JPH03348B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION The present invention relates to flame-resistant paper-like materials, particularly layered,
A high temperature, paper-like material consisting of a woven fabric embedded in an inorganic silicate matrix. Conventional technology There is no conventional technology available for comparison. PROBLEM TO BE SOLVED BY THE INVENTION A flame-resistant paper-like material suitable for writing, typewriting, etc., exhibiting good mechanical properties, high temperature stability and water resistance, flexibility, smoothness and paper feel. There is a demand for Besides their obvious utility as high-security papers, such materials are suitable for many applications, such as protective materials in packaging, thermal insulation, electrical insulation and decorative wall panels. Means for Solving the Problems It is an object of the present invention to provide a flame-resistant paper-like material exhibiting good mechanical properties, high temperature stability, water resistance, flexibility, smoothness and paper feel. be. The material of the invention having the aforementioned properties has a
The fabric has an average charge per structural unit in the range of from to about -1 and is embedded in an inorganic, layered silicate matrix selected from the group consisting of guanidine and multiamine derived cations. These materials are referred to herein as "embedded textiles" or "embedded textile materials." The embedded textile materials of the present invention typically, and desirably, (1) have an average charge per structural unit ranging from about -0.4 to about -1 and contain exchangeable interstitial cations; swelling, contacting the layered silicate gel, and (2) contacting the silicate in situ with at least one guanidine, or a compound closely related to guanidine, and/or a multiamine-derived cation. By aggregating the silicates, at least some exchangeable interstitial ions and at least some guanidines, or compounds closely related to guanidines, and/or multiamine-derived cations are formed. It is produced by a two-step process consisting of an ion exchange reaction to form a layered, inorganic silicate matrix. Suitable examples of swollen, layered silicate gels used as starting materials to form the silicate matrices used in the present invention include synthetic silicate mica materials. For example, U.S. Pat. No. 4,239,519 teaches a method for making gelling silicates of several precursors, including (a) fluorohectolite, hydroxyl hectorite, boron fluorophlogopite, Fluorophlogopite, hydroxyl
Boron phlogopite, and these, talc,
Substantially lithium and/or sodium water selected from the group of solid solutions with other structurally compatible substances selected from the group of fluorotalc, polylithionite, fluoropolylithionite, phlogopite and fluorophlogopite. - producing a fully or preferentially crystalline body comprising crystals consisting of swollen mica; (b) contacting said crystalline body with a polar liquid (usually water), resulting in swelling and disintegration of the crystalline body with the formation of a gel; and (c) adjusting the solid:liquid ratio of the gel to a desired value depending on the application. glass-
Ceramic is a preferred crystalline starting material.
As another example of a synthetic layered silicate starting material, U.S. Pat. Are considering. Also, US Pat. Nos. 3,325,340 and 3,454,917 teach methods for making aqueous dispersions of vermiculite flake crystals that can also be utilized as swollen, layered silicate gel starting materials. These references indicate that such crystals contain (1) alkylammonium cations having 3 to 6 carbon atoms in each carbon group, such as methylbutylammonium, n-butylammonium, propylammonium and iso-aluminum-ammonium; 2) teaches the swelling of such crystals by introducing cationic forms of amino acids such as lysine and ornithine, and/or interstitial ions such as lithium; The inorganic matrix utilized in the present invention is prepared by contacting the silicate gel starting material described above with a source of exchange cations selected from guanidine or compounds closely related to guanidine and/or multiamine derivatives to form a matrix between the starting materials. It can be prepared by an ion exchange reaction between at least some of the cations and the guanidine and/or multiamine derived cations. The particular interstitial cations in the starting material depend on the silicate gel utilized. For example, U.S. Pat.
Synthesis made according to the method of No. 4239519 or No. 4067819; No. 4045241; or No. 3936383;
When utilizing induced gelling silicates as starting materials, the interstitial cations are generally Li ⁺ and/or
or Na ⁺ ions. When utilizing natural vermiculite dispersions made in accordance with U.S. Pat.
Contains other cations specified in No. 3325340.
Silicate gel starting materials, whether synthetic or natural, generally have a morphology typified by thin flakes that are disks, strips and/or ribbons. Although we do not intend to limit flakes to specific measurements, they are typically about
500Å~100000Å, preferably 5000Å~100000Å
It has a length of 500 Å to 100000 Å, and a thickness of less than 100 Å. As used herein and in the claims, the term "charge per structural unit" is defined by Lagary and Weiss (G.
