TWI280261B - Highly branched poly amine organic exfoliation agent with multiple functional groups and amorphous nano silicate platelet prepared by its exfoliation inorganic clay - Google Patents

Abstract

This invention relates to a kind of highly branched poly amine organic exfoliation agent with multiple functional groups and amorphous nano silicate platelets prepared by its exfoliation inorganic clay. The inorganic clay exfoliation agent is formed by polymerizing poly(oxypropylene)triamine and diglycidyl ether of bisphenol A (DGEBA). Through the use of the acidification of the hydrophilic amine group of the exfoliation agent, siloxane layered inorganic clay can undergo ion exchange to achieve physical complete exfoliation to obtain a novel nano silicate platelets.

Description

1280261 - Nine, the invention relates to: [Technical field of the invention] The present invention relates to a polyfunctional and high-branched polyamine organic delaminating agent and a disordered nano-clay prepared from the delaminated inorganic clay, the delaminating agent It is formed by polymerization of polyether triamine and bisphenol A glycidyl ether; by using the hydrophilic amine group of the delaminating agent, the bismuth oxide layered inorganic clay can be completely delaminated. The invention also relates to a method of producing the inorganic clay delaminating agent and utilizing the delaminated clay and extracting to obtain a nano crepe sheet. [Prior Art] 'Background of the Invention' Basically, layered inorganic substances (such as montmorillonite or synthetic fluorinated mica) can increase the interlayer spacing from 10 A to about 20 A via an ion exchange reaction of an organic quaternary salt. It allows monomer to enter and exit. The intercalation state means that the layer is dispersed in a crystalline form at a fixed distance; the exfoliation state means that each single layer exists at an irregular distance and direction, usually by an ionic interface. The active agent disperses the clay to a single-layer structure of the nanometer order, and further obtains an organic/inorganic polymer nanocomposite by polymerization. In the literature, the intercalated agents have been reported to include quaternary ammonium salts such as 12-aminolauric acid, hexadeeykmine, fatty amine, and bis(2-hydroxyethyl)methyl tallow alkyl ammonium chloride. The low molecular type intercalation agent is a polar ammonium salt chemical group, which can form a polar mussel bond with the interlayer charged inorganic layered molecule, and has the property of changing the hydrophilicity of the clay to become an organophilic solvent. Improve the affinity of clay for organic monomers or polymers to facilitate the next delamination reaction. In addition, T. J. pinnavaia (MicWgan State University) found that diglycidyl ether of bisphenol_A (epoxy resin EP〇n828) can be polymerized into a nano-plylate/clay composite by intercalation agent chxch^nh. The intercalation agent has a different structural formula, up to d Spacing = lg 〇A, and then self-polymerized to an epoxy/clay material of 34·1 A by an epoxy resin of about 75 ° C, and proves the heat distortion temperature (hot, heat) Distortion temperature), the regularity of the intercalation agent, from single layer (m_layer) • 1280261 to biayer (biiayer) and three-layer structure (pseud〇_trim〇lecular), the layer spacing is expressed as i3 8 A to Between 18.0 A. In this width intercalation layer, the epoxy resin (Ink_η) can be polymerized, and the layered inorganic substance can be more advanced to achieve the application effect of the nano material. The traditional technique is to change the vf silk soil to the miscellaneous soil of the ship's layer. Step: The paste interface active agent is modified into clay, and then mixed with the polymer. The inventors of the present invention have proposed a polyetheramine and polyqing yw _ing_maleic smear (referred to as an intercalating agent to enlarge the interlayer spacing of montmorillonite in the patent Να 6,822, also proposed in U.S. Patent No. 6,765, The deuterated polyamine is an intercalating agent to make the montmorillonite reach an unprecedented interlayer spacing; and the composite obtained by intercalating the polyetheramine and the PP strip in U.S. Patent No. 7,022,299, is further emulsified and then deuterated. The replacement reaction is carried out to remove the limbs, and the gamma (a family) is large, and the nanometer is turned up. In addition, the inventors also proposed in the US patent application Μ 面 face,航D_合船彳, 幽_使魏土达敢魏层的效果, this delaminating agent can change the layered clay in one step to delaminate the clay. The present invention again proposes different high branching band energy... A polyamine salt with a polyfunctional amine group in the form of a silk, and the delaminating agent, through intercalation and displacement reaction, can achieve the effect of direct delamination of inorganic clay such as earthworms and mica. Extraction ion exchange to form disordered nano-slice tablets. Muscle-1280261 The object of the present invention is to provide a polyfunctional and highly branched form polyamine organic delaminating agent and a method for producing the same, which are characterized by polyether triamine and bisphenol A glycidyl ether to form a structural formula which is multifunctional and highly branched. A polyamine organic substance is formed. Another object of the present invention is to provide a nano bismuth sheet and a method for producing the same, which comprises a delaminating agent formed by a polyether triamine and a bisphenol A glycidyl ether to make a cerium oxide layered inorganic The clay achieves a delamination effect and forms a disordered nanosecond film. A further object of the present invention is to apply the nanosheet to an antibacterial effect to develop into an antibacterial material. The present invention produces a polyfunctional and highly branched form polyamine. The organic delaminating agent method mainly comprises the following steps: (4) mixing a polyether triamine (p〇ly (OXypropylene) triamine) having a molecular weight of 100 to 10,000 with a polyglycidyl ether (DGEBA) to form a ΝΉ2 function at both ends. Amine_terminated BPA epoxy oligomer (AEO) delaminating agent. The polyether triamine of the above step (a) generally has the following structural formula:

