TW200538414A - Nano silicate platelet-organic polymer nanocomposite and use thereof - Google Patents

Abstract

The present invention provides a nano silicate platelet-organic polymer nanocomposite comprising an organic polymer and a nano silicate platelet, the nano silicate platelet is the reaction product of an intercalating agent represented by the following formula (I): and siloxy-layered nano silicate platelet in an acidic condition: wherein POP is a divalent moiety having the following formula (II): R is C1~C4 alkyl group, and n is an integer of between 1 and 68, and m is an integer of between 10 and 100. The present invention also provides a coating film with high hardness, which is obtained by coating a substrate with the above nano silicate platelet-organic polymer nanocomposite and heating for a sufficient time.

Description

200538414 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a nano silicon wafer / organic polymer nano composite material and its application. In particular, the present invention relates to a nano-composite material in which 5 nano-silicon wafers are dispersed and dispersed in an organic polymer, and the nano-composite material can be further prepared to have excellent mechanical properties, transparency and thermal properties. Its coating. [Previous technology] Inorganic clay- · 10 organic polymer nanocomposite is one of the important materials that the industry is working hard to develop. In recent years, many literatures and patents on nanocomposite materials have been reported. For example, Toyota Japan has dispersed [NHACHOhCOCT] montmorillonite in Nylon 6 and developed the first inorganic material that can be practically used in the market. Clay / organic polymer nano composites. These 15 documents and patents disclose natural or artificial layered clay as an inorganic filler to be added to catalysts and polymer materials, to improve the solvent resistivity of polymer materials, Gas barrier property, mechanical property and thermal property. Since the surface of the unmodified layered clay is hydrophilic 20, it has poor compatibility with general hydrophobic organic polymers, so that it is easy to produce uniform dispersion due to aggregation. Shortcomings. Therefore, the improvement of the mechanical and thermal properties of the composite material depends on whether the organic polymer has good compatibility with the layered clay, that is, the degree of dispersion of the layered clay in the organic polymer. 200538414 In order to improve the compatibility between organic polymers and layered clay, the interlayer distance of layered clay can be loosened by adding an intercalating agent to the clay, resulting in a larger interlayer distance to allow monomers. (Monomer) enters, and then through the polymer polymerization reaction to obtain intercalated 5 or exfoliated dispersed inorganic clay / organic polymer nano composite material. Intercalating agents mentioned in conventional literature include: 12-aminolauric acid, hexadecylamine, fatty amine, and bis (2- Hydroxyethyl) methyl tallow alkylammonium chloride® -10 (bis (2-hydroxyethyl) methyl tallow alkyl ammonium chloride), amines such as stearylamine or quaternary ammonium salt . These low-molecular polar salt-recording groups will form polar bonds with the charged layered inorganic clay, and make the clay's original hydrophilicity become oleophilic, so it can enhance the layered inorganic clay. Compatibility with organic 15 macromolecules is conducive to the next step of the delamination reaction. However, the improvement of the mechanical properties of materials still needs to be improved. The technology of adding layered clay treated with organic onium. Salt to organic polymers has been disclosed in many patent documents, for example: US Patent Nos. 6,552,113, 6,552,114, 6,486,252 and European 20 patent No. 1,235,876, etc., the purpose of these patents is mainly to use the treated layered clay to prepare coatings with good gas barrier properties and haze. In addition, in the National Patent Publication No. 550246, the inventor used a series of polyoxyalkylene amines with a molecular weight of 1800 or more as an intercalating agent to modify the layered clay, and the intercalation type 7 200538414 ( intercalation type) The interlayer distance of layered clay can be extended to 50 ~ 92A, and a nano silicon wafer / organic polymer nano composite material can be further prepared. Among these polyetheramine intercalating agents, polyoxypropylene diamine is preferred, for example: polypropylene glycol bis (2-aminopropyl ether 5) [poly (propyleneglycol) bis (2-aminopropyl ether)], whose trade names are Jeffamine (R) D-4000 and D-2000. However, when the present inventors further used layered clay dispersed by Jeffamine ^ DdOOO intercalation to react with organic polymers, although intercalating type of nano, silicon wafer / organic polymer nano can be prepared Composite materials, but because the intercalating agent D-2000 is easy to mix, 10 can be mixed into organic polymers, and it will interfere with the cross-linking reaction of organic polymers, which cannot greatly improve the hardness and thermal properties of composite materials. From the above, it is known that there is still a need for an inorganic / organic nano composite material with a uniform degree of dispersion and good mechanical properties (particularly hardness), transparency and thermal properties. 15 [Summary of the Invention] Summary of the Invention-Since conventional low-molecular-weight intercalating agents cannot be used to obtain uniform and dispersed nano-silicon wafers with high interlayer distances, the inventors of the present case further used intercalating agents with larger molecular weights to increase The distance between layers, in order to obtain better dispersion of the silicon wafer 20 (the technical content of this part has been disclosed in National Patent Bulletin No. 550246). However, in National Patent Publication No. 550246, the inventors of this case used polyetheramine intercalating agents (such as Jeffamine® D-2000 or D-4000) to modify the inorganic clay, although the intercalation type of the distance between the upper layers was obtained. Nano silicon wafers, 8 200538414 But when polymer materials are added to make nano composite materials, there is still room for improvement in the hardness, transparency and thermal properties of the obtained nano composite materials. The inventor of this case further improved the compatibility of 5 10 15 20 between organic polymer and layered clay to improve the mechanical properties, transparency and thermal properties of the composite material, and continued the concept of intercalation, in addition to making the sheet structure of layered clay There can be a distance between the upper layers, and the intercalation agent can be improved to make the layered clay reach a delaminated state, thereby improving the compatibility between the organic polymer and the layered clay. 'Therefore, the inventors of this case have made further improvements on the intercalating agent, and this change β ”is based on making polypropylene glycol bis (2-aminopropyl ether) with a molecular weight of 2000 (commercially available product Jeffamine® D-2000 ), P-phenol (p-cresol) and formaldehyde are polymerized to obtain a linear intercalating agent, that is, Amine-terminated Mannich polymer (Amine terminal-Mannich Oligomer (hereinafter simply referred to as "AMO intercalating agent") as an intercalating agent, as shown in the following chemical formula (I):