Lagaly and A. Weiss, “Determination of
Layer Charge in Mica−Type Layer
Silicates”Proceedings of International Clay
Conference, 61−80 (1969)) and G. Lagaly. “Charactrization of Clays by
Organic Compounds”, Clay Minerals, 16 , 1
-21 (1981). The starting material silicate gel is US Pat. No. 4,239,519.
No.; No. 3325340; No. 4067819; No. 4045241;
No. 3,936,383 or No. 3,434,917, or other methods that provide a release layer material with a desired range of charge densities. In this regard, it has been found that silicates having a charge density of about -0.4 or higher fail to provide articles exhibiting good durability when used in the present invention.
The starting material has a charge density of about -1 or less:
These materials cannot be prepared in dispersed form and therefore cannot be used in the present invention. The term "guanidine or a compound closely related thereto" means an aminomethyleneimine group=N-C
(-)=N-, and especially =N-C(-C)=N- or =N-C(-N)=N- groups and resonant structures derived therefrom; Used to refer to compounds with heavy bonds and cations derived from them. More specifically, their cation formulas [R ¹ C(R ² ) R ³ ] ⁺ (where R ¹ , R ² and R ³ are NH ₂ and
one or more hydrogen atoms in one or more of R ¹ , R ² and R ³ separately selected from CH ₃ with the proviso that at least two of R ¹ , R ² and R ³ are _NH 2 The above are substituents, such as C ₁ -C ₅ alkyl,
_C2 - _C5 alkenyl or _C2 - _C5 alkenyl can be substituted, and two or more groups of such substituents are combined to form one or more rings that are saturated, unsaturated or aromatic. form). It can be seen that the cation has a localized or delocalized positive charge on one group, depending on the nature of the compound from which the cation is derived, giving it a resonant structure. Examples of compounds in which cations are formed are guanidine, aminoguanidine, diaminoguanidine, methylguanidine, tetramethylguanidine, melamine, 2-aminopyridine and 2,6-diaminopyridine. Conveniently, the compounds can be used in the form of their hydrochloride or other corresponding soluble salts. For the sake of brevity,
The term "guanidine-derived cation" refers to "guanidine or a compound closely related thereto" as previously defined.
It is used to collectively refer to. The term "multiamine-derived cation" when used in reference to exchange cations utilized in the present invention refers to low molecular weight, non-polymeric di-, tri-, and/or tetra-amino functional compounds; The moieties are modified to become positively charged, for example by being protonated. Diamines are the multi-amine compounds of choice. Desired diamines generally have the following formula R ₃ N-(CX ₂ ) _o -NR ₃ , where R ₃ is each hydrogen, C ₁ to _{C 8} straight or branched chain alkyl group, and C ₃ to _{C 6} are acrylic.・Selected from alkyl groups or aryl groups, provided that one or more aryl groups are not present at each nitrogen;
each X is selected from hydrogen, an alkyl group or an aryl group; and n represents an integer from 2 to 15;
Optionally, when n is 3 or more, CX ₂ can form an aromatic cyclic moiety. ) corresponds to In multi-amino derived cations, the center of cation activity is placed on the nitrogen group in the multi-amine. Generally, this is accomplished by protonating the multiamine to generate positively charged ammonium groups. This protonation must occur before cation exchange can take place on the starting silicate gel. As mentioned above, starting with ion exchange between guanidine and/or multiamine derived cations and interstitial cations in the silicate gel to produce exchanged macroagglomerated particles to form a silicate matrix, The silicate gel is reacted with an exchange cation source derived from guanidine and/or multiamine compounds. The specific nature of the source will depend on the exchange cation utilized. and can be easily determined by a person skilled in the art. For example, if the exchange cation is guanidinium or melaminium, the silicate will be reacted with the corresponding hydrochloride or other compatible compatible salt. As mentioned above, one or more exchange cations can be utilized in the cation exchange reaction. Various cations provide a floc or matrix,
The particular cation or combination of cations will be selected by the practitioner of the invention based on the end use, as each ultimately provides a final product with different physical properties. In a preferred method of manufacturing the embedded textile material of the present invention, a layered silicate gel starting material is applied to at least one side of a suitable textile by a suitable method so as to coat the fibers making up the textile with said silicate gel. At the same time, the spaces between the fibers are completely filled.
