TWI284138B - 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

1284138 发明, DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a nano crepe sheet/organic polymer nano composite material and use thereof. In particular, the present invention relates to a nanocomposite in which an organic polymer is doped into a delaminated nanosheet, and the nanocomposite can be further prepared to have excellent mechanical properties, transparency, and thermal properties. Coating film. [Prior Art] Inorganic clay-10 organic polymer nanocomposite is one of the important materials currently being developed in the industry. In recent years, many literatures and patents on nanocomposites have been reported. For example, Sakamoto Toyota has [NKb+CCHOuCOCT] montmorillonite dispersed in Nylon 6 and developed the first piece to be practically used in the market. Inorganic clay/organic polymer nanocomposite. These 15 documents and patents disclose the addition of natural or synthetic layered clay as an inorganic filler to the catalyst and polymer materials to improve the solvent resistance of the polymer material. Gas barrier property, mechanical properties and thermal properties. Since the surface of the unmodified layered clay is hydrophilic 20, it has poor compatibility with the general hydrophobic organic polymer, so that it is easy to be uniformly dispersed due to aggregation phenomenon. Shortcomings. Therefore, the improvement of the mechanical and thermal properties of the composite material depends on whether there is good compatibility between the organic high molecular layer and the layered clay, that is, the degree of dispersion of the layered clay in the organic polymer. 1284138 In order to improve the compatibility between organic polymer and layered clay, a large interlayer distance can be caused by the intercalating agent in the clay to loosen the interlayer distance of the layered clay to allow the monomer. (monomer) enters, and further, an intercalated or exfoliated dispersed inorganic clay/organic polymer nano composite material is obtained through a polymer polymerization reaction. Intercalating agents mentioned in the prior art include: 12-aminolauric acid, hexadecylamine, fatty amine, bis(2-hydroxyl) An amine or a quaternary ammonium salt such as bis(2-hydroxyethyl)methyl tallow alkyl ammonium chloride or stearylamine. These low-molecular polar salt groups form a polar bond with the charged layered inorganic clay, and the original hydrophilicity of the clay becomes oleophilic, thereby enhancing the layered inorganic clay. The compatibility with the organic 15 polymer is beneficial to the next step of the delamination reaction, but there is still room for improvement in the mechanical properties of the material. The technique of adding a layered clay treated with an organic onium salt to an organic polymer has been disclosed in many patent documents, for example, U.S. Patent Nos. 6,552,113, 6,552,114, 6,486,252 and Europe. 20 Patent No. 1,235,876, etc., the purpose of which is to use a treated layered clay to prepare a coating having good gas barrier properties and haze. Further, in the National Patent Publication No. 550246, the inventors have used a series of polyoxyalkylene amines having a molecular weight of 1800 or more as an intercalation agent to modify a layered clay, and the intercalated type 7 1284138 obtained ( Intercalation type) The interlayer distance of the layered clay can be expanded to 50 to 92 A, and a nano-sheet/organic polymer nano composite can be further prepared. Among the polyetheramine intercalators, polyoxypropylene diamine is preferred, for example, polypropylene glycol bis(2-aminopropyl ether 5 ) [poly(propyleneglycol) bis (2-aminopropyl) Ether)], its trade names are Jeffamine® D_4000 and D-2000. However, when the present inventors further reacted with an organic polymer by layered clay dispersed by Jeffamine® D-2000, an intercalating type of nanosheet/organic polymer naphthalene can be obtained. Rice composite material, but because the intercalating agent D-2000 is easily mixed into the organic polymer, it will interfere with the cross-linking reaction of the organic polymer, and cannot greatly improve the hardness and thermal properties of the composite material. From the above, there is still a need for an inorganic/organic nanocomposite material having a uniform degree of dispersion and good mechanical properties (especially hardness), transparency and thermal properties. 