CH3 OH ▲ CH2NH-POP-NH ~ H (I).

Jn

Among them, POP is a bivalent moiety having the following chemical formula (II): RR —CHCH2- [〇CH2Ch] ^ (II) and R is an alkyl group, and η is an integer between 1 and 68 and m is an intermediate An integer between 10 and 100. 9 200538414 5 10 15 20 The inventor used the above-mentioned AMO intercalating agent to perform an intercalation reaction with the siliceous layered inorganic clay in an acidic environment, and further achieved a delamination state by controlling the degree of acidification, and then a substitution reaction To obtain a primary structure of AMO / inorganic clay nano silicate platelet. Therefore, in view of the above experimental results, the present invention provides a nano silicon wafer / organic polymer with good mechanical properties, transparency and thermal properties. Nanocomposite material, which is composed of an organic polymer and the above-mentioned AMO / inorganic clay nano silicon wafer. The present invention promotes the AMO by acidifying the terminal amine group of the AMO intercalator to form a quaternary ammonium cation, and using the quaternary ammonium cation as a cation initiator. / Inorganic clay nano silicon wafer and the organic polymer cross-linking reaction, so that the nano silicon wafer in the organic polymer can reach the degree of nano-scale dispersion, and further enhance the composite material Mechanical properties, transparency and thermal properties. In addition, the present invention also provides a high-hardness coating film, which is prepared by coating the above-mentioned nano-silicon wafer / organic polymer nano-composite material on a substrate and then heating it for a sufficient period of time. DETAILED DESCRIPTION OF THE INVENTION The present invention provides a nano silicon wafer / organic polymer nano composite material, which comprises an organic polymer and a nano stone chip. The nano silicon wafer is a product obtained by reacting an AMO intercalating agent having the following chemical formula (I) with a siliceous layered inorganic clay in an acidic environment:

10 (I) 200538414

OH

CH2NH-P〇P-NH-H Jn 5 wherein POP is a bivalent moiety having the following chemical formula (II):

