NL8600740A - Flocculated mineral materials and water-resistant products made therefrom. - Google Patents

Description

NL 33283-Kp / dJ / vD - 1 - *. _ '

Flocculated mineral materials and water-resistant products made therefrom.

The present invention relates to a process for the preparation of a flocculated mineral material which can be used to form an asbestos-free high temperature product, which is water-resistant, as well as to such flocculated mineral materials, water-resistant products manufactured therefrom and to a process for the manufacture of the latter products.

It is known that asbestos-free sheets and / or sheets can be made of water-swellable inorganic materials and, in particular, swollen silicate gels. U.S. Pat. 4,239,519 relates, for example, to the manufacture of synthetically obtained inorganic, crystal-containing gellable, water-swellable silicate sheets and certain products made therefrom, such as sheets, fibers, films, plates and coatings. These asbestos-free blades and / or sheets have good high temperature stability and good chemical resistance. Moreover, such products do not pose health hazards inherent in asbestos-containing products, since no asbestos fibers are used in their manufacture.

The U.S. Patent No. 4,239,519 describes the method of making gellable precursor silicates used for the manufacture of said sheet or sheet products / which method comprises three essential steps; (a) a full or predominantly crystalline mass is formed containing crystals consisting essentially of a water-swellable lithium and / or sodium mica selected from the group of fluorhectorite, hydroxylhectorite, boron fluorophlogopite, fluorophlogopite, hydrophobopite droxyl boron phlogopite and solid solutions between these and other structurally compatible species selected from the group of talc, fluorine talc, polylithionite, fluoropolylithionite, phlogopite and fluorophlogopite; (b) this mass is brought into contact with a polar liquid, usually water, to effect the swelling and disintegration of the mass, which is - - - · 7 '; «-J -s' ·. . : *. & - 2 - does not involve the formation of a gel; and (c) the solid: liquid ratio of the gel is adjusted to the desired value depending on its application. Glass ceramic materials are preferred as crystalline starting materials. Those products are then contacted with a source of large cations, that is, with an ion beam greater than that of the lithium cation, to cause macro-flocculation of the gel and ion exchange reaction between the large 10 cations and the Li + and / or Na + ions from the interlayer of the crystals.

Alternatively, the US describe U.S. Pat. Nos. 3,325,340 and 3,454,917 to prepare aqueous dispersions of vermiculite chip crystals that have been swelled by incorporating interstitial ions such as

Ss will contain * in all carbon groups 3-6 carbon atoms, such as methyl butylammonium, n-butylammonium, propylammonium and iso-amylammonium, (2) the cationic form of amino acids, such as lysine and ornithine, and / or (3) li -20 thium.

While the products, such as sheets, sheets and films, which have been produced by the above-described prior art methods, have excellent heat resistance and are very useful in a wide variety of applications, it has been found that such products generally do not exhibit good sealing properties, limiting their use as packing materials. The known products also have a certain degree of water sensitivity, which is generally exhibited by the products which, exposed to environments of high humidity or immersed in water or other polar liquids, have a significant loss of strength and a general deterioration of mechanical and electrical have properties. Accordingly, this sensitivity to water limits the utility of these products in certain applications, such as, for example, head gaskets, electrical insulators, environmental protection coatings, and washable and environmentally stable building materials.

A related application US SN 662,057, filed October 18, 1984, teaches that fireproof, asbestos-free pro-, ¾ a * λ -T ’a n ** / s f &

ν.ίί ’A / \ 3 J

3 * products can be made from a puffy, layered flocked silicate gel material prepared using an exchange cation selected from guanidine derivatives. Surprisingly, such products have been found to have better water resistance than the products made by the known methods, as well as excellent electrical properties.