Where a = 4~5, 16~17 or 27~28. For example, the Huntsman Chemical Co. manufacturer's name is Jeffamine2 POP-T-403, POP-T3000 or POP-T500. The bisphenol A glycidyl ether (DGEBA) of step (a) usually has the following a a

Where b = 〇~2. 1280261 In the reaction of the step (a), the polyether triamine and the DGEBA molar are preferably 〇·3 ··丨~丨·· i; the reaction temperature is preferably 20 to 200 ° C, and the reaction time is preferably § ~24 hours. According to the above method, the present invention can produce a novel inorganic clay delaminating agent. The inorganic clay delaminating agent of the present invention preferably has the following structural formula:

Ch3 where a = 4~5, 16~17 or 27~28, b = 1~3.

In addition, the method for producing a nano-stone tablet by using the delaminating agent mainly comprises the following steps: (the delaminating agent is mixed with the inorganic acid to completely acidify, and the delaminating agent is molecularly-sized. One of them is mixed with a double-aged A纟fg glycerol _ (DGEBA) to form a double S^A Weisel (Lex epd epGxy Glig_r, AEO) (c) acidified at both ends. The delaminating agent is mixed with an oxygenated layered inorganic clay to carry out an intercalation reaction to form a first mixture, and (d) the first mixture is dissolved in the first solvent, and at least one equivalent of the metal or society The metal residue is subjected to a displacement reaction to form a second mixture containing nano-stone tablets. The inorganic acid of the above step (b) may be hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid or any acid having the same effect; delaminating agent The equivalent of the intermediate salt and the inorganic acid is preferably 〇·3: 卜 3 ·· j; the acidification reaction temperature is preferably 30 to 70 ° C. The oxon layered inorganic clay of the above step (c) may be montmorillonite , mica, kaolin, vermiculite, Kio Λ SWN (layered double hydroxides ^ LDH)^^ It is a reduced mica or montmorillonite for the combination of w; the cation exchange #4 (CEC) of the oxygen-free layered soil of the present invention is preferably a5~2G/g, · nh2 and 9 oxygen in the delamination 71 The equivalent of the cation exchange equivalent (cjgc) of the layered inorganic clay is preferably greater than 12:1; the equivalent of the cation exchange equivalent of the polyether triamine and the ruthenium layered inorganic clay of the delaminating agent is 1280261 = c) _ preferably α3 : η : 丨. The reaction temperature of the step (6) is preferably from the side of the C' reaction time of from 3 to 5 hours. 〃 In the above step (4), the first solvent is usually methanol or other suitable solvent; the volume of the first mixture and the f / mixture is preferably α 〇 3 ··丨~ such as: 丨; metal hydroxide of the metal or soil test Or chlorine recording is preferably NaQH or a compound without metal nucleus gold hydride hydroxide. When Wei Wei 〇 3 : 丨 ~ 3 : 丨; the reaction temperature of step (6) is preferably entangled, reaction time It is preferably 1 to 3 hours. In addition, it is also possible to repeat d) to make the reaction more complete. The above step may further include a step of: (6) mixing the second mixture with water and a second solvent φ to obtain an extract of nanosecond tablets. In the above step (e), the second ray may be f benzene or any suitable surface; the volume ratio of the f alcohol, the second solvent and the water is 0.3:0.3:1·〇~3 ··3:1; Good for 3〇~7〇. 〇, extraction • The day guard ί father is 1 to 3 hours. The above step may further comprise a step of: (f) removing the first solvent and/or the second solvent in the nanocrystalline extract. According to the above method, the present invention can be prepared as a kind of Ninashu #, and its organic/inorganic weight ratio is usually 10/90 to 90/10, and its composition preferably includes si (2() to 5〇 plus %). ,Mg (1〇~3〇# Imitation%) 'A1 (〇~10 M %), Na (1~10 Wt %), Fe (0~1.0 wt %) and F (1~15 wt %); The size of the rice stone tablets is about 50~15〇〇nm and the thickness is about 0.5~1.5nm. Further, it has been found from the test results that the nano-stone tablets of the present invention are still applicable to antibacterial treatment. Hereinafter, preferred embodiments will be described to illustrate the manufacturing process of the present invention, and the comparative examples will be understood to understand the manufacturing conditions and results. 1280261 [Embodiment] Raw materials used in the examples and comparative examples of the present invention include: (1) polyether diamine (p〇ly (propylene glycol) diamine): Huntsman Chemical Co. or Aldrich Chemical Co., trade name Jeffamine 8 D- 400, average molecular weight (Mw) = 400, the structural formula is as follows:

