FR2579198A1 - PROCESS FOR PREPARING FLOCULATED MINERAL MATERIAL, FLOCULATED MINERAL MATERIAL OBTAINED THEREBY, WATER-RESISTANT ARTICLES PREPARED THEREFROM, AND PROCESS FOR PREPARING THE SAME - Google Patents

Abstract

FLOCCULATED MINERAL MATERIALS WHICH CAN BE USED TO PREPARE HIGH TEMPERATURE RESISTANT, WATER RESISTANT ARTICLES. THESE MATERIALS ARE PREPARED USING AS A STARTING MATERIAL, A GELIFIABLE LAYER INFLATED SILICATE WHICH HAS A MEDIUM LOAD PER STRUCTURAL PATTERN RANGING FROM APPROXIMATELY 0.4 TO 1 AND WHICH CONTAINS INTERSTICIAL CATIONS WHICH PROMOTE SUFFERING. 'AT LEAST ONE SPECIES OF CATIONS DERIVED FROM A MULTIAMINE. APPLICATION IN PARTICULAR TO THE MANUFACTURE OF ELECTRICAL INSULATION AND PRINTED CIRCUIT BOARDS.

Description

PROCESS FOR PREPARING FLOCULATED MINERAL MATERIAL, MATERIALS

  FLOCULATED MINERALS SO OBTAINED, ARTICLES RESISTANT TO WATER

  PREPARED THEREFROM AND PROCESS FOR PREPARATION THEREOF

  The present invention relates to a process for preparing a flocculated material and to the flocculated mineral materials thus obtained. The materials may allow the production of water-resistant articles which are also the object of the invention as well as their preparation process. It is known that papers and / or leaves

  asbestos can be produced from

  Inflatable hydrodynamics, and in particular inflated silicate gels. For example, U.S. Patent No. 4,239,519 relates to the preparation of inorganic, hydrophilic, water-swellable, synthetically produced, inorganic sheet silicates, and certain articles such as papers, fibers, films,

  plates and coatings produced therefrom.

  These papers and / or sheets without asbestos present a good

  high temperature stability and good chemical resistance.

  Moreover, since their manufacture does not use asbestos fibers, these articles do not present the dangers for the

  health of articles containing asbestos.

  U.S. Patent No. 4,239,519 discloses

  that the process for producing precurable gelling silicates

  used to produce these papers or sheets

  three fundamental stages: (a) formation of a complete body-

  or predominantly crystalline which contains crystals consisting essentially of a sodium mica and / or lithium swelling with water selected from fluorohectorite,

  hydroxylhectorite, boron fluorophlogopite, fluoro-

  phlogopite, boron phlogopite, and solid solutions between these compounds and structurally

  selected from talc, fluorotalc, poly-

  lithionite, fluoropolylithionite, phlogopite and fluorophlogopite; (b) contacting this body with a

  polar fluid, normally water, to cause swelling

  ment and disinfection of the body accompanied by the formation of a gel; and (c) adjusting the solid: liquid ratio of the gel to a desired value depending on the application for which it is intended. Glasses ceramics are the preferred crystalline starting materials. These products are then put in contact

  with a source of large cations, that is,

  have an ionic radius greater than that of the lithium cation, to cause macrofloculation of the gel and an ion exchange reaction between large cations and Li and / or Na ions from the intermediate layer

crystals.

  In addition, U.S. Patent Nos. 3,325,340 and 3,454,917 disclose the production of aqueous dispersions of vermiculite flake crystals whose swelling has been caused by the introduction therein of interstitial ions. such as (1) alkylammonium cations having from 3 to 6 carbon atoms included in each carbon group such as methylbutylammonium, n-butylammonium, propylammonium and isoamylammonium cations, (2)

  cationic form of amino acids such as lysine and

thine, and / or (3) lithium.

  Although articles, such as papers, sheets and pel-

  additives, prepared by the processes of the prior art

  above have excellent thermal resistance.