15 SUMMARY OF THE INVENTION Summary of the Invention Since the nano-powder sheet having a uniform dispersion and a high-level distance cannot be obtained by using a conventional low-molecular type intercalating agent, the inventors of the present invention further utilize a larger molecular weight intercalating agent to increase the interlayer distance. In order to obtain better film 20 dispersion (the technical content of this part has been disclosed in National Patent Publication No. 550246). However, in the National Patent Publication No. 550246, the inventors of the present invention used a polyetheramine intercalating agent (for example, Jeffamine® D-2000 or D-4000) to modify the inorganic clay, although the intercalation type of the inter-high-rise distance was obtained. Nano-ruthenium, 1284138 However, when it is added to a polymer material and made into a nano-composite material, there is still room for improvement in hardness, transparency and thermal properties of the obtained nano-composite material. The inventor of the present invention further improved the compatibility between the organic polymer and the layered clay to enhance the mechanical properties, transparency and thermal properties of the composite material, and continued the concept of the intercalation layer, except that the sheet-like structure of the layered clay can have a high-rise layer The distance and the intercalation agent are modified to achieve the delamination state of the layered clay, thereby improving the compatibility between the organic polymer and the layered clay. Ίο 15 Therefore, the inventors of the present invention further improved the intercalation agent by using polypropylene glycol bis(2-aminopropyl ether) having a molecular weight of 2000 (i.e., commercially available Jeffamine 8D-2000), p- The phenyl age (p-cresol) is polymerized with phthalic acid to obtain a linear intercalating agent, that is, an amine-based Mannich oligomer (Amine terminal-Mannich). Oligomer, hereinafter referred to as "AMO intercalating agent" as an intercalating agent, is represented by the following chemical formula (I): η2ν-ρορ-ην|η2ο

CH2NH-POP-NHj-H (丨)

Wherein POP is a divalent moiety having the following chemical formula (II): RR-6hCH2+〇CH2Ch]^ (II) and R is an alkyl group, and η is an integer between 1 and 68 and m is between 10 An integer between 100 and 100. 20 1284138 The present inventors used the above-mentioned AMO intercalating agent to carry out an intercalation reaction with the niobium oxide layered inorganic clay in an acidic environment, further controlling the degree of acidification to achieve a delamination state, and then obtaining a primary structure through a substitution reaction. AMO/inorganic clay nano silicate platelet 〇5 Therefore, in view of the above experimental results, the present invention provides a nano sized sheet/organic polymer nano composite having good mechanical properties, transparency and thermal properties. The material comprises an organic polymer and the above-mentioned AMO/inorganic clay nanosheet. The present invention facilitates the formation of a quaternary ammonium cation 10 by acidifying the terminal amine group of the AMO intercalating agent and using the quaternary cation as a cation initiator. The crosslinking reaction between the AMO/inorganic clay nanosheet and the organic polymer further enables the nanosheet to reach the nanometer level of dispersion in the organic polymer, 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-ruthenium sheet/organic polymer nano composite material onto a substrate and then heating for a sufficiently long period of time. . DETAILED DESCRIPTION OF THE INVENTION The present invention provides a nanosheet/organic polymer nanocomposite, 20 comprising an organic polymer and a nanocrystalline sheet. The nanosheet is a product obtained by reacting an AMO intercalant of the following chemical formula (I) with a bismuth layered inorganic clay in an acidic environment: 10 1284138 OH h2n-pop-hn|h2c