m CH3 H^NCHCH, 40CHC CH3 a + b = 5~6, b = 0

(2) Poly(propylene glycol) triamine: Huntsman Chemical Co. or Aldrich Chemical Co. under the trade name Jeffamine® T-403, average breaking amount (Mw) = 440, structural formula: CH, CH3 CH2^-〇CH2CHj-NH2 H2N j CHCH2〇+ CH2CCH2CH3 ch2-^och2ch^-nh2 CH, a = 4~5 (3) Liquid diglycidyl ether ofbisphenol-A (DGEBA): Taiwan South Asia Company , trade name BE-188, average molecular weight (Mw) = 350, epoxy equivalent (EEW) = 188, eight ch3 oh _/=\ 1 /=\ I 1 /=\ Ty=\ Λ h2c-chch2o- ?&quot ;vj^OCH2CHCH2〇~ -χΌτ -och2ch—ch2 b = 0 〜2 〇ch3 ch3 (4) Synthetic fluorinated mica: Japan CO-OP Chemical Co., SOMASIF ME-100, chemical composition including Si ( 26·5 wt %), Mg (15.6 wt %), A1 (0.2 1280261 wt %), Na (seven) Μ %), Fe (〇1 milk%) and F (8 8 s%), cation exchange capacity (CEC) = L2 〇meq/g〇(5) Natural montmorillonite (Jianji: Nan〇e〇rInd·c.·, cation exchange capacity (coffee) = 1.15 meq/g. Natural mica cannot be swelled, but the above-mentioned human fluorosis Synthetic cloud side Therefore, natural montmorillonite can be swollen by water. Since the polar structure of natural montmorillonite (or synthetic mica) is combined with water and water, it can be uniformly dispersed in aqueous solution. The inorganic clay of the application should be swelled as follows: (10) g of the inorganic clay is dispersed in 10 L'8 G C of hot water for 4 hours. The aqueous solution forms a stable and uniform dispersion of earth color. " Example 1~2 Xuefei Chami Tablets Example 1 Interest (4) Synthesis of polyfunctional and highly branched form polyamine delaminating agent T403 (71·5 g, 163 mmoles) and DGEBA (28·5 g, δ1· 4 face 〇 1 prevention) added to the 2S0 齓 three-necked bottle (Χ4〇3 and DGEBA 莫 tb2:1), mechanically turbulent reaction at room temperature for 8 hours, monitored by FTIR (Fouriertransfomxinfrared spectroscopy), epoxy The disappearance of the characteristic absorption peak (910 cm) indicates that the reaction is completed, and a viscous liquid is obtained, that is, an amine-terminated BPAepoxy oligomer delaminating agent. Figure 1 shows the process of this reaction. Acidification reaction T-403 AEO (48 g, 39 mmols) was dissolved in decyl alcohol (1 〇〇g), hydrochloric acid (35 milk%, 7.5 g) was diluted with water (50 mL), and then slowly dropped into T-403AEO. An amine/HCl amine salt is formed at room temperature. :t Li (c) intercalation reaction 1280261 and then poured into synthetic mica (10 g dispersed in 1 L of deionized water), stirred at 80 ° C for 3 hours, filtered, and the solid was vacuumed at 7 Torr. Drying gives the first mixture of τ_4〇3^〇/mica. Step (d) Filtration The Τ-403 AEO/mica mixture was taken at 8 Torr. The underarm was dispersed in methanol (2 〇〇), and then - times equivalent of NaOH (4.8 g) was added. At this time, the T-4G3AEO/mica mixture was mixed to form a pale white viscous viscous solution, which was filtered to give a pale white half. A second mixture of transparent τ_4〇3^〇/mica, TGA analysis results in an organic/inorganic ratio of about 5〇/5〇. Face (6) displacement reaction A second mixture of T-403AEO/mica was added to decyl alcohol (2 〇〇 mL) in hydrazine. Mix well under the armpit, add deionized water (2 〇〇 ') and mix well, then add twice the equivalent of Na〇H (9.6 g) and mix well to obtain a liquid containing nano-stone tablets. Step fff extraction is added to the liquid containing the nano tablet. Toluene (2 〇 ()) is uniformly mixed, and after standing for one day, it is divided into one layer, the upper layer of armor is stupid with T_4〇3 AEO, the middle layer is methanol, and the lower layer is ^^ > Aqueous solution, the solution of the lower layer was taken, and the product was reduced to 1 〇wt% of the mica nano-smear solution at 8 G °C. Same as Example 1. ^MAb) A(c) Same as Example 1, except that the dose used was reduced by 1/1 times. Same as in Example 1, except that the dose used was reduced to 1/10 times. A pale white translucent 丁4〇3 〇/mica mixture SI body was obtained, and the TGA analysis silk organic/inorganic ratio was about 5〇/5〇. 12

