C. C. not quite E. E.

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109825/1571

The conclusions to be drawn from the preceding table are:

The addition of synthetic clays improves the behavior when the mortar or building material settles in in the sense that mixtures that are initially thin and pumpable settle sufficiently quickly in an hour to be able to remove them from the mold, but remain plastic for nearly a day. Such mixtures do not set in an hour without synthetic clay. The optimal level is approximately $ 0.12 on a dry basis weight.

With the addition of $ 0.12 synthetic clay, mixes with varying cement / fly ash ratios, down to about 25 to 30 $ cement content, generally give satisfactory results. Yienri uses a smaller proportion of cement, the building material sets very well in an hour, but is too weak after 24 hours.

Naturally occurring hectorite (Ben-a-Gel and Ben-a-Gel-EW) in 30:70 cement / fly ash mixes cause some improvement with regard to the behavior when sitting down, but are not sufficient to form a mixture that in an hour. The optimal addition is about $ 0.12 for synthetic clay, however the addition of Phosphate no other benefit. Other advantages of synthetic clay preparations are (a) less liquid loss and (b) lack of deformation after removal

-53- 109825/1571

- 55 out of shape during the first day.

Clay 2 is a synthetic clay produced according to Example 2.

-54- 109825 / 1S71

Claims (1)

(i2-2a- <b ~ e) "* has »where (1) M is a sodium, a lithium or an equivalent of an organic cation» (2) the value of a, b and c is such that either a <6, b> 0 »c> Ö and b + c <2, + (a + b + c-6) <2 »or a <6, b = Ö, + Ö <2 _t and + (a + c-6) <2 (5) there is a Kationemustauaelikapazität of about 50 to 120 ma <i- / iÖÖ g and (4) when M is Ka ⁺ or Ii ⁺ is a "Binghaa Yield Value" (lingham result value) of from about 50 to 250 dynes / om is achieved with a 2 $ dispersion in tap water. 2. Synthetic son according to claim 1, characterized in »that b is from about 0.6 to 1 _f 05 · 3 * Synthetic clay according to claim t, characterized in that b Hull and a from 4 » 5 to 5.9», preferably 5 * 0 to 5 _{f is} 8. 4. Synthetic »clay-like mineral according to claim 1 108825/1571 characterized in that M Ka ⁺ and (1) a is 5.29, b is 0.47 and c is 0.49 or (2) a is 5.03, b is 0.63 and c is 0.78 or (3) a is 5.09, b is zero and c is 1.38 or (4) a is 5.38, b is zero, and c is 0.78. 5. Synthetic clay according to claim 1, characterized in that M is a sodium or lithium cation in admixture with up to a total of 25 wt. ^, based on the synthetic Clay, one or more peptizers selected from alkali metal salts with polyvalent anions be is. 6. Synthetic clay according to claim 5, characterized in that a mixture with up to a total of 5 $ the "designated peptizing agent. 7. Synthetic clay according to claim 6, characterized in that in a further mixture with (a) cement and (b) Fly ash and / or another filler of the synthetic clay in up to a total of $ 5, preferably $ 0.1 up to 1.0 wt. # of the total amount of (a) plus (b) is present 8. Synthetic clay according to claim 1, characterized in that M is an organic ammonium cation with at least 10 carbon atoms. ■ ./· -56- 109825/1571 9. Synthetic clay according to claim 8, characterized in that that the cation has at least 18 carbon atoms, for example dimethyldioctadecylammonium. 10. A method for the synthesis of a mineral-like clay, characterized in that it comprises the precipitating together from a solution containing the desired cations and anions to be present in the clay, holding at a pH of at least 8 throughout the process and, without washing free of soluble salts, heating of the co-precipitated product under pressure to grow crystal. 11. The method according to claim 10, characterized in that the pH is kept between 8.0 and 12.5. 12. A method for the synthesis of a mineral-like clay according to claim 1, wherein M is sodium, characterized by the steps (1) the co-precipitation from an aqueous, alkaline (sodium compound) solution at a pH of 8 to 12.5 and contains a water-soluble magnesium salt, a lithium salt if b> 0 and a silicon releasing material, for example a silicate, is each in a calculated amount to form the desired one Si, Mg, Li ratio (2) Heat this precipitate without washing free soluble salts under pressure of at least 100 psi -57-109825 / 1571 (7.05 kg / cm), preferably 700 to 1000 psi (49.2 to 70.3 kg / cm) for a period of time which is suitably lasts from 1 to 8 hours to produce a Kristallwuehs, (3) Separating the resulting residue and the aqueous phases, (4) washing to remove the soluble by-products, (5) drying the washed product. 13 · The method according to claim 12, characterized in that the co-precipitation by mixing a hot solution causes the (1.) the magnesium salt and (2.) the lithium salt, if used, with a cold solution containing (1.) the silicon-releasing material, (2.) the desired sodium compound to maintain the alkaline pH contains. 14. The method according to claim 12 or 13, characterized in that the concentrations of the reactants are selected ao v / ground that the concentration of the resulting precipitate does not exceed essentially 5% by weight. 15. The method according to any one of claims 12 to 14 daduroh characterized in that the precipitate formed in step (1) is boiled prior to heating under pressure in step (2). 16. The method according to any one of claims 12 to 15 daduroh 109825/1571 / characterized in that after stage (4) or stage (5) the Product is reacted with a lithium compound, whereby the exchangeable sodium cation M is replaced by lithium 17. The method according to any one of claims 12 to 15, characterized in that after step (4) or step (5) the Product is reacted with an organic amine salt, whereby the exchangeable sodium cation M is replaced by a. equivalent to of the organic ammonium cation is replaced. 18. The method according to claim 17 characterized in
that the organic ammonium cation has at least 10, preferably at least 18 carbon atoms. 19 · The method according to claim 17, characterized in that
that the organic cation is dimethyldioctadeey ammonium. 109825/1571