CH2NH-POP-N juice Η (I) wherein POP is a divalent moiety having the following chemical formula (II):

RR —CHCH2-f〇CH2CH]^ (II) ίο 15 and R is (^~the alkyl group, and η is an integer between 1 and 68, and m 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 ruthenium intercalation agent of the formula (I) It is a reaction product of polyether diamine, p-cresol and furfural; and preferably, the polyether diamine is a polypropyl ether diamine; more preferably, the polyether diamine is a polypropylene glycol double ( 2-Aminopropyl ether], which is commercially available as Jeffamine® D_2000. For the preparation of the AMO intercalant having the formula (I), it can be synthesized according to the conventional method. Prepare, or according to the following reaction formula: 20 (1) in benzene, stirring at 90 ° C (2) adding 37 wt% aqueous solution of p-cresol + D-2000 - ► ΛΜΟ intercalant

(3) 90 ° C ^ 130 ° C (4) 130 ° C, 5 hours The oxygen-containing layered inorganic clay suitable for use in the present invention may be selected from the group consisting of 11 1284138 5 10 15 20: Montmorillonite, kolin, mica, talc, and combinations of these. Preferably, the layered inorganic clay is montmorillonite. In a specific example of the present invention, the cerium-oxygen layered inorganic clay is a sodium-containing cation exchange type montmorillonite having a cation exchange equivalent ("CEC") between 50 and 200 meq/100 g. And preferably, the cerium-oxygen layered inorganic clay is a sodium-containing cation exchange type montmorillonite having a cation exchange equivalent of between 100 and 150 meq/100 g. When the CEC is lower than 50meq/100g, the organicization achieved by ion exchange is not enough, and the clay is not easy 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 to swell. . The nano-ruthenium sheet for preparing a nano composite material in the invention is a product obtained by reacting an AMO intercalating agent of the formula (I) with a cerium-oxygen layered inorganic clay in an acidic environment, and In one embodiment of the invention, the nanosheet is prepared according to the following procedure: (a) Dispersing a sodium-containing cation exchange type montmorillonite at about 80. (: in hot water to form a uniform dispersion; (b) mixing the AMO intercalant with aqueous hydrochloric acid at about 80QC to form a mixed solution; (c) dispersing the step (a) Mixing with the mixture of step (b) to form an intercalant-clay mixture; and (d) adding an alkaline solution to the intercalant-clay mixture obtained in the step (c), Performing a delamination reaction to obtain a reaction solution; (e) washing and filtering the reaction liquid obtained in the step (d) with a suitable solvent, 12 1284138 to obtain a nano-deposited lysate dispersed by the AMO intercalation agent Preferably, in the organic polymer composition of the present invention, the content of the nano tablet in the composition is 0.1 to 70% by weight based on the total weight of the organic polymer composition, preferably Less than 10% by weight, more preferably not more than 5% by weight. Further, organic polymers suitable for use in the present invention include, but are not limited to, the following: epoxy resin, polyamide, poly Styrene (PS), polypropylene (PP), polyurethane (PU), polyethylene terephthalate (polyethylene terephthalate, PET), polymethyl phthalic acid methyl ester (PMMA), and a combination thereof. Preferably, the organic polymer is an epoxy resin; and in a specific example of the present invention, the organic The polymer is diglycidyl ether of bisphenol-A ("DGEBA", trade name "BE-188"), and the molecular formula is as follows: 15 c

3Φ 5RCH3 Η2 HCDH H2CIO c I o η

CICI