/ (A 1280261, step (6) and (Τί / same as in Example 1, except that the dose used is reduced to a multiple. The concentrated by-product of the rotary concentrator is S) is a 1% by weight solution of mica naphthalene solution. 1, the ratio is also 18/6/1. 1. The synthetic mica of step (c) is changed to montmorillonite, and the ratio of the reactants of the T-403AEO delaminating agent on the surface of the smectite (10) montmorillonite is repeated only Step (a) of the first example, except that the ratio of the polymyric triamine τ_· is changed to 3:1 and 4, respectively, to form a viscous liquid. 1-5 Repeat steps (a) to (1) of the first embodiment; The ratio of the delaminating agent τ_4〇3 mica is shown in Table 1. Table 1 Example/Comparative Example T-403 AEO/HC1/mica (Morby) NH2/HV mica (equivalent ratio) Examples 1 to 2 3 /6/1 18/6/1 Comparative Example 1 - Comparative Example 2 1/1/1 6/1/1 Comparative Example 3 1/2/1 6/2/1 Comparative Example 4 1/3/1 6/ 3/1 Comparative Example 5 2/4/1 12/4/1 13 8 1280261 More than the vehicle example 6 to 8 Repeat the steps (4) to (1) of Example 3; except the delaminating agent τ_4〇3 at the simple (3) montmorillonite Than Table 2 Table 2 Example / Comparative Example T-403 AEO/HC1/Montmorillonite (Morbi) —-—1 .......——-—nh2/hV Montmorillonite (equivalent ratio) f Example 3 3/6/1 18/6/1 ^ Comparative Example 6 - Comparative Example 7 2/4/1 12/4/1 ^ Comparative Example 8 1/2/1 6/2 /1 A comparative example 9 The steps (a) to (f) of Example 1 were repeated; however, the polyether triamine Τ-403 of the step (a) was changed to the polyether diamine D-400, thereby forming a delaminating agent d_400 AEO The ratio of mica is the same. Fig. 2 is a reaction diagram of a synthetic intercalant prepared by using this amine amine Jeffamine 1)-400. Comparative Example 10 Steps (a) to (f) of Example 3 are repeated; The polyether triamine T-403 of a) is changed to the polyether diamine D-400, thus forming the delaminating agent D-400 AEO. The ratio of NH2/HV montmorillonite is the same. The delaminating agent analysis examples of different reaction conditions The amine equivalent of 1 was titrated to obtain 2.6 meq/g of primary amine, 2.2 meq/g of secondary amine, and 0 meq/g of tertiary amine. The amine titration results of Examples 3, 8 and 9 were 3.06 meq/g and 3.05 meq, respectively. /g and 2.92 meq/g, wherein the product of Example 9 has a tertiary amine, indicating that the temperature increase causes the secondary amine to start reacting into a tertiary amine, so the reaction temperature of the delaminating agent needs to be controlled. ) (c) Gel Permeation Chromatography (GP) of T-403 AEO delaminating agents of Examples 1, 4 and 5, respectively C) Atlas. Wherein, Example 1 has four different fractions of 14 1280 261 '3, 161, 1, 897, 630 and 237, respectively, and the degree of polymerization of the oligo polymer is estimated to be between one and three by molecular weight and amine equivalent. The compound having a broad molecular chain distribution has three different molecular weights, which are 2462, 1777, and 65 Å, respectively. Example 