It has now unexpectedly been found that high temperature, fireproof, asbestos-free, water-resistant products, such as sheet, sheet, plate, film, fiber and coating products, can be made from a swollen, layered flocked silicate gel material prepared by use of an exchange cation selected from polyamine derivatives. Surprisingly, in general, such products have been found to show greatly improved results in tensile strength and dielectric strength tests performed when the products are wet, compared to materials made using the prior art exchange cations. In addition, the products made according to the present invention usually have electrical and mechanical properties superior to those of materials made using prior art methods.

With regard to heat resistance, the products made according to the present invention are completely stable to temperatures of about 350-400 ° C and maintain their structural stability up to about 800 ° C.

The products and flocculated mineral suspensions of the present invention are prepared, in one embodiment, by using as the starting material a water-swellable silicate sheet having an average charge per structural unit of about -0.4 to about -1 and containing interstitial exchangeable cations that promote swelling. The specific exchange cations in the starting material 35 will depend on the silicate to be used. For example, when a synthetic gelatable silicate prepared according to the procedure of U.S. Patent 4,239,519 is used as the starting material, the. exchange cations usually Li + and / or Na + io- - υ

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- 4 - nes. When a natural vermiculite dispersion is used, as prepared according to US Pat. No. 3,325,340, the exchange cations are usually alkyl ammonium cations and the other cations described in US Patent 3,325,340. The silicate, whether of synthetic or natural origin, often has morphologies represented by thin flakes, which are generally disc, strip and / or ribbon shaped. The peel-

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fers have typical dimensions which are about 500-100,000 A and o o 10 preferably 5,000-100,000 A in length, 500-100,000 A in

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width and less than 100 A in thickness, without however being limited thereto.

The term "charge per structural unit" used in the description and claims refers to an average charge density as defined by G. Lagaly and A. Wëiss, "Determination of Layer Charge in Mica - Type Layer Silicates," Proceedings of International Clay Conference, 61-80 (1969) and G. Lagaly, "Characterization of Clays by Organic Compounds", Clay Minerals, 16, 1-21 (1981).

The starting silicate can be prepared according to the aforementioned processes from US Patents 4,239,519; 3,325,340; or 3,434,917 or by other methods leading to dissociated layer materials with charge densities in the desired ranges.

The silicate is then contacted with a source of at least one kind of polyamine-derived cations to thereby effect an ion exchange reaction between the cations and the interstitial ions. This ion exchange reaction can be performed between the cations and the silicate material to form a flock material which is then used to manufacture the products of the present invention. In another embodiment of the present invention, the starting silicate can be directly formed into a product, such as a lithium fluorhectorite fiber or film, using the methods of U.S. Patent 4,239,519, and a cation exchange reaction using the polyamine-derived cations, can be performed with the product, for example, by under ·. - ** Λ - 5 - k * immersion of the product in a solution of the polyamine-derived cations. The ion exchange reaction can therefore be carried out in situ during the actual formation process of the product.

The term "polyamine-derived cations", used to refer to exchange cations that can be used in the present invention, refers to low molecular weight, non-polymeric, dl, tri and / or tetraamino functional compounds, wherein the amine moieties modified, eg protonated, to be positively charged. Diamines are the preferred polyamine compounds. The preferred diamines will generally correspond to the formula R ^ N - (CX2 ^ n “NR3 wherein (1) each R is independently selected from hydrogen, a C 1 -C 8 straight or branched chain alkyl, a C 8 -C 8 acylalkyl group or an aryl group, provided that there is no more than one aryl group on each nitrogen atom, (2) each X is independently selected from hydrogen, an alkyl group or an aryl group, and (3) n represents an integer of 2-15, 20 and optionally the CX2 groups, when n is greater than 3, may form ring portions which may be aromatic.

For example, the flocked mineral suspensions of the present invention are prepared by reacting, usually with stirring, a suitable silicate gel with a source of exchange cations obtained from suitable polyamine compounds to effect an ion exchange between the polyamine-derived cations and the interstitial cations in the silicate gel to form exchanged macro-flocculated particles.

