DE1567503A1 - Process for the production of an organically modified, synthetic mineral of the hectorite type - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENTANWÄLTE 8 MÜNCHEN 2, HILBLESTRASSE 2O

■ pf, 8 Munich 2, Hllblestrafle 20

Our reference 12 693

Date January 30, 1970

P 15 67 503.3-41 New documents

Lawyer file no. 12 693

Laporte Industries Limited Hanover House, 14 Hanover Square London »W.l / England

"Process for the production of an organically modified, synthetic mineral of the hectorite type"

oo The basic invention of DBP 1 184 742 relates to a process

ω for the production of a synthetic mineral of the hectorite

] ^ Type with improved theological properties with the

to mark · that · initially a magnesium ion-containing

solution and an alkaline sodium silicate solution are brought together slowly outer heating and stirring in an aqueous preparation containing fluoride ions so that in the reaction mixture atomic ratios in the ranges Si / F * 0.5 to 5.1; Li / mg -0.1 ice 1.0; Si / (Mg + Li) = 0.5 Dis 1.5; Äa / (2Mg + F-Li) -1 to 2 are present and then the reaction mixture is heated with stirring, preferably boiled under reflux conditions, ice a sample of this product after filtration, washing and drying oil 110 ⁰ O on Ge wiohtskonstanz in 5 ^ -iger dispersion ia Wa * aer a forms. This product can then gewasehen, dewatered and are heated to "in" tone temperature about 11O ⁰ Q to 450 ^e C to entwiokeln need to dare aqueous öelierungseigenschaften.

The product of the basic invention has (before and after scalding treatment) the general formula

in which M is an exchangeable cation equivalent, ζ greater than zero and less than 6 and y at least 1.0 and is less than 4. From a leaktionsgemiseh with the Atomic ratio a Sl / Y «2.7; Ll / Mg - 0.6 | 81 / (Mg-Hd) « 0.9; * a / (2Mg + f-Li) »1.0; is a synthetic * tdü

009i33 / 14Sl BAD ORIGINAL _Ä | _m

testifies, which has the above general formula, in we 1 your M J sodium, π 0.53 and y 2 iit.

The present invention öeirifft this Yerfahren eoen · »trap, and that after completion, hydrothermal, but before mentioned Hitse-Jäehaiidlung oei temperatures of about 110 ⁰ C to 4-3O ⁰ O, wherein said synthetic clay mineral product in the form of a water-based insulation or a wet cake-like mass. Thus, the product Jcuenenartig © mass oeispielsweise get oei termination of the proceedings before the washing and Entwäßserungsstufen as a slurry, while "wet during subsequent completion & 1, is applicable. If, in the latter case fessteat dewatering in a filtration" dami the product is in the ÜDliohen Filtericuckeii-Form before ·

Conveniently, the thinning of the various constituents which are used to form the slurry is such that, after d © 3? hydrothermisonen j ^ ehaadlung the product in amounts of 1 t> is 8, preferably 4 wt. -i "is present. Furthermore, the process stage of combining the components is preferably carried out over a period of 4 to 6 hours, and finally it is also preferred to extend the hydrothermal treatment to a period of 10 to 12 hours.

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1587503

Although the product oei about 110 ⁰ O to 45O ⁰ O nicnt the useful aqueous Gtelierungseigensohaften of hiteeDehandelten product possesses gate of Hitaebehandlung, both products have a very useful common property, namely the ability organic adducts su form, on "which desirable organophilic Eigensehaften to have.

Accordingly, the present invention further provides new synthetic clay-mineral adducts wherever they can new clay minerals of the general formula given above, which are modified in such a way that at least some of the exchangeable cations from one or there are several organic cations that are capable of a Baaenaustauech reaction with the synthetic Son to enter into and to give this organophilic nature.

In the meantime, at least the greater part of the exchangeable cations ought to be made up of the organic cations mentioned. .Examples of organic compounds or salts from which such cations may be derived can be found under the following classes: organic ammonium, organic phosphonium, organic Stibonium, organic arsonium, organic ozonium, organic sulphonium

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In general, as far as the present invention is concerned relates to the nitrogen-based cations, i.e. the organic Jkamonlumaalsa, of prime importance. For example, "this class of compounds" incapacitates the Salse (a generally quaternary Salse) τοη primary, secondary and tertiary amines, as well as the mono-, di-, iri- and Polyamines, as well as the aliphatic, aromatic, cyclic and heterocyclic amines and substituted ones DeriTate of this. Other mono- or polyvalent compounds, which τοη special »value for the practice in the context of the present invention are the so-called "ithemeene" (Armor ft Company). To know this affection a as tertiary amines, which are unique ACyl group and two polyoxyethylene groups associated with the StieJcstoffatom round en are, have. In a similar way The so-called "Sthoduomeens" (Armor ft Company) are also valuable.