  Although they are useful in a wide variety of applications, it has been found that these articles generally do not exhibit good sealing characteristics, which limits their use as joint materials. The articles of the prior art also have a certain sensitivity

  to water, which usually manifests itself in a considerable loss of

  resistance and general degradation of mechanical and electrical properties when exposed to high humidity environments or immersed in water or other polar liquids. This sensitivity to water

  therefore limits the possibilities of using

  these articles in certain applications such as, for example, cylinder head gaskets, electrical insulators, environmental protection coatings and washable and environmentally stable building materials. A related patent application, U.S. Patent Application No. 662,057, filed October 18, 1984, indicates that flame retardant articles without asbestos can

  be made from silicate gel flocculated in

  dried, and swollen, which is prepared using an exchange cation selected from guanidine derivatives. These articles, from

  surprisingly, have superior water resistance

  than those prepared by the processes of the art

  prior, and have excellent electrical properties.

  It has now been unexpectedly found that high-temperature, flame retardant, asbestos-free, water-resistant articles such as sheets, papers, plates, films, fibers and

  coating, can be made from a silicone gel

  flocculated, swollen cate, which is prepared using

  an exchange cation chosen from multiamines derivatives.

  These articles were surprisingly presented,

  in general, greatly improved results in resistance tests

  Tensile strength and puncture resistance that are performed when the articles are wet, compared to materials that have been prepared using the exchange cations of the prior art. In addition, articles made in accordance with the present invention generally have higher electrical and mechanical properties than

  materials made according to the methods of the prior art.

  With regard to the thermal resistance, the articles which are produced in accordance with the present invention are completely stable at temperatures of about 350-400 C and

  retain their structural stability up to about 800 C.

  Articles and flocculated mineral suspensions of - 4 -

  the present invention are prepared according to a method of

  of the invention, using as a starting material a water-swellable sheet silicate which has an average charge per structural unit of about -0.4 to about-1 and which contains interstitial exchangeable cations which promote swelling. The particular exchange cations of the starting material will depend on the silicate used. For example, if a synthesized gelling silicate material manufactured according to the procedures of U.S. Patent No. 4,239,519 is used as the starting material, the exchange cations will generally be Li + ions and / or Na +. If a natural vermiculite dispersion is used as manufactured in accordance with US Pat. No. 3,325,340, the exchange cations will generally comprise alkylammonium cations and the other cations specified in the US Pat. United States No. 3,325,340 Silicate, whether of synthetic or natural origin, will often have morphologies represented by fine scales which are generally disks, bands, and / or ribbons. Although the Applicant does not wish to be limited to particular scale sizes, these will generally have dimensions of about 50 nm to 10,000 nm, and preferably about 500 nm to about 1,000 nm in length. , 50 nm to 10 000 nm wide, and less than

10 nm thick.

  The expression "load per structural unit" used in

  the description and the claims refers to a density

  of average charge as specified by G. Lagaly and A. Weiss, "Determination of Layer Charb in Mica - Type Layer Silicates", Proceedings of International Clay Conference, 61-80 (1969) and by G. Lagaly, "Characterization of Clays by

  Organic Compounds ", Clay Minerals, 16, 1-21 (1981).

  The starting silicate may be prepared in accordance with the aforementioned procedures of U.S. Patent Nos. 4,239,519, 3,325,340, or 3,434,917 or by other methods which result in dissociated layered materials having

  charge densities in the desired intervals.

  The silicate is then contacted with a source of at least one species of cations derived from multiamines to effect an ion exchange reaction between the cations and the interstitial ions. This ion exchange reaction can be carried out between the cations and the silicate to thereby form a floc which is then used to form the articles of the present invention. According to another embodiment of the invention, the starting silicate can be converted directly into a product, such as lithium fluorohectorite fiber or film using the procedures of U.S. Patent No. 4,239. 519, and a cation exchange reaction using the cations obtained from multiamines, can be carried out with the product, for example by immersing the product in a solution of cations obtained from multiamines. Thus, the ion exchange reaction can be carried out in situ during

  the actual operation of product formation.