-O-CHp \7 Further, the nanosheet/organic polymer nanocomposite of the present invention may optionally further comprise a curing agent. The choice of curing agent is known to those skilled in the art and can vary depending on the application and the type of organic polymer used, for example, when the organic polymer is an epoxy resin and the composite material is hard coated. In the case of a layer, a preferred curing agent is a phenol type curing agent. In a specific example of the present invention, the curing agent is an amino triazine novolak (trade name "LA-7751"), and the molecular formula is as follows:

13 1284138 Che Jia is also in the organic molecular composition of the present invention, the equivalent ratio of the organic high molecular weight to the curing agent is from 0.1:1 to 1:1.5. Further, the nanosheet/organic polymer nanocomposite of the present invention is also selectively incorporated into a catalyst for increasing the crosslinking density between the organic polymers. The catalyst may also be varied depending on the organic polymer to be used and the curing agent, and is also known to those skilled in the art, and therefore will not be described here. The nanosheet/organic polymer nanocomposite of the present invention can be widely applied to various packaging materials, coatings, etc., and is particularly suitable for the manufacture of coatings. In the specific example of the present invention, the nanosheet/organic polymer nanocomposite is applied to a substrate and then heated for a sufficiently long period of time to obtain a high hardness coating film. The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting. &lt;Preparation Example&gt; Preparation of ΑΜΟ/ΜΜΤ奈矽片 2〇(I) Preparation of ΑΜΟ Intercalating Agent································ '757.6 g (0.38 m〇le) of polypropylene glycol bis(2-aminopropyl ether) (manufactured by Aldrich Chemical Co., trade name: Jeffamine® D_2000) and 600 mL of toluene, and heated to reflux at 90 ° C 3 14 1284138 hours. Then, 6 i.4 g (〇.76 mole) of a 37 wt% aqueous formaldehyde solution (manufactured by ACR®) was added to the reaction flask. During the reaction temperature being raised from 9 ° C to 130 ° C and heating for 5 hours, the above mixture became colloidal, and the reflux was stopped, and finally the AMO 5 intercalant was obtained. (II) Preparation of nanosheets: (a) Disperse 100g of sodium-containing cation exchange montmorillonite (CEC=115ineq/100g of Na+_MMT, trade name Kunipia F) in 10L of 80oC hot water' The mixture was vigorously stirred for 4 hours using a homogenizer (manufactured by Xiangtai Seiki Co., Ltd., model 10 was HD22) to form a stable and uniform dispersion of the earth color in the aqueous solution. (b) 575 g of the AMO intercalant prepared in the step (1) and 12 g of a 35 wt% concentrated hydrochloric acid solution were mixed at 8 ° C for 30 minutes to form a mixed solution. 15 (c) mixing the dispersion obtained in the step (a) with the mixture obtained in the step (b), and vigorously stirring at 80 ° C for 5 hours using a homogenizer to complete the intercalation reaction, and An intercalation agent/clay mixture obtained by separating the upper and lower layers is obtained. (d) adding the intercalant-clay mixture obtained in the step (c) to 46 g (one 20 equivalents) of sodium hydroxide to carry out a delamination reaction and forming a reaction liquid, at which time the reaction liquid is a A viscous liquid in a light yellow emulsified state. (e) Next, the reaction liquid obtained in the step (d) is poured into 7.5 L of ethanol and filtered, and the solid obtained after filtration is poured into 10 L of ethanol and uniformly mixed, and finally filtered. , can obtain and light yellow 15 1284138 translucent AMO intercalation agent delaminated and dispersed nano-powder tablets (organic / inorganic ratio of about 40 / 60, hereinafter referred to as "AMO / MMT nano-slices" ). 5 &lt;Comparative Preparation Example>Preparation of D-2000/MMT Nanosheets (a) Disperse 100 g of sodium-containing cation exchange type montmorillonite (trade name Kunipia F CEC=115 meq/100 g of Na+_MMT) in 10L The mixture was stirred in a hot water of 80 ° C for 4 hours using a homogenizer (manufactured by Xiangtai Seiki Co., Ltd., model HD220) to form a stable uniform dispersion of the earth color 10 in the aqueous solution. (b) 230 g (0.115 mol) of polypropylene glycol bis(2·aminopropyl ether) (manufactured by Aldrich Chemical Co., Ltd., trade name: Jeffamine® D-2000) is intercalated in hexanol, and then added. Hydrochloric acid (HC1) in the ear and reacted at room temperature for 30 minutes to obtain an acidified intercalation solution. 