JPS6197155A - Flock mineral material and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION INDUSTRIAL APPLICATIONS This invention relates to flocked mineral materials, and more particularly to flocked mineral materials that can be utilized in the production of water-resistant, non-asbestos high temperature products.

BACKGROUND OF THE INVENTION Non-asbestos papers and sheets are known to be created from water-swellable inorganic materials, particularly swollen silicate gels. For example, US Pat. No. 4,239,519 discloses an inorganic, crystal-containing gelling material.

The present invention relates to the production of water-swellable sheet silicates and articles made therefrom, such as fibers, films, boards and coatings. These non-asbestos papers and sheets exhibit good high temperature stability and good chemical resistance. Moreover, since no asbestos fibers are used in their manufacture, such articles do not have the health hazards associated with articles containing asbestos.

U.S. Pat. No. 4,259,519 discloses a method for producing a gelling silicate precursor for use in the production of non-asbestos paper and sheet products, which includes five basic steps: . The production method includes (a) fluorohectolite (fl
urhectorite), hydroxyl hectorite, boron fluorophlogopite.

A group of solid solutions of fluorophlogopite, hydroxyl boron phlogopite, and structurally similar substances selected from the group of talc, fluorophlogopite, polylithionite, fluoropolylithionite, phlogopite, and fluorophlogopite. (b) forming a wholly or predominantly crystalline body comprising crystals consisting essentially of lithium and/or sodium water-swellable mica selected from; (b) forming the crystalline body with a polar liquid (usually water); A step of bringing the crystalline substance into contact with it to cause it to swell and disintegrate (accompanied by the formation of a gel); (C) a step of adjusting the solid to liquid ratio of the gel to a desired value depending on the application; Become.

Glass-ceramics are desirable crystalline starting materials. These products are then brought into contact with a large cation source, one with a larger ionic radius than the lithium cations, resulting in large flocculation of the gel.

and L from those large cations and the intermediate layer of the crystal.
An ion exchange reaction is caused between L and or Na ions.

Also, U.S. Pat.
No. 1I 514.917 specifies (1) alkylammonium cations having 3 to 6 carbon atoms in each carbon group, such as methylbutylammonium, n-butylammonium, furobylammonium and isoamylammonium; and (2) lysine. , and cationic forms of amino acids such as ornithine.

and/or (3) teaches the production of aqueous dispersions of swollen vermiculite flake crystals for the introduction of interstitial ions such as lithium.

The problem that the invention seeks to solve Paper manufactured according to the prior art methods described above.

Although articles such as sheets and films exhibit excellent heat resistance and are extremely useful in a wide range of applications,
These items exhibit water sensitivity, which is commonly exhibited by items that exhibit significant loss of strength and deterioration of mechanical and electrical properties when exposed to high humidity environments or submerged in water or other polar liquids. . This water sensitivity reduces the utility of these articles in some applications, such as head caskets, electrical insulators, environmental protection coatings, and washable and environmentally stable building materials.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a high-temperature, fire-resistant, non-asbestos, water-resistant article which has significantly better mechanical and electrical properties than prior art articles.

Sheet paper, paperboard, film according to the invention.

High-temperature, fire-resistant, non-asbestos, water-resistant products such as textiles and coatings are prepared by utilizing exchanged cations selected from guanidine derivatives. It was discovered that it could be made from materials. Surprisingly, the articles were found to exhibit significantly better results in tensile strength and puncture resistance tests when wet than materials prepared utilizing conventional exchange cations. Additionally, articles made in accordance with the present invention generally exhibit superior electrical and mechanical properties over materials made by conventional methods.

Regarding heat resistance, articles produced according to the present invention have a rating of about 5.
They are quite stable at humidity of 50-1100°C and maintain their structural stability up to about 800°C.