  The expression "cations obtained from multiamines", when used in connection with the exchange cations which can be used in the present invention, refers to di-, tri- and / or tetra-amino functional compounds, low molecular weight, non-polymeric, in which

  the amine parts have been modified, for example by proto-

  nation, to charge them positively. Diamines are the preferred multiamines. The preferred diamines will generally be of the formula R3N (CX2) n -NR3 wherein (1) each of R is independently selected from hydrogen, C1-C8 linear or branched alkyl, C3 cyclic alkyl group having C6, or an aryl group provided that there is not more than one aryl group on each nitrogen, (2) each of X is independently selected from hydrogen, an alkyl group or an aryl group and ) n represents a

  integer from 2 to 15, with the proviso that when n is 3 or more

  CX2 groups can form cyclic parts

which can be aromatic.

  The flocked mineral suspensions of the present invention

  The reaction is prepared by, for example, reacting, generally with stirring, a suitable silicate gel with a source of exchange cations from multiamines suitable for ion exchange between the cations from multiamines and the interstitial cations of the gel. silicate

  to form exchanged macrofloculated particles.

  As indicated above, one or more exchange cations may be used in the cation exchange reaction. Since the various cations will give a floc, and finally articles having different physical properties, the particular cation or combination of cations will be chosen by the one who embodies the invention.

  on the basis of the desired end use.

  The expression "cations obtained from multiamines"

  or "cationic derivatives" etc., is used in the description

  and the claims to indicate that the activity

  The focus is on the nitrogen groups of multiamines. In general, this is achieved by protonating multiamines for

  thus form ammonium groups that are positively charged

  is lying. This protonation must take place before the exchange

  cation can be achieved with the inflated silicate gel.

  The flocculated mineral suspension can be used to

  to form the desired articles. The stages of treatment

  applied to the floc will depend on the particular article

  to manufacture. For example, if the articles of this invention

  must be transformed into sheet material, the exchanged floc obtained will be stirred with sufficient shear

  to produce a particle size distribution

  to the proper settlement of the particles in the

  formation of the sheet. After this operation, the floc is washed, if desired, to remove any excess salt solution present, and the consistency of the flocculated slurry is adjusted to about 0.75% to about 2% solids. To promote better drainage rates on a four-wire fabric, polyelectrolyte flocculants can then be added to the slurry at a rate of about 0.1% to about 1%, and preferably 0.2% to 0%. , 3% floc solids. An example of a suitable polyelectrolyte flocculant is Polymin P, which is a registered trademark of BASF

  Corporation for an imine of polyethylene.

  This slurry is then sent to a paper machine where it is dewatered by free drainage and / or vacuum drainage, then pressed and dried on dryers.

  drum. The sheet material thus formed can be used

  in applications such as seals, etc.

  If desired, and depending on the intended end use

  For the articles, additional inert materials may 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 floc to improve its drainage rate and to provide an end product that exhibits strength and / or improved handling ability. For example, where the desired end products are seals, the preferred fibers are cellulose fibers, glass fibers and / or Kevlar fibers (Kevlar is a trademark of Du Pont Corporation for an aromatic polyamide fiber). In addition, a synthetic latex or other binders can be added to the floc

  to provide a product with resistance characteristics

improved.

  The cation exchange reaction can also be effected

  killed directly on a product formed from the silicate starting material. In this case, any additional inert material may be added to the slurry containing the silicate starting material prior to formation of the product,

  and obviously the subsequent cation exchange reaction.

  Epoxy resins have been found to be particularly useful additives for articles formed according to the present invention. The use of these resins adds resistance to the end product and, when used with a diamine exchanged flock, they appear to promote dual functionality in the diamines, which act not only as exchange cations for the silicate material in sheets, but also as crosslinking agent for epoxy resins. The product obtained has a resistance

  mechanical resistance, chemical resistance and dielectric

improved.

  The term "water-resistant" used in the preface

  This description and the claims do not imply that

  articles of the present invention are water-repellent or

  are impermeable to water. On the contrary, the term is used to indicate that the materials do not degrade significantly, at least as regards their tensile strength and puncture resistance properties,

  when exposed to. the water.

  In addition to their resistance to water and their excellent resistance

  In addition to the fire and heat resistance, it has been discovered that the articles of the present invention possess excellent electrical properties and are therefore suitable for various purposes.

  applications including electrical insulators, winding them

  cables and in particular printed circuit boards. In the following examples, unless otherwise indicated, the starting material used is a lithium fluorohectorite prepared according to the methods set forth in US Pat.