5 has two different molecular weights, which are 1743 and 602 母 母 母 ;; ^ 1· X-ray diffraction (X-ray Diffracti〇n, xrd) The intercalation and delamination results of synthetic mica were analyzed by XRD and TGA, as shown in Figure 4 and Table 3. Figure 4 is an x_ray diffracti〇n (xrd) map of mica nanosheets, where t_4〇3 AEO/hV mica molar ratio (a) i/1/i, (9) i/2/i, (c) i /3/i,(6) 2/4/1,and (e) 3/6/1 The diagram and table show that when the poly-triamine t_4〇3, hydrochloric acid and mica of Comparative Example u are reacted in different proportions, A layer spacing of 15·2 to 60 A is obtained, and the layer spacing cannot be effectively pulled out to achieve a delamination effect. When the molar ratio of the delaminating agent T-403 AEO/HC1/mica is 3/6/bu mulver, the mica is 18/6/1, the interlayer spacing disappears to reach the delamination effect. The medium delaminator/clay weight ratio is 76/24. Table 3 Example / Comparative Example _403AEO/HC1/mica (Morby) NHb/tfV mica (equivalent ratio) Interlayer distance (A) Delaminator/clay (w/w) Example 4 to 5 3/6 /1 18/6/1 Delamination a 76/24 Comparative Example 1 — — 12.6 — Comparative Example 2 1/1/1 6/1/1 15.2 30/70 Comparative Example 3 1/2/1 6/2/1 38.9 58/42 Comparative Example 4 1/3/1 6/3/1 32.8 50/50 Comparative Example 5 2/4/1 12/4/1 60.0 68/32 a disordered XRD structure. 15 1280261 Table 4 shows the intercalation or delamination effect of the de-intercalation agent τ-403 and D_400 AEO on mica in Example 1 and Comparative Example 9, in the same NH2/HV mica equivalent ratio. Underneath, τ_403 ΑΕΟ can reach complete delamination, while D-400 ΑΕΟ can only extend the interlayer distance of mica to 25·5 Α. Table 4 Example / Comparative Example Intercalant NH2/HV Mica (Equivalent Ratio) Interlayer Distance (A) Delaminator/Clay (w/w) Example 1 T-403 AEO 18/6/1 Delamination a 76/ 24 Comparative Example 9 D-400AEO 18/6/1 25.5 — a disordered XRD structure. 2. Transmission Electronic Microscopy (TEM) Figure 5 is a TEM observation of mica nanosheets embedded in epoxy resin. The original mica itself is in the polymer because of van der Waals. Force) or ionic bond (i〇nicb〇nding) effects, etc., and there is a tendency to self-aggregate. However, after delamination, it can be observed from the TEM slice in the TEM slice, and the structure of the lamellae mica has been scattered. Among them, (a) and (b) show the delamination and state, the molar ratio of 11403 fine milk mica is over, the lion is analyzed as disordered sheet structure; (7) and (d) shows the state of intercalation, its T-403 The AEO/HV mica has a molar ratio of 2/4/1, and Na's analysis dspacing = 60.〇A, which is a parallel stack of sheets and sheets. • Atomic Force Micrograph (AFM) f 6 is a single-chip mica nanometer in aqueous solution observed by AFM. The diameter of the two-dimensional microstructure is about 3〇0~lOOOnm, and the TEM observation is In order to match, the thickness is i-mail, which means that it has a high card ratio. Due to the complete de-allocation of the original layer structure, the surface is adsorbed with Na+ ions and has strong ionicity. #路出末