15 (c) The acidified intercalation solution obtained in the step (b) is poured into the dispersion of the step (a), and vigorously stirred at a temperature of 60 to 70 ° C for 6 hours to carry out a cation exchange reaction. After the reaction was completed, the reaction solution was allowed to stand to separate layers. (d) The reaction liquid obtained in the 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 an oxygenated layered inorganic clay (hereinafter referred to as "D-2000/MMT nanosheet") modified with a D-2000 intercalator was obtained. 16 1284138 &lt;Examples&gt;&lt;Physical property test&gt; The following examples and comparative examples were respectively prepared using the nanosheets prepared in the above Preparation Examples and Comparative Preparation Examples to prepare a nanocomposite material, and further prepared into 5 parts. The coating of ΙΟΟμιη was evaluated by the following test methods: (i) Particle dispersion: The SiO 2 particle size was observed using a transmission electron micrograph (hereinafter referred to as "TEM" manufactured by Zeiss Corporation, Model EM902A). And the dispersion in the polymer. 10 (ii) Pencil hardness: A pencil hardness tester manufactured by Jinliang Industrial Co., Ltd., model B-3084T3, was used and tested according to the standard method of ASTM D3363-74. (iii) Thermal expansion coefficient: Measurement was carried out using a thermomechanical property analyzer (TMA) manufactured by Du Pont, Model TMA2940. 15 (iv) Transparency: UV-visible (UV-VIS) spectrometer manufactured by Perkin-Elmer, model Lambda 20, was measured at 550 nm/T% ultraviolet-visible spectral range. &lt;Chemical Source&gt; (i) Organic Polymer (Double-A diglycidyl ether): manufactured by Nanya Chemicals 20 Co., Ltd. under the name "BE-188", epoxide equivalent weight is 188 〇(ii) Curing agent (amino-based saponin): manufactured by Dainippon Ink & Chemicals, under the trade name "LA-7751". &lt;Example 1&gt; 17 1284138 (1) Preparation of nanocomposite containing AMO/MMT nanosheet: 29.98 g (85.66 mmol) of ΒΕ-188 and 8.62 g (26.85 mmol) were added to a 100 ml ΡΕ bottle. LA-7751, and stirred by a homogenizer by mechanical stirring (1000 rpm) for 5 minutes, and then slowly added 0.65 g of the AMO/MMT nanosheet prepared in the above Preparation Example 1 in 5, and continuously stirred. (3500 rpm) 15 to 20 minutes, and a nanocomposite containing 〇.5 wt% of AMO/MMT nanosheets was obtained. (2) Preparation of coating film: 10 The nanocomposite obtained in the above (1) was defoamed in a vacuum oven until no bubbles were present. Then, it was coated with a flat film coater (manufactured by Universal Co., Ltd., model UNI 012) and baked in an oven at 180 ° C for 3 hours to obtain an AMO/MMT containing 0.5 wt%. The film of the nano-film was coated with 15 films, and the pencil hardness, thermal expansion coefficient and transparency were tested. The results are shown in Table 1. &lt;Example 2&gt; (1) Preparation of nanocomposite containing AMO/MMT nanosheet: In addition to the addition amount of the AMO/MMT nanosheet to 1.3g 20, the remaining steps were Example 1 is the same. Finally, a nanocomposite containing 1% by weight of AMO/MMT nanosheets was obtained. (2) Preparation of coating film: The procedure was the same as in Example 1, except that a coating film containing 1 wt% of 18 1284138 AMO/MMT nanosheets was obtained, and the pencil hardness, thermal expansion coefficient and transparency were tested. The results are shown in Table 1. &lt;Example 3&gt; (1) Preparation of nanocomposite containing ruthenium/niobium nanosheet: 5 Except that the addition amount of the ruthenium/iridium nanosheet was changed to 4.0 g, the other steps were Example 1 is the same. Finally, a nanocomposite containing 3 