  U.S. Patent No. 4,239,519.

Example 1

  This example illustrates a process for preparing both a flocculated silicate of fluorohectorite exchanged by a

  diamine and a shaped sheet prepared therefrom.

  a slurry of 1,6-hexanediammonium fluorine is prepared

  hectorite (prepared from the corresponding diamine) by adding 200 g of a 10% lithium fluorohectorite dispersion to 2 liters of a 1 N solution of 1,6-hexanediamine HCl. The slurry is then agitated with a high shear mixer to reduce the particle size of the resulting floc, and is washed and analyzed for water content and diluted to a 2% slurry of solids. The slurry was passed through a 292 mm x 292 mm (11.5 inch x 11.5 inch) hand-held tablet (manufactured by Williams Apparatus Co.) and dehydrated. The shaped sheet obtained is then wet-compressed and dried on a tumble dryer. The sheet presents a good

  flexibility and behaves well in sealing tightness test.

  Example 2 Using the procedures of Example 1, a form is prepared from the following slurry:% by weight Hexamethylene diammonium fluorohectorite 58.7 Latex NBR 3.2 Alum 2.9 Micro talc 5.9 Fiber sequoia 2.9 Kevlar (R) fiber 2.9 Mineral wool 23.5 Total 99, 2 The resultant form is subjected to joint leak tests which are electromechanical air leak tests performed in accordance with the specifications of the pages 1-3 of Society of Automotive Engineers, Inc. (SAE) technical paper

  No. 83022 (ISSN 0148-7191 (83 / 0228-0220, 1983)).

  The results of the tests are as follows: Initial flange pressure Leakage velocity in MPa (psi) in kPa / min (psi / min)

3.93 (570) 9.577 (1.389)

6.31 (915) 10.94 (1,587)

17.2 (2500) 3,647 (3,647)

Example 3

  This example illustrates a process for producing films

  of the present invention in which the cationic exchange

that is done in situ.

  A gelled dispersion of lithium fluorohectorite at 10% solids was prepared according to the procedures set forth in U.S. Patent No. 4,239,519. A film was made from this material using a Byrd applicator. , 3 microns (4.5 mil) having 127 mm (5 inches) wide, to deposit a wet film of 114.3 microns (4.5 mil) of the dispersion on a glass plate. The glass plate, to which the film is attached, is then immersed in a 0.25 M solution of 1,6-hexanediamine HCl to induce a cation exchange between the 1,6-hexanediammonium cations and the intermediate layer cations. fluorohectorite. A skin appears, apparently instantaneously, on the film which indicates that this exchange has occurred. After 10 minutes the film is removed from the plate, washed with deionized water to remove residual salts and dried. The film has good flexibility and good retention of the

  resistance when wet.

  Examples 4-15 For each of these examples, the procedure of Example 3 is practically repeated with the exchange cation (prepared from the corresponding diamine) as it is

  indicated to form the corresponding film.

  Example Exchange cation 4 N, N, N ', N-tetramethylethylenediammonium Ophenylenediammonium 6 1,2 diammonium propane 7 1,8 diammonium octane 8 2,5 toluenediammonium 9 1,7 diammoniumheptane 1,9 diammoniumnonane 11 1,5 diammoniumpentane 12 1 1,3 Comparative Examples 1-3 These diamines are exemplified by fluorohectorite films which are made with various exchange cations of the prior art. 114.3 micron (4.5 mil) thick films of potassium fluorohectorite (KFH) and ammonium fluorohectorite (NH4FH) are prepared separately by the method disclosed in US Pat. A film is then cast from both the KFH slurry and the NH4FH slurry. A film of Kymene (trademark of Hercules, Inc. for a cationic polyamide epichlorohydrin resin) fluorohectorite was also prepared according to the procedure of Example 2 except that (1) a 3.0% Kymene solution was used. (2) The lithium fluorohectorite film should be immersed in the Kymene solution for 2 hours until the resulting exchanged film is sufficiently self-supporting to be removed from the glass plate. The films produced in Examples 2-9 are then subjected to the tensile strength and puncture resistance tests which were carried out as follows: Tensile Strength Measurements The dry tensile strength measurements were carried out as follows: summer

  performed using an Instron dynamometer with a separate

  feeding of the jaws of 38.1 mm (1.5 inch) and a crosshead speed of 5.08 mm / min (0.2 inch / min). Wet resistance measurements are made by bringing saturated sponges of water into contact with both sides of the film sample for 10 seconds, while the sample is placed in the tongs of the Instron just before carry out

the resistance test.