A cation exchange reaction utilizing at least one guanidine and/or multiamine derived cation is then performed. For example, silicate gel-coated fabrics can be embedded in a guanidine-derived cation solution at room temperature by causing an ion exchange reaction between at least some gel interstitial ions and at least some guanidine-derived cations. Soaking can be allowed for a sufficient time to form a textile material. In the material production method of the present invention, a layered, silicate gel starting material is first reacted with a guanidine and/or multiamine derived exchange cation source, generally with stirring, to form an aggregated mineral suspension; can be applied to at least one side of the fabric. As used herein and in the claims, the term "fabric" refers to a material consisting of a plurality of interwoven threads, fibers or filaments. The fabrics used in the invention can be woven or non-woven with organic and/or inorganic yarns, fibers or filaments. In general, all fibers, filaments or threads present are smooth and flexible with good mechanical properties, such that the fibers, filaments or threads are coplanar and do not interfere with the film-forming properties of the silicate starting material. Can be used in paper preparation. Materials from which textiles can be made include (non-limiting) examples such as glass (e.g.
web), polyester, polyamide, polyolefin, polyacrylate, cellulose, rayon and mixtures thereof. The terms "web and mat" herein are used interchangeably, eg glass web or glass mat. The material of the invention made by the above method is flame resistant, exhibits good mechanical properties and has flexibility and smoothness. However, the mechanical properties of such materials make it possible to laminate a compatible flame resistant, swellable, layered silicate coating on one or both sides of the material to produce a laminate composite that is within the scope of this invention. I found out that things can be improved by doing this. Appropriate compatibility, swelling, and
Layered silicate coatings (without limitation) 1984
Guanidine cation exchange silicate coating prepared according to the method disclosed in U.S. Co-pending Application No. 662,057, dated Oct. 18, and disclosed in U.S. Co-pending Application No. 7,159,733, dated March 25, 1985. A multi-amine cation-exchanged silicate coating prepared by a method disclosed in the present invention. Furthermore, depending on the end use of the laminated material, swellable, compatible, organic or inorganic coatings other than layered silicate coatings can also be laminated to one or both sides of the embedded textile material according to the present invention. . for example,
Paints can be advantageously used which further improve the water resistance of the embedded textile or laminate materials of the invention. An example of such a paint is a polysiloxane/silica paint. The term "water resistant" as used herein does not mean that the articles of the invention are water resistant or completely impermeable to water; Used to indicate that tensile strength is not substantially reduced. In the following examples, unless otherwise specified,
The starting material used was lithium fluorhectorite made by the method disclosed in US Pat. No. 4,239,519. Example 1 This example describes the preparation of a guanidinium-exchanged fluorohectolite agglomerated silicate that can be applied directly to textiles by the material preparation method of the present invention. A slurry of guanidium fluorohectolite was prepared by adding 475 g of a 10% dispersion of lithium fluorhectorite to 1.4 g of a 1N guanidine hydrochloride solution. The slurry was then agitated in a high shear mixer to reduce the particle size of the resulting floc, which was washed, separated for water content, and diluted to a 2% solids slurry. Example 2 Inorganic paper-like material has a gap of 0.114 mm (4.5 mil)
The slurry of Example 1 was prepared by coating a 21.6 cm x 28 cm x 4 mm thick nonwoven glass mat using a film applicator. The coated pine was then air dried and a white mineral paper-like material was obtained. Example 3 This example demonstrates the preparation of a guanidine-exchanged layered silicate coating for use in making the laminated composite article of the present invention. 10 by the method disclosed in U.S. Pat. No. 4,239,519.
% solids lithium fluorohectolite gelled dispersion was prepared. The gap between the coating film is 0.114mm
Apply a 0.114 mm thick wet film of the dispersion onto a glass plate using a (4.5 m) film applicator.