R R -CHCH2 {〇CH2CH ^ (II) 10 15 and R is an alkyl group of CrC #, and η is an integer between 1 and 68, and · is an integer between 10 and 100. Preferably, in the formula (I), R is a methyl group, m is 33, and η is an integer between 1 and 10. In a specific example of the present invention, the AMO intercalating agent having the chemical formula (I) is a reaction product of one of polyetherdiamine, p-cresol and formaldehyde; and preferably, the polyetherdiamine is polypropyl Ether diamine; more preferably, the polyether diamine is polypropylene glycol bis (2-aminopropyl ether) [poly (propyleneglycol) bis (2-aminopropyl ether)], and its trade name is Jeffamine® D-2000. @ · Regarding the preparation of the AMO intercalating agent having the chemical formula (I), it can be prepared according to the known synthetic method, or according to the following reaction formula: 20 (1) Stir in toluene at 90 ° C ( 2) Add 37wt% aqueous solution of Pyrogallol + D-2000 -►AMO intercalation agent

(3) 90oC—130oC (4) 130 ° C, 5 hours The siliceous layered inorganic clay suitable for the present invention can be selected from the group consisting of 11 200538414: montmorillonite, kaolin (kolin ), Mica, talc, and one of these combinations. Preferably, the layered inorganic clay clay is montmorillonite. In a specific example of the present invention, the siliceous layered inorganic clay is a sodium-containing cation exchange type montmorillonite having a cation exchange equivalent (CEC) of 50 to 200 meq / 100g. And preferably, the siliceous layered inorganic clay is a sodium-containing cation exchange type montmorillonite having a cation exchange equivalent between 100 and 150 meq / 100 g. When the CEC is less than 50meq / 100g, the organicization achieved through ion exchange is not enough, which makes the clay difficult to swell. When the CEC is higher than 200meq / 100g, the bonding force between the interlayers is too high, which also makes the clay difficult. Swelling. The nano silicon wafer used for preparing nano composite materials in the present invention is a product obtained by reacting an AMO intercalating agent having a chemical formula 与 and a layered silica clay in an acidic environment. In the present invention, In a specific example 15, the nano silicon wafer is prepared according to the following steps: (a) dispersing a sodium-containing cation exchange type montmorillonite in hot water at about 80 ° C to form a uniform dispersion; (b) The AMO intercalating agent and the hydrochloric acid aqueous solution are mixed uniformly at about 80 QC to form a mixed liquid; 20 (c) The dispersion liquid of step (a) and the mixed liquid of step (b) are mixed to form An intercalating agent-clay mixed liquid; and (d) adding an alkaline solution to the intercalating agent-clay mixed liquid obtained in step (c) to perform a delamination reaction to obtain a reaction liquid; e) Wash and filter the reaction solution obtained in step (d) with an appropriate solvent, and 12 200538414 can obtain nano silicon wafers delaminated and dispersed by AMO intercalation agent. Preferably, in the organic polymer composition of the present invention, based on the total weight of the organic polymer composition, the content of the nano silicon wafer in the composition is 0.1 to 70 wt%, preferably less than 10 wt. %, More preferably not more than 5 wt%. 5 Furthermore, the organic polymers suitable for the present invention include, but are not limited to, the following: epoxy resin, polyamide, polystyrene (PS), polypropylene (PP), Polyurethane (PU), polyethylene terephthalate (PET), poly (propylene terephthalate) (PMMA), and one of these combinations. Preferably, the organic high fraction #. 10 is epoxy resin; and in a specific example of the present invention, the organic polymer is diglycidyl ether of bisphenol-A (referred to as "DGEBA", trade name "BE-188"), the molecular formula is as follows:

15 In addition, the nano silicon wafer / organic polymer nano composite material of the present invention optionally further includes a curing agent. The choice of curing agent is known to those who are familiar with this technology ® field, and can be changed according to the application and the type of organic polymer used. For example, when the organic polymer is epoxy resin and the use of composite 20 materials When it is a hard coat layer, a preferred curing agent is a phenol type curing agent. In a specific example of the present invention, the curing agent is amino triazine novolak (trade name “LA-775 1”), and its molecular formula is as follows:

13 200538414 T 佳 地 ’The equivalent ratio of the organic polymer molecules to the curing agent in the present invention is 0.1: 1 to 1:15. 〒 This organic high 5 10 15 can: the crosslink density between. The catalyst is also based on the molecules used and will not be described here.丨 It is well known to those in this technical field that the nano-stone chip / organic polymer nano-composite material of the present invention can be widely applied to various packaging materials, coatings, etc., and is especially suitable for coating systems, &;. In a specific example of the present invention, the nano-organic polymer polymer is coated on a substrate, and then heated for a period of time long enough to collect: to obtain a high-hardness coating film. [Embodiment] The present invention will be further described in the following examples, but it should be understood