  Puncture Resistance Measurements A film sample is attached to a fastener that securely holds the film. A stylet that can be loaded is dropped onto the film in the direction perpendicular to the surface of the film and loaded with increasing weights until the stylet penetrates through the film. In the wet test, the film in the fastener is immersed in

  deionized water for 10 seconds, proceeding immediately

  Puncture resistance test.

  The results of these tests are given in the table

below.

BOARD

  Pelli- Resistance Resistance to tensile strength perforation (psi) in g / mm exem- à au ple n cation dry exchange dry wet wet 3 1,6 hexanediammonium 110,32 117,21 13,000 6,000 4 N, N, N ', N-tetramethyl (16000) (17000) ethylenediammonium 124.19 110.32 11000 51000

(18000) (16000)

  0-phenylenediamine 89.63 103.4 7600 3000

(13000) (15000)

  6 1,2 diammonium propane 81.63 75.84 14000 4200

(13000) (11000)

  7 1,8 diammoniumoctane 82,74 75,84 6500 1700

(12000) (11000)

  8 2.5 toluenediammonium 65.67 75.84 6500 1800

(9800) (11000)

  9 1,7 diammoniumheptane 50,33 60,67 16,000 7500

(7300) (8800)

  1.9 diammoniumnonane 48.26 34.47 3600 1400

(7000) (5000)

  11 1.5 diammoniumpentane 45.5 303.38 5700 5200

(6600) (44000)

  12 1,2 ethylenediammonium 358.5 24.82 1200 600

(5200) (3600)

  13 1,3 diammonium propane 22,75 9,65 3500 680

(3300) (1400)

  14 1,4 diammonium butane 20,68 9,65 6600 900

(3000) (1400)

  1,12 diammoniumdodecane 12.4 20.0 3100 570

(1800) (2900)

Example

  comparative n 1 Kymene (protonated) 48.2 18.6 900 260

(7000) (2700)

2 Ammonium 22.75 9.65 3.500 680

(3,300) (1,400)

3 Potassium 7,58 1,38 3,300 440

(1,100) (200)

  The results indicate that the films made in accordance with the procedures of the present invention have a much higher wet tensile strength and / or superior wet puncture resistance.

  to those of the compositions of the prior art.

  Resistance to fire and smoke Fire and smoke tests are carried out

  in accordance with the procedures specified in ASTME-E-

  662-79, a film prepared according to Example 3, and dried. Three separate tests are conducted, the results of which are given below: Test 1 - Flammability

  (The numerical values correspond to the optimum density

  that maximum specified by the technical note of N.B.S. No. 708).

  Flame Combustion 0 Flameless Combustion 0 Test 2 Type C Oxygen Index ASTM D2863-77 Critical Oxygen Index 100% of 02 Test 3 Radiant Panel ASTM-E162-79 Flame Spread Factor 1.00 Heat Release 0.0 Flame Spread Index 0.0 Electrical Properties A film of Example 2 is subjected, after drying, to dielectric constant and dissipation factor tests using the procedures of ASTM D150, and to dielectric strength tests using the

  procedures of ASTM D149. The results, given

  underneath, indicate that the film is useful in various

  applications in electrical insulation.

  Constant Dielectric Dissipation Factor

H2 at 25 ° C 26.53 0.288

H at 300 C 37.9 0.37

H back to 25 C 10.7 0.049

KH2 at 25 C 12.19 0.153

100 KH2 at 300 C 15.0 0.202

  KH2 back to 25 C 9.52 0.024 Dielectric resistance measured at 577 V / 25.4 microns (577 V / m: Comparative examples 4 and 5 These examples illustrate the use, as a starting material, of silicates which come out of the range of the present invention with regard to their charge per structural unit

and their physical properties.