As previously explained, one or more exchange cations can be used in the cation exchange reaction. Since the different cations yield flocculated materials and optionally end products with different physical properties, the specific cation or combination of cations is selected by the user of the present invention for the desired end use.

The terms "polyamines derived from polyamine" or "cation derivative" or the like used in the specification and claims serve to indicate that the center for cations. The activity is located on the nitrogen groups in the polyamines. Generally, this is accomplished by protonating the polyamines to form positively charged ammonium groups. This protonation must take place before the cation exchange can be carried out with the swollen silicate gel.

The flocculated mineral suspension can be used to form the desired end products. The specific treatment steps applied to the flock material depend on the particular product to be formed. For example, if the products of the present invention are to be formed into sheet materials, the resulting exchanged flock material is stirred with sufficient shear to produce a particle size distribution leading to a suitable particle packing in the sheet forming operation. According to this method, the flocked material is optionally washed to remove any excess saline and the consistency of the flocked suspension is adjusted to about 0.75-ca. 2% 20 solids. To obtain better draining rates on a fourdrinier gauze, polyelectrolyte flocculants can then be added to the slurry at a concentration of about 0.1 - about 1%, and preferably 0.2-0.3%, of the flocculated solids. One example of a suitable polyelectrolyte flocculant is Polymin P, which is a trademark of BASF Corporation for a polyethylene imine.

This slurry is then fed to a papermaking apparatus, where it is dewatered by free drainage and / or vacuum drainage followed by pressing and drying on drum dryers. The sheet material thus obtained can be used in applications such as gaskets and the like.

If desired and depending on the intended final application of the products, additional inert materials can be added to the flocculated mineral suspension. For example, if desired, one or more fibrous materials from the group of natural or synthetic organic fibers or inorganic fibers may be added to the flocculated material to improve its draining rate and a. ; i.

to provide final product that has improved strength and / or manageability. For example, when the desired end products are packings, the fibers of choice are cellulose fibers, glass fibers and / or Kevlar fibers (Kevlar is a trademark of DuPont Corporation for an aromatic polyamide fiber). In addition, synthetic latex or other binders can be added to the flocculated material to provide a product with improved strength properties.

Alternatively, the cation exchange reaction can be carried out directly on a product formed from the silicate starting material. In this case, any desired additional inert materials may be added to the slurry of the silicate starting material prior to product formation and, of course, the subsequent cation exchange reaction.

It has been discovered that epoxy resins are particularly suitable additives for the products formed according to the present invention. The use of such resins gives strength to the final product and, when used in conjunction with diamine-exchanged flocculated material, has been found to elicit a two-sided function in the diamines, which not only act as exchange cations for the silicate sheet material but also as a cross-linking agent for the epoxy resins. The product obtained has improved strength, chemical resistance and dielectric properties.

The term "water resistant" used in the description and claims is not intended to indicate that the products of the present invention are waterproof or completely impervious to water. In contrast, the term has been used to indicate that the materials do not deteriorate substantially, at least in their tensile and dielectric strength properties, upon exposure to water.

In addition to being water-resistant and having excellent fire and heat resistance, the products of the present invention have been discovered to have excellent electrical properties and are therefore suitable for a variety of applications, such as electrical insulators, cable coatings and in particular printed wiring boards.

In the following examples, unless otherwise specified, the starting material used is one according to the methods described in U.S. Pat. 4,239,519, prepared lithium fluorhectorite.

EXAMPLE I

This example illustrates a process for preparing both a diamine-exchanged flocculated fluorhectorite silicate and a molded sheet made therefrom.