As a precaution, the present organic best has one Chain τοη at least 10 carbon atoms, torsionally at least 12 and Torteilhafterwelsc 18.

Specific examples of suitable organic ammonium ions are; Mmetayldiootadeoylammonium, trimethyl-

Dodecylammonium,

BATH ORIGINAL 009833 / U89 ... ₆ ...

Ootadeoylammonium, dioctadeoyliorpholinium, 1-propyl-2-octadeeylimidasolinium and Ms (-2-hydroxyethyl) -OQtadecylammonium. These can be used alone or in combinations to divide an organosilicate of the desired Properties are used *

Lerner creates the Torliegcnde invention a method for Production of synthetic clays of this type modified by cations, with this process leading to the reaction synthetic ionaineral · of the general formula given herein in an aqueous or other suitable medium with an organic compound or Bucket SaIs hierrom, welenee in Asm Meilum tie Äntetemung one, as defined herein, organ! see cation "" acts, Change.

When an essentially rolling cation exchange if it is desired to pull the torso from 0.9 to 1.4 itquiTalents of the organic cation should always be used Method described method oenutst be what it is not essential if, for example, the synthetic Clay mineral exchange has hydrogen ions, which with the organic compound can react.

009833 / U89 MD ORKä ««.

The product can go through the usual process steps. Wasohening, dewatering and drying separated and then finally, if desired »be ground ·

The process described in the three previous etchings can use the heat-treated synthetic clay as the starting material. However, if »as preferred is, the reaction is carried out in an aqueous medium it is undoubtedly beneficial to hate the aqueous slurry or cake-like hate without heat treatment to use. It is also possible to carry out the tone synthesis in the presence of the organic pollution, whereby the organic adduct is formed directly.

Certain of these clays modified by cations according to the invention have oleophilic and gelling properties, which they become usable materials in the manufacture make of greases.

For example, the dimethyldioctadecylammonium adduct is oenetzt in powder form with an alcohol and then in one fat-based oil, for example a light spindle oil, dispersed. The mixture is stirred by a suitable The mill was allowed to dry and finally centrifuged to remove entrapped air bubbles. See the result

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Product has the properties of a lubricating grease.

Optionally, a slurry or filter cake of the organic adduct is dispersed in the oil and that Water removed by distillation with, for example, toluene, the excess toluene being removed at the end will. The product is, as in the previous paragraph beschrieoen oehandt.

In all cases such quantities of the organic Adducts that used in the final grease about 5 to 10 percent of the same.

In a modification, a lubricating grease can be used during the preparation of the organic adducts in situ in a medium which contains the desired oil, for example a light spindle oil, can be produced «

In addition, if the cation-modified clay using an organic material, which Has a chain of at least 18 carbon atoms and is present in an amount such as to produce at least 1.5 equivalents of the cation which was prepared Sound special characteristicsa. This is special then the pail, if up to 2.2 equivalents are used,

009833 / ■ U 8 9 -9 "

where the preferred amounts are Dei 1.7 Dia 1.8

As a result of using 1.5 or more equivalents, there are essentially all interchangeable in the product. Cations as organic cations. The remaining "cations used in the reaction (e.g. the 509 ^ or larger Üoersohufl) are held back by the clay." The anion of the organic compound is not held back.

The Röntgenstralilenbeugungeanalyee dta product showed a d ^ _Q0 distance of 53 - 32. This means "DAFL a multi-layer deposition of organic Sudstanz on the Siliciumdioxydsehioht synthetic clay structure has taken place. (Compounds which have been produced with, for example, only 30 to 40% QoersohuB of organic compound, show d _Q0 ^ Ao levels of approximately 25 Å). With exhaustive extraction with an organic solvent, the excess can be removed from the clay.