16 !28〇261 虞恩主奈米石夕分析光光射 (XRD) Figure 7 is the X1® map of the montmorillonite intercalation and nanosheets obtained in Example 3 and Comparative Examples 7 and 8. Example 3 has no significant layer spacing to achieve a complete delamination effect. Table 5 shows the interlayer distances caused by the ratios of different T-403 AE0/HC1/montmorillonites in Example 3 and Comparative Examples 6 to 8. Table 5 Example / Comparative Example T-403 AEO/HC1/montmorillonite (Morby) Montmorillonite (equivalent ratio) Interlayer distance (A) Delaminator/clay (w/w) j Example 3 3/ 6/1 18/6/1 Delamination a - Comparative Example 6 - 12.6 - Comparative Example 7 2/4/1 12/4/1 19.1b - Comparative Example 8 1/2/1 6/2/1 38.2 — a disordered XRD structure. b peak is not obvious (weakpeak), indicating that there has been partial delamination. Table 6 shows the intercalation or delamination effect of the delamination agent T-403 AEO and EM00AEO on montmorillonite in Example 3 and Comparative Example 1 in the same stomach 2/1^/montmorillonite Under the soil equivalent ratio, T-403AEO can be completely delaminated, while D-400AEO can delaminate part of montmorillonite, but most of the interlayer distance of montmorillonite can only be extended to 22 A. (The two delaminators can delaminate the montmorillonite with a smaller diameter and a lower density of 4, The difference is attributed to the platelet size (100~1000 nm for the mica and 80~100 nm for MMT) And the charge density (76.92 e7nm2 for Mica and 0.925 e7nm2 for Na+-MMT). The number of functional groups possessed by each of the two delaminating agents is different, with T-403 AEO/HC1/montmorillonite =18/6/1 ; D-400AEO/HC1/montmorillonite = 12/2/1 (equivalent ratio) can all be obtained as a result of delamination of montmorillonite. Therefore, the above seems to be somewhat inferior.) 17 !28 〇261