  For Comparative Example 4, a 10% aqueous dispersion of a natural hectorite from the clay mineral deposit of the Clay Minerals Society, Bloomington, Indiana is used. For Comparative Example 5, an aqueous dispersion of 10% sodium montmorillonite, supplied by the same source, is used. In each of the examples, a film is stretched

  using the procedures set forth in Example 2.

  The glass plates are then immersed for 10 minutes in a 0.25 M solution of 1,6-diammoniumhexane. In both

  case, one does not obtain a coherent film.

Example 16

  This example illustrates a process for preparing a film

  According to the present invention, using vermiculite as starting material: It is cast as a film on a glass plate

  according to the procedures of Example 2, a suspension

  10% n-butylammonium vermiculite solids prepared according to the procedures specified in US Pat. No. 3,325,340. The glass plate to which the film is attached is immersed for 0.25 M solution of 1,6-hexanediamine HCl The resulting film was removed from the plate, washed and dried The film exhibited wet strength in tensile strength and puncture resistance tests that a film of vermiculite

  comparable not exchanged does not present.

Example 17

  This example illustrates the preparation of fibers using

  the process of the invention. It is extruded through a 280 micron (11 mil) opening needle into a 2N solution of 1,6-hexandiamine HCl, a 15% suspension of materials.

  Lithium fluorohectorite solids (prepared as above).

  The extruded fiber is conveyed by a porous belt and sent to a second bath of 2N hexane-1,6-hexanediamine. The resulting fiber is washed by immersion in deionized water and dried. The obtained fiber is resistant

and flexible.

Example 18

  This example illustrates the addition of an epoxide to

silicate sites in sheets.

  Codispersions of the diglycidyl ether of bisphenol A (GDBA) and lithium fluorohectorite (LiFH) are prepared by adding the epoxide to a 10% aqueous dispersion (solids) of lithium fluorohectorite. We blend

  codispersion by means of a high shear process.

  LEMENT. The codispersions are formed in the following ratios of LiFH to DGBA:

  1. 100 g of dispersion of LiFH with 10% solids

  (10 g of LiFH solids), 0.1 g of epoxide (1%

  approximately on the basis of solids).

  2. 10 g of dispersion of LiFH with 10% solids

  1.1 g of epoxide (about 11%).

  3. 10-0 g of LiFH dispersion at 10% solids,

2.5 g of epoxide (about 25%).

  The films are prepared by making films

  4.5 mil wet tablets on glass plates with a Byrd applicator and dipping the film in a 0.25 M solution of hexamethylenediamine HCl at a pH of 7.0. The films obtained have the good wet-strength characteristics of fluorohectorite exchanged with hexamethylene diammonium. The film obtained is washed with deionized water to remove excess hexamethylenediamine HCl and dried at 600C. Dried films that are

  flexible, are heated at 1500C for 3 hours. Films

  The results obtained have increased rigidity as

  expect it with hardening by the epoxies. As a result

  it appears that the hexamethylene diammonium cation effectively acts as a layered silicate exchange and

hardening of the epoxides.

  In another process for making the articles, epoxid / fluorohectorite codispersions as described above were converted into a floc form by adding codispersion to a 0.25 M solution of hexamethylenediamine HCl with stirring. After washing the hexamethylene diamine HCl in excess of the floc, the solids content was adjusted

  floc at 2% and subjected to a mixture with a high shear

  to reduce particle size. The resulting material was passed through a non-porous mold and allowed to dry to give coherent flexible films of

  thickness of about 250 microns (10 mil).

  The films were hot pressed at 150 ° C for

  3 hours, and dandruff became more rigid.

  From 1 to 80 parts by weight of epoxy resins based on the weight of solids of the sheet silicate starting material can be used to produce

  articles according to the present invention.