I stretched the film and made it with 12.7cm wide material. The glass plate with the film attached is next
It was immersed in a 0.25M guanidinium hydrochloride solution to allow cation exchange between guanidinium cations and interlayer cations of fluorhectorite. A skin immediately formed on the film, indicating that such exchange had occurred. After 10 minutes, the film was removed from the glass plate, washed with deionized water to remove residual salts, and dried. The film showed good flexibility and strength retention when wet. Example 5 Inorganic paper was prepared by coating a 10% lithium-fluorhectorite suspension onto a 21.6 cm x 28 cm x 4 mm thick non-woven glass mat using a film applicator with a gap of 0.114 mm. Prepared. The coated glass was then immersed in 1000 ml of a 0.25 M aqueous solution of guanidine hydrochloride (60°C) to obtain flocculation of fluorohectolite via an ion exchange process. The guanidinium fluorohectolite was then removed from the salt solution and washed with fresh water to remove excess salt. The coated pine was then air dried to yield a white, flexible, smooth mineral paper. Example 6 A 21.6 cm x 28 cm guanidinium fluorohectolite coating was prepared by spreading a 10% lithium fluorohectolite suspension onto a 21.6 cm x 28 cm glass plate using a film applicator with a gap of 0.114 mm. The coated solution was prepared by immersing it in 1000 ml of 0.25M aqueous guanidine hydrochloride solution (60°C). After 10 minutes in the salt solution, the glass plate containing the coating was removed and excess salt was removed from the coating by immersing it in a bath containing fresh water. The two guanidinium fluorohectolite coatings thus prepared were then coated with guanidinium fluorohectolite coatings prepared as described in Example 5.
Laminated on one side of the fluorohectolite pine. The coatings and mats were pressed together while wet using a roller press laminator. The resulting laminated guanidinium fluorhectorite mat was then air or oven dried to yield a strong white, flexible, smooth, inorganic paper. Comparative Example This comparative example shows that the use of polymeric amine compounds as exchange cations in the process of the invention is unsuitable for reasons of technical processing. The method of Example 6 was repeated, except that the lithium fluorohectolite coated plates were soaked in 1000 ml of 3% Kymene solution for 24 hours at 25°C. The resulting structure was not complete and broke when handled by hand. Applications The inorganic papers prepared in Examples 5 and 6 were tested for use as substrates for recording information. These papers were typed using an IBM typewriter, usually equipped with carbon ribbon. They were written and copied using a blue ink plain ballpoint pen and a photocopy machine, respectively. In all cases of testing, text typed, written or photocopied on mineral paper showed excellent visual contrast with the paper. Additionally, carbon, ink, and photocopier toner all maintained good adhesion to the mineral paper without smudging, similar to that seen when using regular bond paper. When other inorganic materials, such as glassy ceramic surfaces, were similarly tested, ink or carbon adhesion was poor. Flammability The inorganic papers prepared by the methods of Examples 5 and 6 were tested for flammability. The paper prepared in Examples 5 and 6 was typed and exposed to the flame of a Bunsen burner for 30 seconds. These experiments were repeated using similar papers from Examples 5 and 6 that were typed and then coated with the polysiloxane/inorganic paint described in Example 9 below. Next, observations were made regarding (1) ease of ignition, and (2) legibility of print after 60 seconds of exposure to flame.

[Table] Later type size
Poor Very good Very good readability
Good * (a): Paper does not catch fire even when heated to red.
From the above data, it is clear that no burning of the paper was observed even after prolonged heating until the paper became red hot. After cooling, the paper remains intact and characters typed on the paper can still be read when using laminated paper (Example 6). Smoothness Electron micrographs of the papers prepared in Examples 5 and 6 show a very smooth surface compared to sheets containing loose fibers. Paper prepared according to the invention does not exhibit surface voids as seen in sheets containing loose fibers. Since the fibers used in the present invention are parallel to the surface, no interruptions in the alignment of the laminae occur during papermaking, resulting in a smooth surface. Example 7 A colored inorganic paper was prepared by adding 0.5% by weight of chromium oxide pigment to a 10% lithium fluorohectolite suspension. A paper was prepared by the method described in Example 11 using a colored lithium fluorhectorite suspension mixed with the pigment and then stretched onto a glass mat and plate. . The final paper product had a green color. Example 8 The method of Example 7 was repeated except that red pigment was utilized in place of the chromium pigment. The final paper product had a red color. Example 9 Both sides of dry paper were coated with 0.0254 mm of a 30% solids solution of a 70/30 parts by weight polysiloxane/silica inorganic paint.