Antibacterial effect of disordered XRD structure of Chami Shixi tablets. To understand the antibacterial effect of the nanosheets produced by the present invention, ρ π step in the blood of the group containing Escherichia coli - NovaBlue, respectively, adding montmorillonite α One%), montmorillonine tree tablets (l.Gwt%), mica (1%%) and mica nanometers (Im.) The results were selected and compared with those without added soil or navel. The results are shown in Table 3. The growth of the strainer was good without adding, adding montmorillonite and mica. The addition of montmorillonite shixi tablets did not increase the growth of mica navel (4) culture dish. There is no strain growth at all. Table 3 Addition of residual montmorillonite, montmorillonite, t-mica, mica, nano-stone, growth, +++, the mountain ridge, by the above yoke example and analysis, by proper control The ratio of the terminal deuterated plate of the ether triamine delaminating agent can be simplified and the synthetic mica-step delamination, and then through the replacement «and the extraction residue can be obtained from the self-dispersing naphtha. In addition, the large intestine Bacillus 4 test also shows that as long as the content of the nanosheet of the present invention is properly controlled, good results can be obtained. Antibacterial effect, especially mica is better.

18 1280261 [Simple description of the diagram] Figure 1 is a reaction diagram of the intercalation agent synthesized by trifunctional amine amine Jeffamine T403. Figure 2 is a reaction diagram of an intercalant prepared by difunctional amine amine Jeffamine D-series Amines. Figure 3 shows the GPC spectra of T-403 AEO and D400AEO delaminators. Figure 4 is an XRD pattern of mica nanosheets. Figure 5 is a TEM observation of mica nanosheets embedded in epoxy resin. Figure 6 is a view of the mica nanosheet in aqueous solution by AFM.

Figure 7 is an XRD pattern of montmorillonite bracts.

19

Claims (1)