In one embodiment, the articles of the invention and the flocculated mineral suspensions are made of water-swellable silicates having an average charge of about -α5 to -1 per structural unit as the starting material. (contains interstitial exchangeable cations that promote swelling). The particular exchange cation in the starting material depends on the silicate utilized. For example, when synthetically derived gelling silicates prepared according to the method of US Pat. No. 14,259,519 are utilized as starting materials, the exchange cations are generally Li+ and/or Na ions. be. U.S. Patent No. 3,525
．． When a natural vermiculite dispersion made according to No. 3110 is utilized, the exchange cations generally include the alkylammonium cations and other cations specified in that patent.

Silicates, whether synthetic or natural, generally have a morphology represented by thin flakes, which are disks, strips or ribbons. Their flakes typically range from about 500 to
100,0OOA, preferably 5oooX to 100.
It has a length of OOOA, a width of 500 to 100 degrees, a width of 100 degrees or less, and a thickness of less than 100 degrees. In the present specification, the term "charge on the structural unit" is +Lagal
CG, which refers to the average charge density defined by Y and Weiss, LagaLy and A, Weiss,
”Determination of Layer
CharFein Mica-Type Layer
5ilicates', Proceedivgso
f International C1ay Conf
erence+ 6140 (1969) and G,
LagaLy, “Characterizationo
f C1ays by Organic Compou
nds', ClayMinerals, 16.1
-21-21 (19,1.

The starting silicate material is described in the aforementioned U.S. Pat. No. 4,239,5.
No. 19; No. 3.325.3140; and No. 3. li
The silicate, which can be made by the method of T.T., No. 917, or another method that results in a dissociation layer material with a charge density within the desired range, is then contacted with at least one guanidine-derived cation source. By that.

An ion exchange reaction occurs between cations and interstitial ions. This ion exchange reaction takes place between the cations and the silicate material to produce flocs.

This flock is then utilized in the form of the article of the invention. In another embodiment of the present invention, the starting material silicate is directly formed into a product such as a lithium fluorohectolite fiber or film by utilizing the method of U.S. Pat. No. 11,259,519. let A cation exchange reaction utilizing guanidine-derived cations is then carried out with the product, for example, by soaking the product in a solution of guanidine-derived cations. The ion exchange reaction is therefore carried out in situ during the actual production of the product.

The exchange cations utilized in the present invention are derived from compounds corresponding to the following formula: where R-C-R is selected from -bTHz and -CH, respectively, where R, R At least two of R2 are -NH, ash, R, R+ and/or R
1019 or 19 or more hydrogens can be substituted with substituents such as CI CI + alkyl, C-C6 alkenyl, C-C, alkynyl, and two 19 or more groups of those substituents are combined to form any However, they can form rings such as aromatic rings.

The 70% mineral suspension of the present invention is prepared by stirring, for example, in order to allow the ion exchange between the guanidine-derived cations and the interstitial cations to take place in a silicate gel to form exchanged giant agglomerated particles. It is prepared by reacting a suitable silicate gel with an exchange cation source derived from a guanidine compound of the formula above. For example, if the exchange cation is guanidium or melanium, the silicate is reacted with the corresponding hydrochloride.

As mentioned above, one or more cations derived from the above formula can be utilized in cation exchange reactions. The particular cation or mixture of cations is selected based on the desired end use, as different cations provide flocs and finished products of different physical properties.

Flocked mineral suspensions are used to produce desired end products. The particular processing steps applied to the flock will depend on the particular article being formed. For example, when an article of the present invention is made into sheet material, the resulting exchange floc is agitated with sufficient shear to obtain a particle size distribution that will lead to appropriate particle size control in the sheet forming operation. After this process.

The floc is optionally washed to remove excess salt solution. The consistency of the flocked slurry is then adjusted to about 0.75-2% solids. To increase the rate of dewatering on the Fourdrinier screen, a polyelectrolyte flocculant is added to the slurry at a level of floc solids of about 0.1-1%, desired L<Ho2-05%. I can do it.

One example of a suitable polyelectrolyte is Polymine (Pol
ymin) P (this is BASF's trademark for polyethylene imine).

This slurry is then sent to a smelter where it is dewatered by free dehydration or vacuum dehydration, followed by pressing and drying on a drum dryer. The sheet material thus formed is used for applications such as gaskets.

If necessary, further inert materials can be added to the flocked mineral suspension depending on the application of the product. For example, one or more fiber materials from natural or synthetic organic or inorganic fibers may be selected and used, if necessary, to improve the dewatering rate and provide a final product with superior strength and handling properties. can be added to the floc.

for example.

If the final product is a gasket, the fibers to choose are cellulose fiber, glass fiber, and/or Kepler (Kev
In addition, latex or other binders can be added to the flock to provide a product of superior strength.

If the cation exchange reaction is to be carried out directly on the product formed from the silicate starting material, the slurry of the silicate starting material is Add necessary inert materials.

The term "water resistant" as used herein does not mean that the article of the present invention is water resistant or completely impermeable; it does not mean that the article is water resistant or completely impermeable; Used to indicate that their tensile strength and puncture resistance are not substantially reduced.

In the examples described below, unless otherwise specified, the starting material utilized was lithium fluorhectorite, prepared according to the method disclosed in US Pat. No. 11,239,519.

Example 1 This example shows fluorohectolite with guanidium exchanged.
A method of manufacturing flocked silicates and sheets prepared therefrom is described.

Guanidium fluorohectolite slurry is IN
Guanidine hydrochloride solution LLjjl! It was prepared by adding 1j75,9t of a 10% dispersion of lithium fluorohectolite. The slurry was then agitated in a high shear mixer to reduce the particle size of the resulting floc, washed, and analyzed for water content, with a solids content of 2%.
It was diluted to make a slurry. The obtained slurry was molded into a 29.2x2CA2m hard sheet mold (W
illiams Apparatus). The resulting sheet was then wet pressed and dried in a drum dryer. The sheet had good malleability and showed good gasket seal test results.

EXAMPLE 2 This example illustrates a process for making a film of the invention in which cation exchange is performed in situ. A gelatinized dispersion of light was prepared.・2 4.5ml/l with this material
The film was made using a (approximately 0.14 um) applicator, a coating tool capable of drawing a wet film of the dispersion 5 inches wide and 0.1111 um thick onto a glass plate. The glass plate with the film attached was then immersed in a 0.25 M guanidium hydrochloride solution to immediately coat the surface of the film to allow cation exchange between the guanidium cations and the fluorohectolite interlayer cations. was formed. This clearly indicates that such cation exchange has occurred; after 10 minutes the film was removed from the glass plate and washed with deionized water to remove residual salts.

Dry. The resulting film showed good flexibility and strength retention when wet.

Examples 5-9 The method of Example 1 was essentially repeated for each of these examples to produce the corresponding films with the specific exchanged cations. In Example 7, a 01N melamine hydrochloride solution was used. In all other examples, 0.25 N solutions of the respective exchange sources were used as follows: 5 Diaminoguanidine hydrochloride 4
Aminoguanidine hydrochloride 5 Tetramethylguanidine hydrochloride 6 Methylguanidine hydrochloride 7 Melamine hydrochloride 8 2,6-diamitubiridine hydrochloride 9
2-Aminopyridine Hydrochloride Comparative Examples 1-3 These comparative examples illustrate fluorohectolite films made with various prior art exchange cations.

Potassium fluorohectolite (KFH) and ammonium fluorohectolite (NH4FH) of O.l 1 inch thickness were prepared separately by the method specified in US Pat. No. 14,239,519. Next, KFH
A film of slurry of NH and FH was poured. Kymene (Hercules trademark for cationic polyamide-epichlorohydrin resin) fluorohectolite film also contains (1) 5.0% K;
ymene solution, and (2) the lithium fluorohectolite film was Ky.
It was prepared by the method of Example 2, except that it was immersed in the mene solution for 2 hours. These films, along with the films made in Examples 2-3, were first subjected to tensile strength and puncture resistance tests as described below.

Dry tensile strength was measured using an Instron.
, jaw spacing L 5 in (5,8 Crr) - crosshead speed 0,2 in (0,5 tCrn)/
I went in minutes.

Wet strength measurements were performed by contacting water-saturated sponges to both sides of the film for 10 seconds while the sample was placed in the Instron clamp immediately prior to strength testing.

The film sample was secured to a holding device and a loadable needle was applied against the film in a direction perpendicular to the surface of the film, increasing the load until the needle penetrated the film. The film in the holder in the wet test was immersed in deionized water for 10 seconds prior to the puncture resistance test.

These test data are shown in the table below.

Table 2 Guanidium 14,000 9,000 7
,100 Il, 600 radiaminoguanidium 13,000 11,000 lit,
000 11,2004 Aminopyridium L5,000 11,000 g5oo
5,5005 Tetrame fk'ζr=Dium 11,00 (111,00013,0004J40
06 Methylguanidium 5200 2!3
00 6600 5.11007 Melami Lam 19,001+ 20.000 10,
000 5. U008 2.6-, ;7 minoff 1 nojiy 13,000 5,300
7,900 3.600 (protonation) 9 2-aminopyridy 11,0OLI 7.
+100 7.800 3.600 (protonation) i Kimene (protonation) 7,000
2,700 900 2602 77
Monium U, 500 1JOO5,500
61!05 Potassium 1,100
200 5.500 11110 The above data show that films made according to the method of the present invention have significantly superior wet tensile strength and superior puncture resistance when compared to conventional compositions.

The film made according to Example 2 had an ASTM-E-
Fire resistance and smoke resistance tests were conducted according to the method specified in 662-79. Five different tests were conducted and the results are shown below. These values correspond to the maximum optical density according to the American Standard Standard Quantity Technology No. 1-Nα 70 g.

U10 Electric property sequence 2 and example 7. And the film of Comparative Example 7 was dried to give an AS
Dielectric strength was tested using the method of TM-D149. The results are shown in the table below.

Film dielectric strength (v/mcm) 1
2 5,000 cases 7
9. OOO comparative example 5
2,920 * 0.025 m in 1 ml Comparative Examples 4 and 5 These examples use as starting materials silicate materials which are outside the scope of the present invention in their charge on their structural units and in their physical fAl constants. Indicates the use of

In Comparative Example 4, C1ay Minerals Co., Ltd. (USA)
A 10% aqueous dispersion was prepared from natural hectorite obtained from a clay mineral deposit in Bloomington, Indiana. In Comparative Example 5, a 10% aqueous dispersion was made using sodium montmorillonite obtained from the same source. In each comparative example, the film was
It was subtracted using the method shown in . The glass plate with the film was then soaked in a 0.25 M guanidine hydrochloride solution for 10 min.
Soaked for minutes. In both cases no coherent films were obtained.

Example 10 This example illustrates the preparation of a film of the invention using vermiculite starting material. U.S. Patent No. 3.325
．． A 10% solids suspension of n-butylammonium vermiculite prepared by the method specified in No. 5110 was cast as a film onto a glass plate according to the method set forth in Example 2.

The glass plate with the film attached was immersed in a 0.25 M guanidinium hydrochloride solution for 10 minutes. The resulting film was removed from the glass plate, washed and dried. The film exhibited tensile strength and wet strength in the punch fold test that similar vermiculite films without cation exchange did not exhibit.

Example 11 This example illustrates the production of fibers using the method of the present invention. A 15% solids suspension of lithium fluorhectorite was extruded into a 2N guanidine hydrochloride solution through a needle with a C279+as (l ml) opening. The extruded fibers are supported by a porous belt and transported to the second
to a 2N quanidine hydrochloride bath. The fibers thus prepared were washed by soaking in deionized water, and upon drying the resulting fibers were strong and malleable.

Claims (1)

Claims: (1) A swollen, layered, silicate gel having an average charge of about -0.5 to -1 per structural unit and containing exchangeable interstitial ions containing at least one type of guanidine; Forming a water-resistant non-asbestos high temperature article characterized by contacting with derivatized cations to effect an ion exchange reaction between exchangeable interstitial ions and at least some guanidine derivatized cations. Methods of manufacturing available flocked mineral materials. (2) Claim 1, characterized in that the gelling, layered silicate is a synthetic, gelling silicate, and the interstitial ions are Li^+ and/or Na^+.
The method described in section. (3) The synthetic silicates include fluorohectolite, hydroxyl hectorite, boron fluorophlogopite, hydroxyl hectorite, solid solutions thereof, and combinations thereof with talc, fluorotalc, polylithionite, and fluoropolymers. Formation of a gel by combining a polar liquid with an object consisting essentially of water-swellable mica crystals selected from solid solution with a structurally similar substance selected from the group of lithionite, phlogonite and fluorophlogonite. 3. A method according to claim 2, characterized in that the method is prepared by contacting the crystals for a period sufficient to cause swelling of the crystals. (4) The method according to claim 5, wherein the crystal is fluorohectolite. (5) The method according to claim 3, wherein the polar liquid is water. (6) The method according to claim 1, wherein the silicate is vermiculite, and the interstitial ions are an alkyl ammonium cation, an amino acid cation, and/or Li^+. (7) The guanidine-derived cation is selected from the group of diaminoguanidine, tetramethylguanidine, guanidine, aminoguanidine, methylguanidine and melamine derivatives. Method. (3) Swollen, layered, having an average charge of about -0.5 to -1 per structural unit and containing at least some interstitial cations that are guanidine derivatives. A flocked mineral material characterized in that it consists of a silicate gel. (9) A flocked mineral material according to claim 8, characterized in that the silicate is synthetically derived. (10) The silicates include (1) fluorohectolite, hydroxyl hectorite, boron fluorophlogopite, hydroxyl boron phlogopite, solid solutions thereof, and combinations thereof with talc, fluorothalc, polylithionite, fluorophlogopite, and solid solutions thereof. water-swellable mica selected from the group of solid solutions with structurally similar substances selected from the group of orpolylithionites, phlogopites, and fluorophlogopites and containing interstitial cations of lithium and/or sodium; An object consisting essentially of crystals of
(2) contacting the gel so formed with at least one cationic guanidine derivative to remove at least some of the lithium; and/or prepared by an ion exchange reaction between sodium cations and at least some guanidine-derived cations.
Flocked mineral materials as described in Section. (11) The flocked mineral material according to claim 10, wherein the crystal is fluorohectolite. (12) The flocked mineral material according to claim 10, wherein the polar liquid is water. (13) The flocked mineral material according to claim 8, wherein the silicate is vermiculite. (14) The interstitial cation which is a guanidine derivative is selected from the group of diaminoguanidine, tetramethyl guanidine, guanidine, aminoguanidine, methyl guanidine, and melamine derivatives. Flocked mineral material according to paragraph 13. (15) A high temperature characterized by being prepared from a swollen, layered silicate having an average charge of about -0.5 to -1 per structural unit and containing at least some interstitial cations that are guanidine. , water resistant product. (16) The high-temperature, water-resistant product according to claim 15, characterized in that it is prepared from silicate floc. (17) The high temperature and water resistant product according to claim 15 or 16, which is a sheet material. (18) The high temperature and water resistant product according to claim 15 or 16, which is a fiber. (19) The high temperature and water resistant product according to claim 15 or 16, which is a film. (20) has a charge of about -0.5 to -1 per structural unit,
An article made from a gelling, layered, water-swellable silicate containing exchangeable interstitial ions is contacted with at least one source of guanidine-derived cations to form at least some guanidine-derived cations. 1. A method for producing a water-resistant, high-temperature silicate product, comprising the step of performing an ion exchange reaction with at least some interstitial ions.