Organic product · · With this _Q0 d ^ distance and the organic Aolageruiif mentioned have the extremely brauoüDare Bif "nsehaft _f · organosol with liquid aliphatic hydrocarbons and aroaatisohtn _v particular

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with petroleum ether, benzene, toluene and xylene. she are of course organosols with a disperse phase of essentially inorganic content. When the organosol mixed with water and an aqueous solution and shaken, it forms an aqueous emulsion, in which generally the organic liquid forms the outer phase

In addition, the following examples illustrate various features of the invention.

Example A

296 g of magnesium sulfate heptahydrate was dissolved in 1 liter of water and placed in a flask with an approximate "Introduced a capacity of 5 liters, which was equipped with a stirrer, heating jacket and reflux condenser. In a separate vessel were 26.5 g of idthium carbonate and 43.28 g of sodium hydroxide was added to 200 ml of water and hydrofluoric acid with continuous stirring added until the reaction against methyl red indicator was neutral. The required amount was approximately 240 ml a 15J * w / w Hydrofluoric acid solution. That The second mixture was then added to the first and, while stirring well, was allowed to boil under ruin.

009833/1489 BADORiGiNAL .11.

A separate solution consisting of 332 g of a sodium silicate solution (29 g SiO ₂ and 8.8 g Wa ^ O per 100 g) and 1.6 liters of water was then slowly introduced into the reaction vessel. They were added over the course of about four hours, the reaction mixture being kept at the boil and stirred well.

A solution of 76.8 g of anhydrous sodium carbonate in 1.1 liters of water was then slowly poured out of about four hours was added to the reaction mixture. The mixture was then refluxed with constant Stir heated for 20 hours. It was then filtered in vacuo and the filter cake was washed with 9 liters of water.

■ Example JB

100 g of the filter cake prepared in Example A (corresponding to 20 g of dry solids) were in 500 ml of Wassor dispersed with stirring for 5 minutes. 15 »5 g one under material available from the tradename "Arquad 2Hf - 75 # E" (Simethyldloctadecylammonium chloride in 7.5 concentration in isopropanol) were dissolved in 1 liter of water and the first dispersion with vigorous stirring added. This proportion of organic compound creates cations in an amount which exactly matches the cation exchange capacity of the synthetic clay with which it

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1567Si

is to be implemented, equivalent to 1st. Me disperse Solids were flocculated during the mixing process and settled while standing, leaving a clear, supernatant liquid which was decanted. The precipitate was filtered off in vacuo and washed with water until the filtrate was essentially free of chloride. The filter cake was dried in a vacuum oven at 85 ^° C. and ground to a fine powder in a ball mill.

Example 0

20 g of the ground powder obtained in Example B. were moistened with 4 ml of methyl alcohol and dispersed in 180 g of light spindle oils (Cam · a 21 variety). The GE* The mixture was stirred for 30 minutes and passed through a colloid mill, wooel the soher fleas of the same a gap of 0.05 im was set after The grease obtained was passed through the mill centrifuged to facilitate removal of trapped air bubbles

The consistency of the Sehmier fat was measured by means of a GaI-Lenkamp miniature peaetrometer using a Kegels with a body angle of 90 ° and a total weight of 15.3 g examined. A value of 81 (1/10

Millimeter units) was obtained.

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example

A synthetic clay in powder form was produced by heating the filter cake obtained in Example k at 130 ° on drying trays and then grinding. 20 g of this powder were then treated in the manner detailed in Example B. The resulting product was an organic adduct in powder form.

example

20 g of the adducts of Example D were as in Example D described in detail. The resulting grease had a Sindring depth value of 38.

Example I.

(a) The procedure of Example k was repeated except that the treatment was completed after filtration and before washing, whereby the synthetic clay material was obtained in the form of an unusual filter cake.

(b) 100 g of the product «were» as described in detail in Example B, treated ·

009833 / U89

(ο) 2ο g dee organic adducts were, as in example 0 described and treated in detail. Bas resulting Sohmierfett had a Sindring depth value of 116.

(d) repeating step (b) using 22 g (ie, 1.4 equivalents) of the organic Ammoniumsalses (instead of 15.5 g), the resultant 'Sohmierfett as prepared in Example O was a Eindringtief e -Value of 53.

example Q

(a) The procedure of Example A was repeated, however Immediately after the treatment on the return flow, the synthetic clay product was rendered watery Slurry was obtained

(b) 500 g of this slurry were mixed with 22 g of an organic ammonium metal in the general manner of Examples B covered.

(o) 20 g of the organic adducts prepared in (b) were treated as described in detail in Example 0 The resulting Sohmierfett had a binding titre value of 112.