Yes' These examples are for illustrative purposes only and should not be construed as limiting the implementation of the invention. x < Preparation example > Preparation of AMO / MMT nanometer silicon wafer 20 (I) Preparation of AMO intercalating agent: Add 27.2g (0.25mole) of the pair-injection (manufactured by ACROS) to the reaction bottle, 757.6 g (0.38mole) of polypropylene glycol bis (2-aminopropyl ether) (manufactured by Aldrich Chemical, trade name Jeffamine® D · 2000) and 600 mL of toluene, and heated to reflux at 90 ° C 3 14 200538414 5 10 15 20 hours. Next, 61.4 g (0.76 mole) of a 37 wt% aqueous formaldehyde solution (manufactured by ACROS) was added to the reaction flask. When the reaction temperature is increased from 90 ° C to 130 ° C and heated for 5 hours, the above mixture will become colloidal, and the reflux will be stopped, and finally the AMO intercalation agent can be obtained. (II) Preparation of nano silicon wafers: (a) Disperse 100g of sodium-containing cation-exchange montmorillonite (CEC = 115meq / 100g of Na + -MMT, trade name Kunipia F) in 10L at 80 ° C, heat In water, a homogenizer (manufactured by Xiangtai Seiki Co., Ltd., β · Model: HD220) was vigorously stirred for 4 hours to make the aqueous solution a soil-colored stable and uniform dispersion. (b) Mix 575 g of the AMO intercalator prepared in step (I) and 12 g of a 35 wt% concentrated hydrochloric acid solution at 80 ° C for 30 minutes to form a mixed solution. (〇)

The dispersion liquid obtained in step (a) and the mixed liquid obtained in step (b) are mixed, and vigorously stirred at 80 ° C for 5 hours with a homogenizer to complete the intercalation reaction, and obtain the upper and lower layers. Separated intercalator-clay mixture. (d) Add the intercalation agent-clay mixed solution obtained in step (c) to 46 g (-fold equivalent) of sodium hydroxide to carry out the delamination reaction and form a reaction solution. At this time, the reaction solution is light. Yellow viscous liquid in emulsified state. (e) Next, pour the reaction solution obtained in step (d) into 7.5L of ethanol and filter. The solid obtained after filtering is poured into 10L of ethanol and stirred well. After the final filtration, Can be obtained and light yellow 15 200538414 translucent nano silicon wafers delaminated by AMO intercalation agent (organic / inorganic ratio is about 40/60, hereinafter referred to as "AMO / MMT nano silicon wafers") .

10 15 20 <Comparative preparation example> Preparation of D-2000 / MMT nano silicon wafer

(a) Disperse 100g of sodium-containing cation-exchange montmorillonite (CE0115meq of KunipiaF / Na + -MMT of 100g) in 10L of 80 ° C hot water, and use a homogenizer (manufactured by Xiangtai Precision Machinery Co., Ltd.) (Α model HD220) was stirred vigorously for 4 hours, so that the aqueous solution formed a stable and uniform dispersion of earth color®. (B) 230 g (0.115 mol) of polypropylene glycol bis (2-aminopropyl ether) (Aldrich Chemical (Product name: Jeffamine® D-2000), an intercalating agent, is dissolved in hexanol, and hydrochloric acid (HC1) of equal molar number is added, and reacted at room temperature for 30 minutes to obtain an acidified intercalating solution. 〇)