A suspension of 1,6-hexanediammonium fluorhectorite (prepared from the corresponding diamine) was prepared by adding 200 g of a 10% dispersion of lithium fluorhectorite to 2 L of 1N 1,6-hexanediamine-HCl solution. The suspension was then stirred with a high speed shear mixer to reduce the particle size of the resulting flocculated material, washed and then analyzed for water content and diluted to a 2% solids suspension. The slurry was transferred to a 29.2 cm x 29.2 cm manually operated sheet former (manufactured by Williams Apparatus Co.) and dewatered. The resulting molded sheet was then wet pressed and dried on a drum dryer. The sheet had good flexibility and passed the packing seal test well.

EXAMPLE II

Using the procedures of Example I, a hand sheet was prepared from the following slurry: wt% 30 Hexamethylenediammonium fluorhectorite 58.7 NBR latex 3.2 alum 2.9 microtalk 5.9 redwood fiber 2.9 35 Klevar® fiber 2.9 mineral wool 23.5 total 99.2

The resulting hand sheet was subjected to gasket sealing tests which were electro-mechanical air leak tests performed according to the specifications set out on pages 1-3 of the SAE ( Society of Automotive Engineers, Inc.) technical paper No. 83022 (ISSN 0148-7191 (83 / 0228-0220, 1983)).

5 The results of the tests were:

Initial flange pressure (kPa) leak rate (kPa / min) 570 9.577 915 10.942 10 2500 3.647

EXAMPLE III

This example is intended to illustrate a process for preparing films of the present invention, wherein the cation exchange is performed in situ.

A gelled lithium fluorhectorite dispersion with 10% solids was prepared according to the procedures described in U.S. Patent 4,239,519. A film was made of this material using a 0.11 mm Byrd 20 applicator, which was 12.7 cm wide, to deposit a 0.11 mm thick wet film of the dispersion on a glass plate. The glass plate, with the film attached, was then dipped in a 0.25M solution of 1,6-hexanediamine-HCl to exchange cation between the 1,6-hexane-25 diammonium cations and the interlayer cations of the fluorine hectorite. to establish. A web was apparently immediately formed on the film, indicating that such an exchange was taking place. After 10 min, the film was separated from the plate, washed in deionized water to remove residual salts and dried. The film had good flexibility and retention of wet strength.

EXAMPLES IV-XV

For each of these examples, the procedure of Example III was essentially repeated with the exchange cation (all prepared from the corresponding diamine) described below to form the corresponding film.

* '* - 10 -

Example Exchange cation IV N, N, N ^ N-tetramethylethylenediamirionium V O-phenylenediammonium VI 1,2-diammonium propane 5 VII 1,8-diammonium octane VIII 2,5-toluene diammonium IX 1,7-diammonium heptane X 1,9-diammonium nonane XI 1, 5-diammonium pentane 10 XII 1,2-ethylenediammonium XIII 1,3-diammonium propane XIV 1,4-diammonium butane

XV 1,12-diammonium dodecane Comparative Examples I-III

These comparative examples describe fluoro-hectorite films made with various prior art exchange cations. 0.11 mm thick films of potassium fluorhectorite (KFH) and ammonium fluorhectorite (NH 4 FH) were prepared separately using the method described in U.S. Patent 4,239,519. Then a film was cast from both the KFH and the NH 2 FH suspension. A Kymene (trademark of Hercules, Ine. For a cationic polyamide-epichlorohydrin resin) fluorhectorite film was also prepared according to the method of Example II, 25 except that (1) a 3.0% Kymene solution was used and (2) the lithium fluorhectorite film was immersed in the Kymene solution for 2 hours until the resulting exchanged film was sufficiently self-supporting to be removed from the glass plate. These films, like the films made in Examples III-XV, were then subjected to tensile and dielectric strength tests, which were carried out as follows:

Tensile strength measurements:

Tensile strength measurements in the dry state were performed on an Instron device with a claw separation of 3.8 cm and a cross slide speed of 0.5 cm / min. Wet strength measurements were made by contacting water-saturated sponges with both sides of the film sample for 10 sec while the sample was in the Instron clamps' r i S - j - "j

"J1 9" Q

-11- S '»confirmed just before the strength test was performed.