(1 mil) thick coating improved the water and flame resistance of the mineral papers prepared in Examples 5 and 6. The solvent was removed by drying. When these papers were treated in this way, the water no longer wet the paper but beaded on the surface. Example 10 Except that the nonwoven fabric was made of polyester,
A paper-like material was made using the method described in Example 5. Example 11 A paper-like laminate composite was prepared by laminating a guanidinium coating on both sides of a guanidinium fluorohectolite coated fabric prepared according to Example 10. Example 12 A paper-like material was prepared using the method described in Example 5, except that a woven glass fiber fabric was used instead of a non-woven fabric. Example 13 A paper-like laminated composite article was prepared by laminating a guanidinium coating on both sides of the guanidinium fluorohectolite coated fabric prepared according to Example 12. Example 14 A paper-like material was prepared according to the method described in the Examples, except that a three-dimensional woven fabric made of nylon was used. Example 15 A laminate composite was prepared by laminating a guanidinium coating to the guanidinium fluorohectolite coated fabric prepared according to Example 14. Mechanical Properties The dry and wet tensile strength of the above materials and of ordinary bond paper are shown in the table below:

TABLE As can be seen from the table above, materials consisting of textiles embedded in silicate matrices exhibit dry and tensile strengths that are very close to or even higher than those of conventional bond papers. Example 16 Using a film applicator with a gap of 0.114 mm, a non-woven glass sheet with a thickness of 21.6 cm x 28 cm x 4 mm was prepared.
Mineral paper was prepared by coating pine with a 10% lithium fluorohectolite suspension. The coated glass pine was then immersed in 1000 ml of a 0.25 M solution of hexamethylene diammonium dihydrogen chloride (60°C) for 10 minutes.
and caused the aggregation of fluorohectolite through an ion exchange process. The guanidinium
The fluorohectolite pine was then removed from the salt solution and washed with fresh water to remove excess salt. The coated pine was then air-dried to yield a white, flexible, smooth mineral paper. Example 17 10% lithium was applied onto a 21.6 cm x 28 cm glass plate using a film applicator with a gap of 0.114 mm.
A 21.6 cm x 28 cm hexamethylene diammonium hectorite coating was created by stretching the fluorohectolite suspension and immersing the coated glass plate in 1000 ml of a 0.25 M aqueous solution of hexamethylene diammonium dihydrogen chloride. I made a membrane.
After 10 minutes in the salt solution, the glass plate containing the coating was removed and excess salt was washed from the coating by immersing it in a bath containing fresh water. The two hexamethylene diammonium fluorohectolite coatings thus prepared were then laminated to both sides of the hexamethylene diammonium fluorohectolite matte prepared as in Example 16. The coatings and pine were pressed together while wet using a roller press laminator. The resulting laminated hexamethylenediammonium fluorohectolite pine is then air- or oven-dried to produce an intensely white,
A flexible, smooth inorganic paper was obtained. Example 18 A 10% lithium-fluorhectorite suspension was spread on a 21.6 cm x 28 cm glass plate using a film applicator with a gap of 0.114 mm, and then the coated plate was coated with a 0.25 M aqueous solution of guanidine hydrochloride at 60°C.
A 21.6 cm x 28 cm guanidium fluorohectolite coating was made by dipping in 1000 ml. After 10 minutes in the salt solution, the glass plate containing the coating was removed and excess salt was washed from the coating by immersing it in a bath containing fresh water. The two guanidinium fluorohectolite coatings thus prepared were then laminated to both sides of a hexamethylene diammonium fluorohectolite matte prepared as in Example 16. The coatings and pine were pressed together while wet using a roller press laminator. The resulting laminated guanidinium fluorhectorite mat was then air or oven dried to yield a strong white, flexible, smooth inorganic paper. Example 19 This example illustrates the lamination of an organic coating to an embedded textile material of the present invention. The laminated composite material was prepared by first making the embedded textile material according to the method of Example 5. 0.0254mm by using a hot press for 10 minutes at a pressure of 700Kg/ ^cm2 and 149℃
(1 mil) thick polyvinylidene fluoride coating was laminated.

Claims (1)

Claims: 1. A layered layer comprising (a) an average charge per structural unit of from about -0.4 to about -1, and (b) interstitial cations selected from the group consisting of guanidine and multiamine derived cations. A method for producing a high temperature, paper-like inorganic material, characterized in that it consists of embedding a fabric in a silicate matrix. 2. Process according to claim 1, characterized in that the layered silicate matrix is derived from synthetic, gelling silicates with interstitial Li ⁺ and/or Na ⁺ cations. 3. The method according to claim 2, wherein the synthetic silicate is synthetic tetra-silicate mica. 4. The method according to claim 2, wherein the synthetic silicate is synthetic taeniolite. 5. The method according to claim 2, wherein the synthetic silicate is synthetic hectorite. 6 The synthetic silicates include fluorohectolite, hydroxyl hectorite, boron fluorophlogopite, hydroxy boron phlogopite, solid solutions thereof, and combinations thereof with talc, fluorothalc, polylithionite, and fluoropolylithionite. , a body consisting essentially of water-swellable mica crystals selected from the group of solid solutions with other structurally compatible materials selected from the group consisting of phlogopite and fluorophlogopite, in a polar liquid and a gel. 3. A method according to claim 2, characterized in that it is prepared by contacting for a period sufficient to effect swelling of the crystals with formation. 7. The method according to claim 6, wherein the crystal is fluorohectolite. 8. Process according to claim 7, characterized in that the guanidine-derived cation is selected from the group of diaminoguanidine, tetramethylguanidine, guanidine, aminoguanidine, methylguanidine and melamine derivatives. 9. The method according to claim 6, characterized in that the polar liquid is water. 10. Claim 1, characterized in that the layered silicate matrix is derived from vermiculite with alkyl ammoniums, cationic forms of amino acids and/or Li ⁺ interstitial ions.