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Example H

(a) 100 g of the unwashed filter cube product of the Example P (a) were treated in accordance with Example B, but using 22 g (i.e. 1.4 Equivalents) of the organic ammonium salt and termination of the process after washing the organic Adducts until it was essentially chloride free.

(b) The filter cake of the washed organic adducts was dissolved in a mixture of 180 g of light spindle oil (grade Caraea 21) and 100 al of toluene with stirring for 30 minutes dispersed. The water was then removed by distillation with the toluene and finally the Excess toluene removed by distillation. The residues were passed through a colloid mill as described in detail in Example o. The final grease penetration value was 24-

Example I.

(a) The procedure of Example A was followed up to Repeated formation of unwashed filter cake, but using a starting reaction mixture Bit the atomic ratio Si /? «1.35J Li / Mg - 1.0; Si / Cüg + Id.) «0.67? I * / (2 Mg + Ϊ-Ιϋ) «1.0.

009833 / U89 ^βΑΟ "- 16 -

("b) 100g of the unwashed filter cake was prepared as in Example H (a) treated "using 22 g (i.e. 1.4 equivalents) of the organic ammonium salts »·

(o) The used filter cake of stage (b) was treated as in example H (b). The resulting grease had a penetration depth value of 75

Example J

(a) The procedure of Example A was repeated, but using 5 »3 g of idthium carbonate, 23.2 g Sodium hydroxide and 96 ml of 15% Hf solution. The synthesis was completed after the unwashed filter cake was formed.

\ (b) 100 g of the unwashed filter cake was treated as in Example H (a) using 22 g (ie 1.4 equivalents) of the organic ammonium alale.

(o) The washed filter cake from step (b) was treated as in example H (b). The resulting grease had a penetration depth of 115.

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Example K

The procedure of Example B was repeated except that 26.4 grams of Arquad 2BT was used. This amount corresponds to a 70% excess of the organic compound over the ion exchange capacity of the synthetic clay with which it was reacted. X-ray diffraction analysis of the product tended to have a d ₀₀₁ distance of 38 to 39Ϊ, which means that a multilayered deposition of organic material on the silicon dioxide surface of the synthetic (ion structure) occurred after exhaustive extraction with freshly distilled and neutralized isopropyl alcohol using a Soxhlet apparatus the resulting extract was analyzed. It was found that it contained essentially all of the 70% organic compound used in the reaction.

Example L

A sample of the organic cation-eyatli "tli © feeii-f © a-Irodukt · de · Example K was treated with lltthylalk ©! * ©! angeftmahtet and iii xylene yaws aaoh usual Jwtwfosmamlm. Hn trensparen-l · · Sol sit Vtwtm'mhQm sohafttn wurä © 9? & C4ttxu Si «

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Viscosity in centipoise of organosols with varying "Solid" content in xylene.

Organic Viscosity Consentration Cation Synthetic Clay (Cp)

1.2

3 * 2.8

8.0 24.0

The sol was stable and did not ^{collapse when heated to 100 °} C. or cooled to ^{0 ° C.}

Claims (2)

Claims 1 · Process for the production of an organically modified, synthetic mineral of the heetorite type by bringing together a solution containing magnesium ions and an alkaline sodium silicate solution in an aqueous preparation containing lithium and fluorine ions, so that atomic proportions in the reaction mixture are the ranges | r »0.5 to 5.1» ft ^s 0.1 to 1, Oj and heating the Reaktionsgemisehes under stirring as long as a sample of this product his after filtration, washing and drying at 110 ⁰ C to constant weight in 5 ^ strength dispersion in water forms a gel and optionally washing, dewatering and. Heating the reaction product to approximately 110 to 450 ⁰ O according to DBP 1 184 742 _9, characterized in that the reaction product in an aqueous medium with vigorous mixing with an organic amine capable of forming exchangeable organic cations, with at least 10, in particular 18, carbon atoms Carbon chain is implemented. New documents (Art751 Aba.2Nr.1 Satz3desXnderunfl8flefcS.Ar8.19 ·?> 009833 / U89 - 20 - 2. The method according to claim 1, characterized in that the salt is used in an amount of 0.9 to 2.2, preferably 1.7 to 1.8 molar equivalents. 3 · Process according to claim 1 or 2, characterized in that dimethyldioctadecylaamonium halide is used. Ü09833 / U89