1280261 X. Patent Application Range: 1. A method for producing a polyfunctional and highly branched polyamine organic delaminating agent, comprising the following steps: (8) a molecular weight of 1 〇〇 〜1 〇, 〇〇〇 polyether triamine (p 〇ly(〇Xypr〇pylene) triamine) is mixed with a double-aged A glycidyl ether (DGEBA) to form an amine-terminated BPA epoxy oligomer (AEO) with NH2 functional groups at both ends. Layer agent. Glycidyl ether 2. The method of claim 1, wherein the bisphenol A (DGEBA) of the step (a) has the following structural formula: 〇ch2ch—ch2 where b = 0~2. 3. The method according to claim 1, wherein the poly-triamine of the step (a) is a compound of Huntsman Chemical Jeffamine® POP-T.403 > POP-T3000 ^ Ρ〇ρ.χ5〇〇 . 4. The method of claim 1, wherein the poly-triamine of the step (4) has the following configuration: CH corpse 3 gh2-[och2ch|.nh2 h2n-^ chch2〇CH2CCH2CH3 a CH24- 〇C : H2 丫H+NH2 ch3 where a = 4~5, 16~17 or 27~28. 5. The method of claim 6, wherein the step (8) has a poly-to-three molar ratio of 0.3:1 to 1:1. The method of claim 1, wherein the reaction temperature is 20 to 200 ° C, and the reaction time is 8 to 24 hours of the polyether triamine of the step (a) and DGEBA. 20 6. 1280261 - A polyfunctional and high-branched heterogeneous organic delaminating agent 'fine' is manufactured by the method described in the article No. VIII. 8. A polyfunctional and highly branched form polyamine organic delaminating agent. Has the following construction: OH CH3 " ch2-^och2ch· h2m chch2o ch2cch2ch3 CH2-^〇CH2CHj-NH2 CH, :ch2chch2o OH V"—〇CH2CHCH2NH^CHCH2〇A*CH2 ch3 CH, ch3ch2〒ch2·^· och2ch*^--nh2 NH2-^CHCH2〇j-CH2 & b CH3 where a = 4~5, 16~17 or 27~28, b = 1~3 9. A method for preparing a disordered naili stone tablet by delaminating gw and bismuth-shaped sorrow polyamine organic delaminating agent, including the following steps: (b) - the delaminating agent is completely acidified by mixing with the inorganic acid, and the delaminated crane is mixed with a molecular weight brain-polyether triamine and a frequency A condensed water _ (DGEBA), and the generated two ends have leg 2 functional groups. (A) an acidified delaminating agent mixed with -Wei layered inorganic clay for intercalation reaction to form a first mixture; and (4) dissolving the first mixture The first reaction is carried out by a displacement reaction of at least a metal hydroxide or a chloride of a metal grade earth metal to form a second mixture containing Nai's tablets. K). The method of claim 9, wherein the inorganic acid of the step (9) is hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid. 11. The method of claim 9, wherein the equivalent ratio of Li 2 to the inorganic acid in the delaminating agent of the step (9) is 0.3:1 to 3:1. !2· For example, the application of fiber, the method of aging, the age of _ _, the acidification reaction temperature of the acid is 30~70 °C. I3. The method of claim 9, wherein the layered inorganic clay of the step (8) is montmorillonite, mother, samarium, vermiculite, K1G montmorillonite, SWN or silky stone or hydrotalcite (iv) (10) 1 21 九 *1280261 double hydroxides, LDH). The layered inorganic clay is a method as described in claim 9, wherein the step (4) is a synthetic fluorinated mica or montmorillonite. 15. The method according to the invention, wherein the cation-exchange equivalent (CEC) of the layered inorganic point soil of the cap step is from 0.5 to 2.0 nieq/g. [6] The method according to claim 9, wherein the delaminating agent of the step (4) has a ratio of (5) 1 (four) of greater than 12: 中. W. The method of claim 9, wherein the delamination ejaculation triamine oxygen-free layered cation-free equivalent (CEC) ratio of the step (4) is a3: W: i. The method described in Item 9 of the claim 4, the reaction temperature range of the cap step (4) is 〇C, and the reaction time is 3 to 5 hours. !9· The method as described in claim 9 The method of the step (6), wherein the solvent is methanol. The method of claim 9, wherein the volume ratio of the first mixture to the first solvent in the step (6) is 0.03: 1 to 30: 1. 21 The method of claim 9, wherein the hydroxide or chloride of the metal or soil metal of the step (d) is NaOH or KOH. ♦ 22. The method of claim 9, wherein the equivalence ratio of the first mixture of the step (6) to the metal test or the 2 earth metal oxide oxide is G·3 ··1~3 ·· 1. The method of claim 9, wherein the reaction temperature of the step (6) is % to % ^ and the reaction time is 1 to 3 hours. • 25, as in the method described in the second paragraph of the patent, the cost of this step (6). (6) The method of claim 2, wherein the step (6) further comprises a step of: 26 I extracting the second mixture of the f and the water and the second solution to prepare an extract of the navel tablet . The method of the invention of the present invention, wherein the volume ratio of the methanol, the second solvent and the water 22 1280261 in the step (4) is 03: 0.3 ·· u~3 ······1. The extraction temperature of the step (e) is 3〇~7〇 28. For example, the method of extracting the scale is K3 hours. The method of claim 9, wherein the step further comprises removing the first solvent and/or the second solvent in the nanoplate extract by a rotation of ω. 30. A disordered naphtha sheet is produced by the method described in claim 9 of the patent application. 31. If the application of the noodles mentioned in item 30 is applied, the ratio of organic/inorganic children is 10/90 to 90/10. % 32. The disordered nano-correction described in the 3° clause of the patent application includes Si (20 to 50 wt%), Mg (10 to 30 wt%), and A1 ((MO wt%) 'Na ( M〇wt%), & (〇~i 〇%) and F (1-45 wt %) 0 33· The disordered nano-stone tablets as described in claim 30, the diameter of the film About, the lungs, the thickness is about 0.5~1.5 nm. % The disordered nano-stone tablets as described in the third paragraph of the patent application, which is based on antibacterial treatment.