Dielectric strength measurements;

A film sample was placed in a holding device which firmly secured the film. A loadable cutting bit was impacted onto the film in the direction perpendicular to the surface of the film and it was loaded with an increasing weight until the cutting bit penetrated the film. In the wet test, the film in the holding device was immersed in deionized water for 10 seconds immediately prior to the impact strength test.

The results of these tests are shown in the table below.

TABLE

15 Film of exchange cation tensile breakdown resistant example strength (g / mm) no .__ (kPa) _ _4 dry wet dry wet III 1,6-hexanediammonium 110,300 117,200 1 3 0 0 0 6 0 0 0 IV Ν, Ν, Ν *, Ν-tetramethyl-20 ethylenediammonium 124,100 110,300 11,000 5,100 V O-phenylenediamine 89,600 103,400 7600 3000 VI 1,2-diammonium propane 89,600 75,800 14,000 4,200 VII 1,8-diammonium octane 82,700 75,800 6,500 1,700 VIII 2,5-toluene diammon 65,600 75,800 1800 25 IX 1,7-diammonium heptane 50,300 60,700 16,000 7,500 X 1,9-diammonium nonane 48,300 34,500 3,600 1,400 XI 1,5-diammonium pentane 45,500 303,000 5,700 5,200 XII 1,2-ethylenediammonium 35,900 24,800 1,200 600 XIII 1,3-diammonium propane 22,800 9,650 3500 680 30 XIV 1,4-diammonium butane 20,700 9,650 6 6 0 0 9 0 0 XV 1,12-diammonium dodecane 12,400 20,000 3,100 570

Comparative example No.

I Kymene (protonated) 48,300 18,600 900 260 35 II ammonium 22,800 9,650 3,500 680 III potassium 7,580 1,380 3,300 440

The data shows that the films made according to the method of the present invention have a significantly higher wet tensile strength and / or higher wet tensile strength than the prior art products. .

Fire and smoke resistance

A film prepared according to Example III, after being dried, was subjected to fire and smoke resistance tests according to the procedures set forth in ASTM-E-662-79. Three separate experiments were performed, the results of which are reported below.

Test 1 - Flammability 10 (The numerical values correspond to the maximum specified optical density in N.B.S. Technical Note No. 708).

Flame type 0 smolder mode 0 15 Test 2 - oxygen index type C ASTM D2863-77 critical oxygen index - 100% 02 Test 3 radiation panel ASTM-E162-79 Flame spread factor 1.00 20 heat development 0.0 flame spread index 0.0

Electrical properties

A film of Example II, after being dried, was tested for the dielectric constant and dissipation factors using the procedures of ASTM D150 and for the dielectric breakdown strength using the procedures of ASTM D149. The results presented below indicate that the film is useful in a variety of electrically insulating properties.

30 dielectric dissipation constant factor 100 HZ at 25 ° C 26.53 0.288 100 HZ at 300 ° C 37.9 0.37 100 HZ back to 25 ° C 10.7 0.049 100 KHZ at 25 ° C 12.19 0.153 35 100 KHZ at 300 ° C 15.0 0.202 100 KHZ back to 25 ° C 9.52 0.024

Dielectric breakdown strength measured at 22.7 kV / mm. Comparative Examples IV and V These examples illustrate the use, as a starting material, of silicate materials which are outside the scope of the present invention in terms of their charge per structural unit and their physical measurements.

For Comparative Example IV, a 10% aqueous dispersion was prepared from a natural hectorite obtained from the clay mineral deposit of the Clay Minerals Society, Bloomington, Indiana. For Comparative Example V, a 10% aqueous dispersion was prepared with sodium montmorillonite obtained from the same source. In each example, a film was deposited according to the procedure described in Example III. The glass plates were then immersed in a 0.25 M 1,6-diammonium hexane solution for 10 min. In both cases, no coherent film was obtained.