The method described in section. 11 The fabric is prepared by (a) coating the fabric with a swollen, layered silicate gel having an average charge per structural unit of about -0.4 to about -1 and containing exchangeable interstitial ions; The swollen spherical silicate is reacted with at least one cation selected from the group consisting of guanidine and multiamines to form ions between at least some of the exchangeable interstitial ions and at least some of the guanidine-derived cations. 2. A method according to claim 1, characterized in that embedding in a layered silicate matrix is carried out by an exchange reaction, thereby forming a layered silicate matrix. 12 The woven fabric has an average charge per structural unit of about -
embedded in a layered silicate matrix by coating with a flocked mineral material consisting of a swollen, layered silicate gel having a swell of 0.4 to about -1, the silicate being a group consisting of guanidine and multiguanidine derived cations. A method according to claim 1, characterized in that it contains at least some interstitial cations selected from: 13. The method according to claim 1, characterized in that the fabric is made of glass mat. 14. The method according to claim 1, characterized in that the fabric is made of polyester. 15. The method according to claim 1, characterized in that the fabric is made of polyamide. 16 comprising the step of embedding the fabric in a layered, silicate matrix (a) having an average charge per structural unit in the range of about -0.4 to about -1, and (b) containing guanidine-induced interstitial cations. A method according to claim 1, characterized in that: 17 embedding the fabric in a layered, silicate matrix (a) having an average charge per structural unit ranging from about -0.4 to about -1, and (b) containing multiamine-derived interstitial cations. A method according to claim 1, characterized in that: 18 (a) (i) has an average charge per structural unit in the range of about -0.4 to about -1, and (ii) contains interstitial cations selected from the group consisting of guanidine and multiamine derived cations. A method for producing a high temperature, paper-like inorganic material, comprising the steps of: embedding a fabric in a layered silicate matrix; and (b) laminating a compatible paint on at least one side of the embedded fabric. 19. A swollen, layered coating having an average charge per structural unit ranging from about -0.4 to about -1 and containing at least some interstitial cations selected from the group consisting of guanidine and multiamine derived cations. 19. A method according to claim 18, characterized in that it is prepared from a silicate. 20 The layered silicate matrix is composed of Li ⁺ or
19. Process according to claim 18, characterized in that it is derived from a synthetic, gelling silicate with Na ⁺ interstitial cations. 21. Process according to claim 18, characterized in that the layered silicate matrix is derived from vermiculite with alkyl ammoniums, cationic forms of amino acids and/or Li ⁺ interstitial ions. . 22. The method of claim 18, wherein the coating is a polysiloxane/silica coating. 23 (a) having an average charge per structural unit in the range of about -0.4 to about -1, and (b) comprising at least some interstitial cations selected from the group consisting of guanidine and multiamine derived cations;
A high temperature, paper-like inorganic material characterized by consisting of a woven fabric embedded in a silicate matrix. 24. The material according to claim 23, wherein the fabric is made of glass mat. 25. The material according to claim 23, characterized in that the fabric is made of polyester. 26. Material according to claim 23, characterized in that the fabric consists of polyamide. 27 (a) a layered structure having an average charge per structural unit ranging from about -0.4 to about -1 and (b) comprising at least some interstitial guanidine-derived cations;
24. High temperature, paper-like inorganic material according to claim 23, characterized in that it consists of a fabric embedded in a silicate matrix. 28 A layered, silicate matrix-embedded fabric that (a) has an average charge per structural unit ranging from about -0.4 to about -1 and (b) includes at least some interstitial multiamine-derived cations. The high temperature, paper-like inorganic material according to claim 23, characterized in that it consists of: