TW577904B - Amine terminal-Mannich oligomer-modified clay, nano silicon sheet derived from the clay, and method for producing the same - Google Patents

Abstract

The present invention provides an amine terminal-Mannich oligomer-modified clay, which possesses excellent surfactant function and can be used as polymer reinforcing agent, and a nano silicon sheet produced from the same. A linear amine terminal-Mannich oligomer (AMO) polymer intercalating agent is synthesized from a polyoxy alkylene amine with a molecular weight of over 1000, p-cresol, and formaldehyde. The intercalating agent is used to modify a siloxane layered inorganic clay (e.g. montmorillonites) to obtain an amine terminal-Mannich oligomer-modified clay. The invented method comprises polymerizing a polyoxy alkylene amine with a molecular weight of over 1000, p-cresol, and formaldehyde to obtain a linear amine terminal-Mannich oligomer (AMO) polymer intercalating agent; using an inorganic acid to acidify the intercalating agent; mixing the resulting mixture with a water-swollen siloxane layered inorganic clay; and strongly mixing the mixture at 60 to180 DEG C to perform a cationic ion exchange reaction in order to produce an amine terminal-Mannich oligomer-modified clay. The produced amine terminal-Mannich oligomer-modified clay can be further extracted by a hydroxide or chloride of an alkali metal or alkali earth metal to obtain a nano silicon sheet. The AMO intercalating agent can be recycled.

Description

5779〇4

[Field of the Invention] The present invention relates to Mannisamine-modified clay and nanostone tablets and a method for making the same, and particularly refers to polyetheramines (bolyoxyalkylene amines) with molecular weight (above 0.0000), p-cresol and formaldehyde. Polymerization reaction: Ί linear nissan polymer intercalating agent, the aforementioned intercalating agent is acidified with i acid, and then mixed with water-swelled silicon under strong stirring to perform cation exchange reaction = system: = Nissamine modified clay. It can be further extracted with alkali metal or alkaline earth metal lice oxide or chloride to obtain a nanostone tablet and its manufacturing method. [Knowledge of Skills] Silicone-layered inorganic clay has been used as a reinforcing material for catalysts and polymer materials in the past. It can be loosened by intercalation of organic quaternary ammonium salts (nte: Calating) to loosen the clay interlayer. At this time, the distance between layers is about i0jOA. This loose interlayer can allow monomers to enter and exit, and then know the delaminated organic / inorganic nano polymer composite material through the polymerization reaction. Material as a reinforcing material for polymer materials can improve the thermal properties, mechanical properties, gas barrier properties and flame resistance of polymer materials. Organic / inorganic nano polymer composites are considered to be important materials in the new century. The development and application of this kind of materials is a very important subject for research and development in academia and industry. In recent years, the literature and patents in this area A lot has been published. For example, ’T · J · Pinnavaia (Michigan State University) found that diglycidyl ether of ΒΡΑ,

577904

Oxygen resin EP〇n8 28) can be polymerized to form nano-scale polyether: clay composite material through intercalation agent CHj ((:)) η—ΝΗγ. Intercalation agent dissociation can be achieved. Reach layer distance 18A, and then 75 The epoxy resin at ° C aggregates by itself; the heat distortion temperature is increased, and the regularity of the two-layered plate is equal to f, which can be from a single layer (m0n〇layer) to a double layer (biUyer), or even a layer structure (Pseudo-trimolecular), the distance between layers is 13. 8 Γ

between. Intercalation at this width allows the epoxy resin to enter the polymerization and further disperse the layered inorganic matter to achieve the application effect of nanomaterials. On the other hand, Toyota Corporation has developed the first commercially successful organic / inorganic nano-polymer composite material with [Ma mine] uc〇〇-]-montmorillonite Nylon 6. It is described in Japanese Announcement No. 8- 2 2 9 4 6 that the intercalation reaction is performed with aminOCarb0xylic acid, and the interlayers of the layered silicic acid hooves are enlarged and separated by caprolactam monoamine The body (^ 1 ^ 〇1 ^ 1 ^ 111) is subjected to a condensation polymerization reaction between sandwiches, so that the layered silicate is thin. 6) A uniformly dispersed structure is formed in the resin. However, it is difficult to uniformly disperse the layered oxalate flakes in other resins other than the polyamide tree. For example, it is very difficult to uniformly disperse a highly layered oxalate in non-polar polyethylene or polypropylene.

Goode solves this problem, and it is described in Japanese Public Patent No. 8-5 3 5 7 2 that the intercalation reaction is performed with 1 ion and 乂 nium ion (〇nium i〇r〇), the layered silicon = t ί ΐ Enlarge it and mix it with the molten polyhydrocarbon resin to make the layered stone eve =: the flakes form a uniformly dispersed structure in the resin. Although organic ions can expand the interlayer distance of the layered silicate, olefin resins are easier

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‘2 continuous, 2’ But because the organic intercalating agent and olefin are not enough, and the strength of the layer is strong, the affinity of a fine is still gluten. The license is 10-1 8 2 8 9 2 Limit ^^ f / difficult. In addition, the olefin oligoacid salt and the hydrogen-bonding bond-like salt of the present binding functional group are infinitely swellable in the resin :, this: insert :::: J bond 2-based olefin polymer 81. Said to Xing a wind bond function, especially the resistance to a large amount of oligomers will make the resin _ [Summary of the invention] Therefore, the object of the present invention is to provide a manganese amine (Amine Terminal) -Mannich Oligomer (referred to as ΑΜΟ) as an intercalating agent to modify silica-based layered inorganic clay to make its lipophilicity compatible with polymers and to extend the distance between layers to 20 ~ 9 to help polymers enter Clay inflammation layer 'makes the clay reach nanometer scale and disperse in the polymer to obtain a new type of organic / inorganic polymer composite. The invention can also use intercalation agent and the ratio of generating quaternary amine, which can be tortuous (Zig- Zag) segmented chain of Mannissamine is stretched into a straight line and the clay with primary and secondary structure is directly delaminated to obtain the basic unit of clay flakes. The basic unit of clay flakes has a high aspect ratio Is a flake-shaped nano material, different from Spherical, layered, and columnar nanomaterials. Therefore, the present invention uses polyoxyalkylene amine with a molecular weight of 1,000 or more, paramethylene and formaldehyde to polymerize into a linear Mannissin polymer intercalating agent, Use it

Page 7 577904 5. Description of the invention (4) The terminal amine group is acidified to form a quaternary ammonium salt with cations, and then undergoes a cation exchange reaction with the sodium ions between the clay layers to intercalate into the clay interlayer to obtain a new type Organic / inorganic polymer complex.

This stable complex has a polar hydrophilic inorganic layered structure and a non-polar lipophilic organic carbon chain structure, so it exhibits a special interface phenomenon at the oil-water interface. At a concentration of 100 ppm, it can make the toluene / water interfacial tension It dropped to about 0.6 dyne / cm. This new type of surfactant has a low critical micelle concentration (CMC) and can form hard structural micelles. This special interface phenomenon facilitates the uniform dispersion of organic / inorganic hybrid materials in polymers, in order to modify polymers to give them inorganic properties. Therefore, the modified manisamine clay of the present invention is a new type of inorganic / organic surfactant, and can also be used as a cationic polymerization initiator, emulsifier, dispersant, etc., and has a layered structure that has not reached the delaminated state. The clay layer can also be a carrier for drugs, and because the clay has reached the nanometer scale, it can be smoothly discharged from the human body without reacting with the human body. The manisamine-modified clay of the present invention can also be used as a high-molecular reinforcing agent. Blending with the high-molecule can improve the mechanical properties of the polymer such as heat resistance, gas barrier properties, rigidity, tensile resistance, and reversibility. The Mannisamine-modified clay of the present invention can be further extracted with alkali metal or alkaline earth metal hydroxide or gas to obtain a completely delaminated nano silicon wafer.

Conventional intercalating agents include 12-aminolauric acid, hexadecylamine, fatty amine, and bis (2-hydroxyethyl) methyl tallow alkyl gasification Bis (2-hydroxyethyl) methyl tallow alkyl ammonium

Page 8 577904 V. Description of the invention (5) Amines or ammonium salts such as chloride) and stearylamine. The polar groups of such low molecular intercalating agents can form polar valence bonds with the charged inorganic layered molecules, and change the hydrophilicity of the clay into an organic solvent-friendly property. In other words, it enhances the affinity of clay for organic monomers or polymers to facilitate the next delamination reaction. However, through intensive research, the inventors have found that using polyoxyalkylene amines with a molecular weight of 1,000 or more, parabens and carbene polymerized into a linear chain of Mannissinyl polymer intercalating agents, and the use of their ends The amine group is acidified to form a quaternary ammonium salt with cations, and then undergo a cation exchange reaction with the sodium ions of the clay interlayer to expand the interlayer distance to 20 ~ 98 "or directly delaminate to obtain a polymer organic / inorganic composite This compound has excellent surfactant effectiveness. Therefore, in the present invention, polyoxyalkylene amine having a molecular weight of 1,000 or more is used to polymerize p-cresol and formaldehyde to form a linear Mannesamine polymer intercalating agent to modify the layered clay. The polyetheramine used in the present invention may be selected from the group consisting of polyoxypropylene diamine, polyethylethylene diamine, and poly (ethylether-propyl ether) diamine (poly (oxyethylene-oxypropylene) ) diamine) 〇 These substances are commercial products such as Jeffamine D2000 [poly (propylene glycol) bis (2-aminopropyl ether), Mw 2000], Jeffamine D4000 [polypropylene glycol Poly (propylene glycol) bis (2-amino propyl ether), Mw 4 0 0 0] and Jeffamine

Page 9 577904 V. Description of the invention (6) ED2001 [(polypropylene glycol block-polyethylene glycol block-polypropylene glycol block) bis i (2-aminopropyl ether) (P〇ly (propylene glycol)- block-poly (ethylene glycol) -block-poly (propylene glycol) bis (2-aminopropyl ether)), Mw 2000], etc., among which Jeffamine D2000 is the best; others such as T3000 [trifunctional polypropylene glycol 2-amino Propyl ether (tri-functional poly (propylene g 1 yco1) 2-amino propyl ether), Mw 3000], T5000 [tri-functional polyCpropylene glycol 2-aminopropyl ether, Mw 5000] and so on. (The structural formula of Jeffamine series is shown below) h2nchch2och2ch ch3 ch: X = 33 (Approx. Mw = 2 0 0 0; JeffamineR D- 2 0 0 0) X = 68 (Approx. Mw = 40 0 0; JeffamineR D- 4 0 0 0) h2n〒 hch2 ochch2 ch3 ch3 J〇CH2CH2) y (〇CH2CH) zNH2CH3

Page 10 577904 V. Description of the invention (7)

Average = x + z = 5, y = 3 9. 5 (Approx. Mw = 2 0 0 0; Jeff amine® ED- 2 0 0 1) The inorganic / organic nanocomposite is a material with two different phases and at least One phase has a dispersion of nanoscale regime. Under uniform dispersion, that is, in the state of high surface to volume ratio, the mechanical properties are increased. Therefore, a good composite structure depends on the compatibility of organic and inorganic phases. The average montmorillonite structure has an average 10-layered parallel lamellar (lamellae), a layer diameter of about 10 nm (i.e. 100X), and the distance between the layers is only about 12 A. Is the smallest primary structure. Its hydrophilic silicate (siHcate) f aggregates finely to form a secondary structure and has a low affinity for organic polymers. Improving the compatibility of the two depends on the exchange capacity of ions and organic fourth-order salt recording between the clay distance, and the quaternary ammonium salt to increase the layer distance by intercalation, usually about 20X. Conjugate valence, this is intercalated to improve the quality of clay. The intercalation state is that the layers and layers are dispersed in an organic crystalline form. The dispersed delamination (ex7 between two and fixed distances exists at a single layer with irregular distances and directions. It is 1 on).

Page 11 577904 V. Description of the invention (8) Often, the clay and polymer in the intercalated state are obtained through further processing. Montmorillonite (MMT) is a hydrophilic aluraino-si 1 icate clay with a structural formula of two-layer tetrahedral silicate and interlayer octahedral alumina. ). Observed by an electron microscope is 〇 · ι ~ 1〇 # Aggregate of large and small, and the structural units are 16 planes or 8 lamelae, and the thickness of each layer is 9.6-10 A. Therefore, the primary particle has a height of 80-1 00 A and a radius of 300 i. The siliceous layered inorganic clay used in the present invention is selected from the group consisting of montmori1loni te, kaolin, mica, and talc (ta 1 c). Among them, modified commercial Chemically modified montmorillonite is better, such as aliphatic salt-salt intercalated clay (Cloisite 2001) and nano-cation exchange type montmorillonite MMT (Kunipia F). And the cation exchange capacity of clay (CEC) of the siliceous layered inorganic clay used in the present invention is preferably 50 ~ 200 meq / 100g. When the CEC is lower than 50 meq / 1 OOg, the organicization achieved through ion exchange is insufficient, and the swelling of the clay is not easy. When the CEC is higher than 200 meq / 1 00g, the interlayer bonding force is too high. It also makes clay swelling very difficult. The manufacturing method of the modified manisamine clay of the present invention is to polymerize polyoxy alkylene amine (molecular weight) or more, and to synthesize methane and formaldehyde to obtain a linear manisamine polymer. Layering agent, the aforementioned intercalating agent is acidified with inorganic acid, and then mixed with water-swelled silicon

Page 12 577904 V. Description of the invention (9)-Oxygen-layered inorganic clay, which is stirred vigorously at 60 ~ 180 ° C for anion exchange reaction to prepare Manisamine modified clay. It is important to find in the present invention that the polyetheramine with a molecular weight of less than 1 800 cannot achieve the effect of high-level intercalation, let alone direct delamination. ’Among them, if the intercalating agent is not subjected to acidification treatment, most of the intercalating agent will not be able to enter the interlayer of clay when the intercalating reaction is carried out, and the intercalating effect is not good. Useful acidifying agents are inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid. The ratio of the Moire number of the Mannisamine polymer intercalating agent used in the present invention to the cation exchange equivalent of Shixi oxygen layered inorganic clay is 1 · 3—2: 1, and the cation exchange equivalent and the Moire of the inorganic acid The number ratio is 丨: ^^ The Mannisamine modified clay system is a Mannisamine modified clay with a layered structure and an interlayer distance of 20 ~ 98A. In addition, the ratio of the Moire number of the Mannisamine molecular intercalating agent used in the present invention to the cation exchange equivalent weight of the Shixi oxygen layered inorganic clay is greater than or equal to 2: 1 and the Moore number of the cation exchange equivalent weight and the inorganic acid The ratio is greater than or equal to 2/1, and the prepared manisamine modified clay system is a delaminated manisamine modified clay without a layered structure. The manisamine-modified clay prepared by the present invention can be further extracted with hydroxides or vapors of alkali metals or soil test metals to obtain a nanostone tablet. The method is to dissolve the prepared manisamine modified clay in an organic solvent at room temperature to 110 ′ ′ to form a slurry A; and then disperse the siliceous layered inorganic clay in hot water to form a strong emulsion. Syringe B; then mix Syrup A and Syringe B, and stir vigorously at 60 to 120 ° C for 10 to 60 minutes, and then add a concentration of 1 to

577904 V. Description of the invention (ίο) 5N alkali metal or alkaline earth metal hydroxide or chloride aqueous solution 1 to 5 ml is vigorously stirred at 60 to 120 ° C for 2 to 4 hours, and then left to stand until layering After that, the upper layer liquid can be recycled and reused, and the lower layer liquid is inorganic, that is, nano silicon wafers dispersed in water. The hydroxide or gaseous agent of the alkali metal or alkaline earth metal mentioned above is preferably sodium hydroxide. In the foregoing extraction step, the organic solvent used is selected from the group consisting of ethers, ketones, esters, broad types, saturated hydrocarbons, chlorinated saturated hydrocarbons, and aromatic hydrocarbons. Specifically, such as tetrahydrofuran, diisopropyl ether, methyl tertiary butyl ether, methyl isobutyl ketone, ethyl acetate, ethyl acetate, pentyl, hexane, heptane, cyclohexane , Methylene chloride, benzene, toluene, xylene, gas benzene and methoxybenzene. Among them, toluene is preferred. The aforementioned invention uses the synthesized polyetheramine-derived polymer to acidify the terminal amine group with an inorganic acid to form a quaternary ammonium salt, and then performs a cation exchange reaction. The intercalation enters the interlayer corridor of the inorganic clay. The reaction is shown below. :

Page 14 577904

V. Description of the invention (11) CH3 CHj HjN-(CHCH ^ MjCHC-HNCW OHπφτ CH ^ HC1

ch2 -CHCH CH ^ CH ^ CH ^ NH ^? Ml I f ch3 XN ^ CMCmO ^ HjCHC-HHCHj-i ^ S-CHjJM-CHCM ^ OCMjCH- ^ NHj

V ch3 Θ © dispersed in hot water

OH ffCHjI.CHjNH- V ch3 〇

-NMCMjJ ^ jj · CH, HH'D20OQ ΝΗ »-^ H ^ N-lttWO-HNCIfjJ ^ -CH ^ NHDIOiO-NMCMj ^^ CH, HHD20OQ K CH3 ch3 OH GH OH Q 〇H ^ i-DMOO-HNCHij ^ jj CMjNH 丨 MM-NHCHxj ^ | · CHjJiH 丨 ΜΜ) · ΝΗί: Ηι | ^ | · CJ ^ NHMOM -Nl ^-CH2 CHj cm3 O 响 Ι15 Page 15 577904 5. Description of the invention (12) Because the surface of natural clay is Hydrophilic, so it can be uniformly dispersed in water ', but is incompatible with most polymers, so phase separation will be formed during melt-kneading, and micro-fine dispersion cannot be achieved. After the modified clay is introduced by organic molecules, it is partially non-polar and is compatible with polymers, so it can be blended with polymers to modify polymers. It can be blended with the compound of the present invention to modify local molecules such as epoxy resin, polypropylene (PP2 triethylene terephthalate (PET), polystyrene (ps), In the meantime, polystyrene (SPS), polyurethane (Pu), Nylon and styrene-propylene wide copolymer (SAN), etc. [Detailed description of the preferred embodiment] The present invention is explained in detail, and the preferred embodiments are given below. When the scope of implementation of the present invention cannot be limited by this, that is, any simple equivalent changes and modifications made in accordance with the scope of the patent application and the contents of the invention description of the present invention should still be It belongs to the scope covered by the patent of the present invention. / / Materials used: 1. Sodium cation-exchange montmorillonite Kunipia F (Nί -MMT) with cation exchange equivalent CEC = 115 meq / 100 g. 2. p-cresol (p- Cresol, manufactured by ACROS Co., Ltd.), molecular weight mw 108, mP · 3 at 34 ° C, bp 202 ° C.

577904 V. Description of the invention (13) 3. Polypropylene glycol bis (2-aminopropyl ether) [(pol (propylene glycol) bis (2-amino propyl ether))] (manufactured by Huntsman Chemical Co., brand name Jeffamine D2000, Mw 2000). 4. Formaldehyde (manufactured by ACROS), an aqueous solution with a molecular weight of Mw 30 and 37 wt%. According to the following steps, a polyetheramine, p-cresol and formaldehyde are polymerized to form a linear chain Amine Terminal-Mannich Oligomer (AMO) polymer intercalator, and the interlayer is used to modify the silicon oxide layer. Like inorganic clay and Mannisamine modified clay. 1. Swelling step of crushed oxygen layered inorganic clay: Take 5 g of Kunipia f (Na + -MMT) and disperse it in 1000 "80 ° C hot water and stir vigorously for 4 hours to make the aqueous solution stable and uniform. Dispersion liquid 2. Synthetic steps of Mannissamine polymer intercalating agent: 5 g of paraben (0046 m〇1) and 185 g of D2 0 0 0 (0.0 9 2 mo1), ie, para-form Mix with Mannis Additive at a Mohr number ratio of 1: 2, reflux in toluene at 90 C for 3 hours, then add 10 g of formaldehyde solution (that is, 0.12 mol), and raise the temperature to 3 〇t heating for 5 hours, at this time the mixture formed ΐ m substance Gan 'and then stopped refluxing. This is the Mannissamine polymer intercalating agent () ° GPC measurement showed four peaks of molecular weight, mw

Page 17 577904 V. Description of the invention (14) 2598, 5842, 9234 and 16952, as shown in Figure 1. The amine titration showed that the primary amine was 0.37 raeq / g, the secondary amine was 0.62 meq / g and no tertiary amine was present, as shown in Table 1. 3. Acidification treatment steps of Mannissamine polymer intercalating agent: Dissolve 13.5 g of Mannissamine molecular intercalating agent (am〇) in water, add hydrochloric acid (HC 1) of equal mole number, and mix in 8 Acidified at 0 ° C for 30 minutes. 4. Intercalation reaction step: Pour the acidified solution into the dispersion of step 1 and stir vigorously at 80 t for 5 hours to carry out the cation exchange reaction. The reaction solution was left to stand to separate the layers. After filtration, it was dried in a vacuum oven at 80 ° C for 24 hours to obtain a light-colored solid complex (ΑΜ0 / ΜΜΤ). The obtained composite was analyzed by X-ray diffraction (X-r a y d i f f a c t i ο η), and the distance between the layers was measured, as shown in Fig. 2. · Nano silicon wafer manufacturing method:. Dissolve 2 g of the complex (AM0 / MMT) prepared above in 100 ml of 100 mg of methylbenzyl, to form slurry A. Take 5 g of -MMT and disperse it in 600 ml of 80 f hot water and stir vigorously to form slurry B. Mix Milk A and Milk B 'and stir vigorously at 80 ° C for 30 minutes. Then add 5ml NaOH aqueous solution with a concentration of 5 N and stir vigorously at 80 ° C for 3 hours. After standing and layering, the layer solution is organic (AM〇) can be recycled and reused, and the lower layer solution is inorganic. Nano silicon wafers dispersed in water.

577904 V. Description of the invention (15) Analysis of experimental results 1. Interfacial properties The polyetheramine-derived polymer intercalated inorganic clay is an organic / inorganic hybrid material with characteristics of both organic and inorganic substances. Its structure has a polar hydrophilic inorganic layered structure and an organic carbon chain non-polar structure, so it exhibits a special interface phenomenon at the oil-water interface, and a low concentration of critical cell concentration (cmc), which can be clearly seen from Figure 3. . This special interfacial phenomenon will help the organic / inorganic hybrid materials to be uniformly dispersed in the polymer, in order to modify the existing polymer and make it have inorganic properties. 2. Interlayer distance analysis The intercalation reaction of sodium cation-type montmorillonite (KF) and the synthesized polyetheramine-derived polymer is carried out by cation exchange, which can be obtained from the degree of acidification of amine groups or the amount of intercalating agent added. The interlayer distance of different intercalated clays (basal spacing: 20 A ~ delamination), the results are shown in Table 2. 3. Effect of acidification reaction on intercalation If the intercalation agent is not subjected to acidification treatment, most of the intercalation agent will not be able to enter the interlayer of clay during the emulsification intercalation reaction, resulting in poor intercalation effect. The results are shown in Table 3. As shown. As mentioned above, a modified manisamine clay of the present invention and its derivative

Page 19 577904 V. Description of the invention (16) Nano-silicon wafers and manufacturing method thereof, provide a mannisamine-modified clay with excellent surfactant performance, and can be used as a polymer reinforcement, and further produced The nano silicon wafer obtained can be recycled and reused AM0 intercalating agent. It fully meets the requirements of invention patents. It is a highly technical creation that uses the laws of nature. patent.

Page 20 577904 V. Description of the invention (18) Table III Effect of acidification on the intercalation reaction Properties of acidifying agent after intercalation agent / clay reaction Interlayer distance (person) Emulsification phenomenon occurs, and the product IIC1 ΛΜΟ / Na -MMT after the reaction is completed Will precipitate 50 + No obvious precipitation occurs, still no ΛΜΟ / Na -MMT Na + -MMT (no intercalation effect) 12 577904 Schematic illustration briefly Figure 1: APC GPC determination (On the basis of PS standard) 〇 Figure 2: X-ray diffraction analysis. Figure 3. · The interfacial tension of AMO intercalated MMT (A) and AMO delaminated MMT (B) in toluene / water. Table 1: Amine amine titration values. Table 2: Interlayer distances for different AM0 / CEC / HC 1 ratios. Table 3: The effect of acidification on the intercalation reaction.

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Claims (1)

577904 Sixth, + please special issue scope-1 · A Mannisamine modified clay, which is polymerized into a linear chain with polyoxyalkylene amine with a molecular weight of 1 0 0 -30 0 0 Amine Terminal-Mannich 01 igomer (AMO for short) polymer intercalating agent, and a modified form of siliceous layered inorganic clay with the intercalating agent. 2 · The Mannisamine-modified clay as described in item 1 of the scope of the patent application is a mannisamine-modified clay with a layered structure and an interlayer distance of 20 to 9 8 A. The ratio of the Moire number of the molecular intercalating agent to the cation exchange equivalent of the silica-layered inorganic clay is 1: 3 ~ 2: 1. 3 · The Mannisamine-modified clay as described in item 1 of the scope of the patent application is a delaminated Mannisamine-modified clay without a layered structure, of which Moire The ratio of the number to the cation exchange equivalent of the siliceous layered inorganic clay is from 2: 1 to 100: 1. 4. The Mannisamine-modified clay according to item 1 of the scope of the patent application, wherein the polyetheramine is selected from the group consisting of polyoxypropy lene diamine, polyoxyethylene diamine, and Poly (ethyl ether-propyl ether) diamine (poly (〇xyethylene-oxypropylene) diamine adduct) 〇5. The modified manisamine clay as described in item 1 of the patent application scope, wherein the polyetheramine is It is polyoxypropy lene diamine. 〇 6. In the Mannissamine-modified clay described in item 1 of the patent application scope, the siliceous layered inorganic clay is selected from montmorillonite and (m ◦ ntm 〇ri 1 1 ο nite), kaolin (ka ο 1 i η), mica (mica) Page 24 577904 VI. Scope of patent application Talc powder (t a 1 c). 7. The mannisamine-modified clay according to item 1 of the scope of the patent application, wherein the cation-exchange equivalent of the siliceous layered inorganic clay is 50 to 2 〇〇meq / 10 0g 〇8 Nano-stone tablets produced by the Ammonium Modified Clay Institute are produced by using Mannisamine modified clay as described in item 1 of the scope of the patent application, and further test the hydroxide or gas of the metal or soil metal. Nano silicon wafers are obtained by extraction. 9 · A nano silicon wafer derived from a Mannisamine-modified clay as described in item 8 of the scope of the patent application, wherein the hydroxide or gaseous substance of the alkali metal or alkaline earth metal is aerosol. 10. · A method for manufacturing Mannisamine-modified clay, which is obtained by polymerizing phenol and formaldehyde with a molecular weight of 1 0-3 0 0 0 0. Amine Terminal-Mannich Oligomer (AMO) polymer intercalating agent, the aforementioned intercalating agent is acidified with inorganic acid, and then mixed with water-swelling siliceous layered inorganic clay, at 60 ~ 180 ° C The cation exchange reaction was performed under strong stirring to prepare Mannisamine modified clay. 11. The manufacturing method as described in item 10 of the scope of the patent application, wherein the Shixian layered inorganic clay system is selected from the group consisting of montmorillonite, kaolin, and mica. ) And talc. 12. The manufacturing method as described in item 10 of the scope of the patent application, wherein the cation exchange equivalent of the Shixian oxygen layered inorganic point soil is 50 ~ 200111 called / 1002. 13. The manufacturing method described in item 10 of the scope of patent application, wherein the Page 25 577904 6. The scope of the application for patents. The amine system is selected from the group consisting of poly (propylene oxide) amine diamine (polyoxypropyl ene diamine), polyethylamine (polyoxylamine amine) (polyylamine), K ethyl ether- Propyl ether) bisamine poly (〇xyethyiene-0 xypr py 1 ene) diamineadduct. 1 4 · The manufacturing method as described in item 10 of the scope of the patent application, wherein the polyamine is polypropylamine (p〇1 yoxypropy 1 ene diamine) ° 1 5 · As of the scope of patent application 1 The method according to the item, wherein the inorganic acid is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid. 16 · The manufacturing method as described in item 10 of the scope of the patent application, wherein the Manisamine polymer intercalating agent is acidified with an inorganic acid, and then mixed with a water-swellable siliceous layered inorganic clay at 80 Strongly stirred at ~ 160 ° C to carry out cation exchange reaction to prepare Manisamine modified clay. 17 · The manufacturing method as described in item 10 of the scope of the patent application, wherein the Manisamine polymer intercalating agent is acidified with an inorganic acid, and then mixed with a water-swellable siliceous layered inorganic clay at 80 ~ The cation exchange reaction was performed by vigorous stirring at 120 ° C to obtain Mannisamine modified clay. 18 · The manufacturing method as described in item 10 of the scope of the patent application, wherein the ratio of the Moire number of the Manisamine polymer intercalating agent to the cation exchange equivalent of the siliceous layered inorganic clay is 1: 3 ~ 2 : 1 and the molar ratio of cation exchange equivalent to inorganic acid is 1 ·· 1. The prepared Manisamine-modified clay system is a man with a layered structure and an interlayer distance of 20 ~ 9 8 A. Nissamine modified clay 0 1 9 · The manufacturing method described in item 10 of the scope of patent application, wherein 577904 6. Scope of patent application: ^ :: ^ Two-digit wide-oxygen layer ^ «Mole number ratio of soil yang ionizing acid" Sub-exchange equivalent and impossible, it is the manufacturer of nano-stone tablets derived from soil The modified clay is dissolved in the Mannisamine oxygen-free sound-free organic solvent prepared by the method described in ~ 10, and the organic solvent is formed to form a slurry A; and then Shi Xi- ^ ί7 / Λ: ίJ ^ Search and mix, and leave it in place, and continue to be strong to obtain the wind-emulsion or wind-water solution of the genus, and you can get the half of the manufacturing method described in item 20 of the patent range of the nano-stone syrup tablet in the water. 3 = Self-centered, ketones, brewed, nitriles: saturated hydrocarbons 22 cheeks and fragrant hydrocarbons. • Manufactured as described in item 20 of the scope of patent application: machine = is selected from tetrazine, diisopropyl squamous acid, second = propyl isobutyl, acetonitrile, ethyl acetate, pentane , Hexane & Cooked, Prepared, Laughed, --t〇i · The gas should be, Lu 1…, Gui, Ca :) ¾, heptane, burned, digas, methylbenzene, benzene, toluene, dimethylbenzyl, gas benzene and methoxy 2 3 metal II application: f patent scope item 20 Said transformation: a manufacturing method, wherein the hydroxide or chloride of the earth metal is sodium hydroxide. The manufacturer is going to apply for the soil manufacturing method described in Item 10 of the patent scope, in which the Mannissamine-modified shellfish prepared by the application of the agent is used as the oily interface activity. 5779〇4 Shen Jing Patent Fan Yuan, 5. J3, the "manufacturing h" described in item 10 of the scope of application for patents, in which the cut-off Mannissamine modified adhesive is used as a polymer material modifier Its application. 26. The manufacturing method as described in item 10 of the scope of application for a patent, wherein the Mannisamine-modified clay system produced by the manufacturing method is used as a 3 hardener for epoxy resin '. 27. The manufacturing method as described in item 18 of the scope of application for a patent, wherein the mannisamine-modified clay system having a layered structure and an interlayer distance of 20 to 98 A produced by the manufacturing method is used as a drug carrier .笫 Page 28