EXAMPLE XVI

This example is intended to illustrate a method of manufacturing a film according to the present invention using vermiculite as the starting material:

A suspension of n-butylammonium vermiculite with 10% solids, prepared according to the procedures described in U.S. Patent 3,325,340, was cast as a film on a glass plate according to the procedure described in Example III. The glass plate, with the film attached to it, was immersed in a 0.25 M 1,6-hexanediamine-HCl solution for 10 min. The resulting film was separated from the plate, washed and dried. The film exhibited wet strength in the tensile and breakdown strength tests, which was not exhibited by a comparable unchanged vermiculite film.

EXAMPLE XVII

This example illustrates the preparation of fibers according to the method of the invention. A suspension of lithium fluorhectorite (prepared as above) with 15% solids was extruded through a needle with a 0.30 mm orifice needle in a 2N solution of 1,6-hexanediamine-HCl. The extruded fiber was carried by a porous conveyor belt and delivered to a second bath of 2N 1,6-hexanediamine-HCl.

The fiber thus prepared was washed by immersion in deionized water and dried. The fiber obtained - 14 - was strong and flexible.

EXAMPLE XVIII

This example demonstrates the addition of an epoxy to sheet silicate mixtures.

Codispersions of the diglycidyl ether of bisphenol A (DGBA) and lithium fluorhectorite (LiFH) were prepared by adding the epoxy to a 10% (solids) aqueous lithium fluorhectorite dispersion. The codispersions were then mixed by a high shear process. The codispersions were formed in the following ratios of LiFH to DGBA: 1. 100 g 10% solids LiFH dispersion (10 g LiFH solids) 0.1 g epoxy (approx. 1% based on solids).

2. 100 g 10% solids LiFH dispersion 1.1 g epoxy (approx. 11%) 3.100 g 10% solids 2.5 g epoxy (approx. 25%).

The films were prepared by depositing 11 mm wet films on glass plates with a Byrd applicator and immersing the film in a 0.25M hexamethylene diamine HCl solution at a pH of 7.0 . The films obtained had a good wet strength property of fluorhectorite exchanged with hexamethylene diammonium. The resulting film was washed with deionized water to remove excess hexamethylenediamine-HCl and dried at 60 ° C. The dry films, which were flexible, were heated to 150 ° C for 3 hours. The films obtained exhibited increasing stiffness as expected with epoxy curing. Therefore, it appears that the hexamethylenediammonium cation is effective in performing the exchange function of the layered silicate and in the epoxy curing.

For an alternative method of making products, epoxy / fluorhectorite codispersions as described above were converted into a flocculated form by adding the codispersion to a 0.25M hexamethylene diamine HCl solution with stirring. After washing out excess hexamethylenediamine-HCl from the flocculated material, the solids content of the flocculated material was adjusted to 2% and subjected to high shear mixing to reduce the particle size. The resulting material was transferred in a non-porous form and dried into coherent flexible films about 0.25 mm thick.

The films were hot pressed at 150 ° C for 3 hours and the films stiffened.

For the manufacture of products of the present invention, 1-80 wt% epoxy resins can be used based on the solid weight of the velor silicate starting material.

Claims (23)