The acidified intercalation solution obtained in step (b) is poured into the dispersion liquid in step (a) and stirred vigorously at a temperature of 60 to 70 ° C for 6 hours to perform a cation exchange reaction. After completion of the reaction, the reaction solution was allowed to stand in layer 0 (d). The reaction solution obtained in step (c) was filtered and washed several times with water and ethanol to remove unreacted D-2000 and montmorillonite. The obtained product was dried in a vacuum oven for 24 hours, and finally a siliceous layered inorganic clay modified with a d-2000 intercalator (hereinafter referred to as "D-2000 / MMT nano silicon wafer") was obtained. 16 200538414 &lt; Example &gt; &lt; Physical property test &gt; The following examples and comparative examples use the nano silicon wafers prepared in the foregoing preparation examples and comparative preparation examples to prepare nano composite materials, and are further prepared into 5 IOOμηι coating film, and evaluated by the following test methods: (i) Particle dispersion: Observe the size of Si02 particles using a transmission electron micrograph (hereinafter referred to as "TEM") manufactured by Zeiss, model EM902A. And dispersion in polymers. 1 10 (ii) Pencil hardness: A pencil hardness tester of model B-3084T3 manufactured by Jinliang Industrial Co., Ltd. was used, and tested in accordance with the standard method of ASTM D3363-74. (iii) Thermal expansion coefficient: The thermomechanical property analyzer (TMA) manufactured by Du Pont Co., Ltd. was used for measurement. 15 (iv) Transparency: The ultraviolet-visible light (UV-VIS) spectrometer manufactured by Perkin-Elmer, model No. is Lambda 20, and measured in the ultraviolet-visible light spectral range of 550 nm / T%. &lt; Source of Chemicals &gt; ⑴Organic polymer (bisglycidyl ether of bisphenol_A): manufactured by Nanya Chemical 20, product name is "BE-188", epoxy equivalent weight is 188 ° ( ii) Curing agent (amino-trifluoroacetic acid resin): manufactured by Dainippon Ink & Chemicals, under the product name "LA-7751". &lt; Example 1 &gt; 17 200538414 (1) Preparation of nano composites containing AMO / MMT nano silicon wafers: In a 100 ml PE bottle, 29.98 g (85.66 mmol) of Beta-188 and 8.62 g (26.85 mmol) were added. LA-7751, and stirred in a homogenizer using a mechanical stirring method (1000 rpm) for 5 minutes, and then slowly added 0.65 g of AMO / MMT nanosilica prepared in the above Preparation Example 1 to 5 And agitate (3500 rpm) for 15 to 20 minutes to obtain a nano-composite material containing 0.5 wt% AMO / MMT nano-silicon wafer. (2) Preparation of coating film: &lt; 10 The nanocomposite material obtained in (1) above was defoamed using a vacuum oven until no bubbles existed. Next, a flat film coating machine (manufactured by Universal Ocean Co., Ltd., model UNI 012) was used to apply a coating film (100 μm) to 180 ° C. (: Hard roasted in an oven for 3 hours to obtain a coated 15 film containing 0.5% by weight of AMO / MMT nanostone tablets, and tested for pencil hardness, thermal expansion coefficient and transparency, the results are shown in Table 1 &Lt; Example 2 &gt; (1) Preparation of nano-composite material containing AMO / MMT nano-silicon wafer: Except that the addition amount of the AMO / MMT nano-silicon wafer was changed to 13g 20, the rest of the steps were all Same as in Example 1. Finally, a nano-composite material containing 1% by weight of AMO / MMT nano silicon wafer can be obtained. (2) Preparation of coating film: The steps are the same as in Example 1, except that one with 1% by weight is finally obtained 18 200538414 AMO / MMT nanometer silicon wafer coating film, and tested for pencil hardness, thermal expansion coefficient and transparency, the results are shown in Table 1. &lt; Example 3 &gt; (1) AMO / MMT nano-containing Preparation of silicon wafer nanocomposite material: 5 Except that the addition amount of the ΑΜΟ / ΜΜΤ nanometer silicon wafer was changed to 4.0g, the rest of the steps were the same as in Example 1. Finally, a 3wt% ΑΜΟ was obtained. / MMT nano-silicon nano-composite material. (2) Preparation of coating film: 10 steps are the same as in Example 1. However, a coating film containing 3wt% ΑΜΟ / ΜΜΤ nanometer silicon wafer was finally obtained and tested for pencil hardness, coefficient of thermal expansion, and transparency, and the results are shown in Table 1. In addition, the observation of the dispersion status was also performed. As shown in Figure 1. &lt; Example 4 &gt; 15 (1) Preparation of nano-composite material containing ΑΜΟ / ΜΜΤ nano silicon wafer: In addition to changing the addition amount of ΑΜΟ / ΜΜΤ nano silicon wafer to 6.6 g In addition, the remaining steps are the same as in Example 1. Finally, a nano-composite material containing 5 wt% AMO / MMT nano-silicon wafer can be obtained. 20 (2) Preparation of coating film: The steps are the same as in Example 1, However, a coating film containing 5 wt% of ΑΜΟ / ΜΜΤ nano silicon wafer was finally obtained and tested for pencil hardness, thermal expansion coefficient, and transparency, and the results are shown in Table 1. &lt; Comparative Example 1 &gt; 19 200538414 (1 ) Preparation of epoxy material: Except that the AMO / MMT nano silicon wafer is not added, the other steps are the same as in Example 1. Finally, an epoxy resin material 05 (2) coating film preparation: The steps are the same as in Example 1. Finally, a coating film is obtained, and It was tested for pencil hardness, thermal expansion coefficient, and transparency, and the results are listed in Table 1. &lt; Comparative Examples 2 to 5 &gt; 10 (1) Preparation of nano-composite material containing D-2000 / MMT nano-silicon wafer: Except for replacing the AMO / MMT nano silicon wafer with the D-2000 / MMT nano silicon wafer prepared in the comparative preparation example, the rest of the steps and the amount of each composition are the same as those in Examples 1 to 4. Finally, nano-composites containing D-15 2000 / MMT nano-silicon wafers containing 0-5 wt%, 1 wt%, 3 wt%, and 5 wt% were obtained. (2) Preparation of coating film: The steps are the same as in Example 1, except that coating films containing D-2000 / MMT nano-silicon wafers containing lwt%, 3wt%, and 5wt% were respectively obtained (corresponding to Comparative Example 2 and 2 respectively). 3, 4 and 5), and test the pencil hardness, thermal expansion coefficient and transparency of these coating films for 20 times. The results are shown in Table 1. 20 200538414 Content (wt%) of AMO / MMT nanometer silicon wafer (delamination type) Table 1 Thermal expansion coefficient aoam / m ° C) M000 / MMMΓ Content of nanometer stone wafer (intercalation type) ( Wf / 〇) Hardness (Η) Transparency (%)