Claims (23)

  I. Process for preparing a flocculated mineral material which can be used to form a high-temperature resistant article, without asbestos, endowed with water resistance, characterized in that it consists in bringing into contact a silicate gel in an inflated layer having an average charge per structural unit of from about -0.4 to about -1 and which contains exchangeable interstitial ions, with at least one kind of cations derived from a multiamine, to thereby effect a reaction of ion exchange between at least some of the exchangeable interstitial ions and at least   some of the cations derived from multiamine.   2. Method according to claim 1, characterized in that the cations derived from the multiamine are cations derived from a diamine.   3. Method according to one of claims 1 or 2, characterized by   the fact that the gelled layer silicate is a synthetic gelling silicate   tick, and the interstitial ions are Li and / or Na.   4. Method according to one of claims 1 to 3, characterized by the   said synthetic silicate is prepared by contacting a body consisting essentially of crystals of a water-swellable mica selected from fluorohectorite, hydroxylhectorite, boron fluorophlogopite, boron phlogopite hydroxyl, and / or solutions solids thereof and other structurally compatible mineral species selected from talc, fluorotalc, polylithionite, fluoropolylithionite, phlogopite and fluorophlogopite, with a polar liquid for a time sufficient to cause swelling   crystals accompanied by the formation of a gel.   5. Method according to claim 4, characterized in that the   crystals are fluorohectorite.   6. Method according to one of claims 2 to 5, characterized by the   that the diamine-derived cations are selected from 1,6-   hexanediamine, N, N, N'-tetramethylethylenediamine, O-   phenyldiamine, 1,2 diaminopropane, diaminooctane, and 2579 198 2,5-toluenediamine.   7. Method according to claim 3, characterized in that the polar liquid is water.   8. Process according to claim 2, characterized in that the silicate is vermiculite and the interstitial ions are cations   alkylammonium, the cationic form of amino acids and / or Li +.   9. Flocculated mineral material, characterized in that it comprises an inflated layered silicate gel which has a mean   structural unit ranging from about -0.4 to about -1, this silicate contains   at least some interstitial cations which are derivatives of   tiamines. 10. Material according to claim 9, characterized by the fact   that the derivatives of multiamine are derivatives of a diamine.   11. Material according to one of claims 9 or 10, characterized   in that the silicate is obtained by synthesis.   12. Material according to claim 11, characterized in that the silicate is prepared: (1) by contacting a body consisting essentially of crystals of a mica swelling in water containing lithium cations and / or   interstitial sodium, this mica being selected from the group of fluorohec-   torite, hydroxylhectorite, fluorophlogopite boron, boron phlogopite hydroxyl, and solid solutions of these and other species   structurally compatible minerals selected from talc, fluorine   talc, polylithionite, fluoropolylithionite, phlogopite and fluorophlogopite, with a non-polar liquid for a time. sufficient to cause the swelling of the crystals accompanied by the formation of a gel and (2) to contact the gel thus formed with at least one cationic diamine derivative to thereby effect an ion exchange reaction between at least one some of the lithium and / or sodium cations and at least   some of the cations derived from the diamine.   13. Material according to claim 12, characterized   in that the crystals are fluorohectorite.   14. Materials according to one of claims 12 or 13, characterized   laughed at the fact that the polar liquid is water.   15. Material according to one of claims 12 to 14, characterized by   the fact that the diamine-derived cations are selected from 1,6-   hexanediamine, N, N, N'-tetramethylethylenediamine, O-phenyldiamine, 1,2-diaminopropane, diaminooctane and 2,5-toluenediamine.   16. Material according to claim 11, characterized in that silicate is vermiculite.   17. High temperature resistant article, water resistant, with good electrical properties, characterized in that it comprises an inflated layered silicate which has an average load per structural unit ranging from about -0.4 to about -1, this silicate containing at least some interstitial cations which are diamine derivatives.   18. Article according to claim 17, characterized in that   further comprises an epoxy resin.   19. Article according to claim 17, characterized by the   makes it a leafy material.   20. Article according to claim 17, characterized by makes it a fiber.   21. Article according to claim 17, characterized by makes it a film.   22. Process for preparing a silicate article   high temperature which shows resistance to water and good   electrical properties, characterized by the fact that it consists of bringing into contact an article formed from a water-swellable silicate in gel-forming layers, which has a charge per structural unit ranging from approximately -0.4 to - 1, and which contains interstitial ions exchangeable with at least   a species of cations derived from a multiamine, for   thus kill an ion exchange reaction between at least some of the cations-derived from a multiamine and at least some of the interstitial ions.   23. Process according to claim 22, characterized in that the cations derived from a multiamine are cations. derived from a diamine.