Method for the preparation of a flocculated mineral material useful for forming an asbestos-free high temperature product which is water resistant, characterized in that the method consists in contacting a swollen layered silicate gel containing an average has charge per structural unit in the range of from about -0.4 to about -1 and has interstitial interchangeable ions, with at least one kind of polyamine-derived cations to thereby effect an ion exchange reaction between at least some of the interchangeable interstitial ions and at least some of the polyamine-derived cations. 2. Process according to claim 1, characterized in that the polyamine-derived cations are diamine-derived cations. A method according to claim 1 or 2, characterized in that the gelled layered silicate is a synthetic gellable silicate and the interstitial ions are Li + and / or Na +. 4. Process according to claims: 1-3, characterized in that said synthetic silicate is prepared by a mass consisting mainly of crystals of a water-swellable mica selected from the group of fluorhectorite, hydroxylhectorite , boron fluoro-phlogopite, hydroxylboron phlogopite and solid solutions between them as well as between these and other structurally compatible species selected from the group of talc, fluoralkalk, poly-lithionite, fluoropolylithionite, phlogopite and fluorophlogopite, during contact with a polar liquid. time sufficient to effect the swelling of the crystals associated with gel formation. 5. Process according to claim 4, characterized in that the crystals are fluorhectorite. 6. Process: according to claims 2-5, characterized in that the diamine-derived cations are selected from the group consisting of 1,6-hexanediamine, N, N, N ', N-tetra-methyl-ethylenediamine, 0-phenyldiamine 1,2-diaminopropane, 17-diamino octane and 2.5 toluenediamine. A method according to claim 3, characterized in that the polar liquid is water. 8. Method according to claim 2. m e :::. T h e „t. Characterized in that the silicate is vermiculite and the interstitial ions are alkyl ammonium cations, the cationic form of amino acids and / or Li +. Flocked mineral material, characterized in that it consists of a swollen layer of 10 silicate gel having an average charge per structural unit in the range of about -0.4 to about -1, said silicate being at least some interstitial cations, which are polyamine derivatives. 10. The material according to claim 9, characterized in that the polyamine derivatives are diamine derivatives. 11. Material according to claim 9 or 10, characterized in that the silicate is obtained synthetically. The material according to claim 11, characterized in that said silicate is prepared by (1) contacting a mass consisting mainly of crystals of water-swelling mica containing interstitial lithium and / or sodium cations, wherein said mica is selected from the group of fluorohecto. reed, hydroxyl hctorite, boron fluorophlogopite, hydroxyl boron phlogopite and solid solutions between them as well as between these and other structurally compatible species selected from the group of talc, fluoralkalk, polylithionite, fluoropolylithio-30, phlogopite and fluorophlogopite, with a polar solution for a time that is sufficient to effect the swelling of the crystals associated with the formation of a gel and (2) contact the thus formed gel with at least one kind of a cationic diamine derivative to thereby effect an ion exchange reaction between at least some of the lithium and / or sodium cations and at least some of the diamine-derived cations. 13. The material according to claim 12, characterized in that the crystals are fluorhectorite. Material according to claim 12 or 13, characterized in that the polar liquid is water. 15. Material according to claims 12-14, characterized in that the diamine-derived cations are selected from the group of 1,6-hexanediamine, Ν, Ν, Ν ', Ν-tetramethylethylenediamine, 0-phenyldiamine, 1,2- diamino propane, diamino octane and 2,5-toluene diamine. Material according to claim 14, characterized in that the silicate is vermiculite. 17. High temperature, water resistant product with good electrical properties, characterized in that it consists of a swollen layered silicate having an average charge per structural unit in the range of about -0.4 to about - 1, wherein said silicate contains at least some interstitial cations which are diamine derivatives. Product according to claim 17, characterized in that it additionally contains an epoxy resin. 19. Product according to claim 17, characterized in that it is a sheet-like material. 20. Product according to claim 17, characterized in that it is a fiber. 21. A product according to claim 17, characterized in that it is a film. 22. Process for the preparation of a high temperature. silicate product which is water resistant and has good electrical properties, characterized in that the method consists in contacting a product formed of a gellable layered water-swellable silicate with a charge per structural unit in the range of approx. -0.4 to -1 and containing interchangeable interstitial ions, with a source of at least one kind of polyamine-derived cations to thereby effect an ion-exchange reaction between at least some of the polyamine-derived cations and at least some of the interstitial ions. 23. A method according to claim 22, characterized in that the polyamine-derived cations are diamine-derived cations. > · - «i | 1 - ^