Results: The distribution of AMO / MMT nanopyrene tablets in organic polymers was observed: In general, 'the inorganic dot soil itself has a strong surface force between the flakes and the flakes' and when the crosslinking reaction occurs, Because the masking force with different magnitudes in different positions will cause the tendency of the parts to connect with each other. However, it can be clearly observed from FIG. 1 (Example 3) that it is single-organic polymer, that is, Zhao 0 / Linaiche = D ^ (2) Comparison of hardness and transparency dispersed in organic polymer: From Table 1 It can be seen that the hardness of the film of the embodiment of the present invention is much higher than that of the comparative example (without the addition of nanostone). The ancient coating is obviously improved from 2H to 8h. Transparency is also within the range, so it can be seen that the mechanical properties and maintenance of nano-stone samura ’s good organic composite materials are extremely improved. Comparing 21 15 200538414, it can be seen that the hardness increase by adding AMO / MMT is better than that of D-2000 / MMT. In particular, the present invention only needs to add 0.5% by weight of AMO / MMT nano silicon wafers to obtain Nano composite material with excellent hardness and transparency. (3) Comparison of thermal expansion coefficients: In Table 1, compared with Comparative Example 1, the thermal expansion coefficients of the coating films prepared in Examples 1 to 4 of the present invention 15 20 have a significant downward trend, and the reduction ratio is about It is 30% to 50%. This is because when the delaminated AMO / MMT nano silicon wafer is added to the organic polymer, the movement space of the organic polymer chain segment is limited, and the volume shrinkage problem of the organic polymer system itself is improved. In summary, the present invention is to prepare a nano silicon wafer / organic polymer nano composite material by adding nano silicon wafers delaminated and dispersed by an AMO intercalator to an organic polymer. In particular, the nano silicon wafer of the present invention only needs to add 0.5 wt% to obtain a nano composite material having excellent mechanical properties, transparency, and thermal properties. What's more, it is worth mentioning that in the present invention, the quaternary ammonium cation formed by acidifying the terminal amine group of the AMO intercalating agent can be used as a cationic initiator to promote the nano silicon wafer and the organic polymer. The cross-linking reaction between them further enables the nano silicon wafer to achieve nano-level dispersion in the organic polymer, and further improves the mechanical and thermal properties of the composite material. When the nanocomposite is made into a coating film, it does have excellent mechanical properties (especially hardness), transparency, and thermal properties. However, the above are only the preferred embodiments of the present invention. When the scope of implementation of the present invention cannot be limited in this way, that is, where anyone applies for a patent according to the present invention

22 200538414 and simple equivalent changes and modifications made to the contents of the invention description should still fall within the scope of the invention patent. [Brief description of the figure] FIG. 1 is a drawing of a coating film made of a nano silicon wafer / organic polymer nano composite material containing 3 wt ° / 0 AMO / MMT nano 5 meter silicon wafer in Example 3 of the present invention. TEM image. [Description of Symbols of Main Components of the Drawings] (None) 23

Claims (1)

200538414 Scope of patent application: [-a kind of nano silicon wafer / organic polymer nano composite material, including: an organic polymer; and a nano silicon wafer, 焱 &amp; θ. It is a system with the following chemical formula (I The intercalation agent) and the stone-layered inorganic clay are reacted under an acidic environment. The product J 〇 H2N POP is called H2c ^^ jpCH2NH 屮. p N Yin η ⑴ where POP is a bivalent moiety having the following chemical formula (π); RR —CHCHa + OCHaCHj ~ (丨 丨) and R is (^ ~ (: an alkyl group of 4, and η is between 1 to Integer between 68, m is an integer between 10 and 100. 2. For example, the nano-stone sheet / organic polymer nano-composite material of item #j of the patent application, where the organic high The molecular system is selected from the group consisting of:% oxygen resin, polyamide, polystyrene (ps), polypropylene (pp), polyurethane (PU), polyethylene terephthalate ( pET), polymethyl methacrylate (PMMA), and one of these combinations. 3. The nanometer stone chip / organic polymer nanocomposite material, such as the second item of the patent application scope, wherein the organic polymer It is epoxy resin. 4. For example, the nano silicon wafer / organic polymer nano composite 24 200538414 to the material in the scope of the patent application, where m is an integer between 3 # ίο.丨 In 5. If the nano-silicon material according to the scope of the patent application item 丨, wherein the chemical formula has an insertion ::: nano-composite m ^ 9 is just the reaction product of one of polyetherdiamine, p-cresol and formaldehyde. 6. For example, the nano-silicon U +: iganshijia organic south molecular nanocomposite, medium and financial The oxygen layered inorganic clay system is selected from the group 1 of the following = soil removal-coffee. Xian. _), Kaolin 0, mica, talc, and one of these groups 7. = The nanometer stone chip / organic high-molecular nanometer compound of the first item of the patent scope is compounded therein. The cation exchange equivalent (CEC) of the siliceous layered inorganic clay is between 50 and 200meq / 1OOg. between. 8. For example, please apply the nanometer stone chip / organic polymer nanometer compound 9 in the patent scope No. 7. In the silicon oxide inorganic inorganic clay, the cation exchange equivalent (CEC) is between 100 and 15 〇meq / 1〇〇g. The content of nanometer silicon wafer / organic polymer nanometer composite material in the first item of the monthly patent scope is based on the total weight of the nanometer composite material, and the content of the nanometer silicon wafer in the nanometer composite material property is 〇1 ~ 70% by weight. Female = nano silicon wafer / organic polymer nano composite material in the ninth scope of the patent, where the content of the nano silicon wafer in the nano composite material is based on the total weight of the nano composite material Less than 10 wt%. 1. The nano silicon wafer / organic polymer nano composite material as claimed in item 10 of the patent scope, where 'based on the total weight of the nano composite material, the nano dream tablet is in the nano composite material. The content is not more than 5wt%. 25 200538414 奈 Nano Dream Tablets / Organic Polymer Nano-Patents No. 1 or 3 in the patent scope 奈 12 Nano-chips / Organic Polymer Nano-composite in the patent scope No. 12, wherein the curing agent is a phenol type curing agent. 14, = Please take a full-time job in the 13th edition of _ Tablets / Organic Polymer Nanocomposite I 枓 where “equivalent ratio” of the organic polymer and curing agent contained in the polymer is 1: 1 to 1: 1. 5 〇 15.2 Please use the nano-sheet / organic polymer nano-composite Hoco in item 3 of the patent, which is used in the manufacture of coatings. 16 · ::: Hardness coating film ’is based on the scope of patent application! Or 3 Two = sheet / organic polymer nano composite material is prepared by coating on the substrate and heating it for a long enough time. 26