wt% of lanthanum/niobium iridium chips was obtained. (2) Preparation of coating film: 10 The procedure was the same as in Example 1, except that a coating film containing 3 wt/min of yttrium/yttrium naphthalene film was finally obtained, and the pencil hardness, thermal expansion coefficient and transparency were tested. The results are shown in Table 1. In addition, the observation of the dispersion condition was also carried out, and the results are shown in Fig. 1. &lt;Example 4&gt; 15 (1) Preparation of nanocomposite containing ruthenium/niobium nanosheet: Except that the addition amount of the ruthenium/iridium nanosheet was changed to 6.6 g, the other steps were Example 1 is the same. Finally, a nanocomposite containing 5 wt% of ruthenium/iridium nanosheets was obtained. 20 (2) Preparation of coating film: The procedure was the same as in Example 1, except that a coating film containing 5 wt% of lanthanum/niobium bismuth film was finally obtained, and the pencil hardness, thermal expansion coefficient and transparency were tested. Listed in Table 1. &lt;Comparative Example 1&gt; 19 1284138 (1) Preparation of epoxy resin material: The same procedures as in Example 1 were carried out except that the AMO/MMT nanosheet was not added. Finally, an epoxy resin material 〇5 (2) coating film can be prepared: the same procedure as in the first embodiment, a coating film is finally obtained, and the pencil hardness, thermal expansion coefficient and transparency are tested, and the results are respectively listed in in FIG. 1. <Comparative Example 2 to 5> 10 (1) Preparation of a nano composite material containing D-2000/MMT nanosheets: In place of the AMO/, a D_2000/MMT nanosheet prepared by comparison of the preparation examples was used. Except for the MMT nanosheets, the remaining steps and the composition amounts were the same as in Examples 1 to 4, respectively. Finally, nanocomposites containing D-15 2000/MMT nanosheets containing 〇.5 wt%, 1 wt%, 3 wt%, and 5 wt% were obtained, respectively. (2) Preparation of Coating Film: The procedure was the same as in Example 1, except that coating films containing Dwt2000/MMT nanosheets containing lwt°/〇, 3 wt%, and 5 wt% were respectively obtained (corresponding to comparative examples, respectively) 2, 3, 4 and 5), and 20 lines of pencil hardness, thermal expansion coefficient and transparency test were applied to the films, and the results are shown in Table 1. 20 1284138 Table 1 Content of AMO/MMT nanosheet (delamination type) (wt%) I&gt;2000/MMT content of nano-stone (intercalation type) (Wt°/o) Wei (8) Transparency (% Thermal expansion coefficient a 〇 Ltm / m ° C) Example 1 0.5 0 6 57.5 69.5 Example 2 1 0 7 56.1 51.4 - Example 3 3 ο Ί 7 1 50.3 30.6 Example 4 5 0 8 43.6 1 - Comparative Example 1 0 0 2 60.0 80.1 Comparative Example 2 0 0.5 4 59.3 52.0 Comparative Example 3 0 1 5 58.2 33.5 Comparative Example 4 0 3 5 56.8 32.3 ~~ Specific vehicle example 5 0 5 6 55.4 - (1) AMO/MMT nanometer Observation of the distribution of the film in the organic polymer: 5 In general, the inorganic clay itself has a strong surface force between the sheet and the sheet, and when the crosslinking reaction occurs, the force varies depending on the position. The squeezing will result in a tendency to connect portions between the sheets. However, it can be clearly seen from Fig. 1 (Example 3) that a single sheet is dispersed in the organic polymer, that is, the ΑΜ〇/ΜΜΤ nanosheet is uniformly dispersed in the organic polymer. (2) Comparison of hardness and transparency: As can be seen from Table 1, the hardness of the coating film prepared in Example 4 of the present invention is much higher than that of the comparison (no addition of nano-stone tablets), hardness Month, , , and Becky can be upgraded by 2Η and the transparency is maintained within a good range of 15'. Therefore, the addition of nano-slices can effectively improve the mechanical properties of inorganic/organic composites and maintain excellent transparency. Furthermore, it can be seen from the comparison of the example 4 and the comparative example of the corresponding amount of 21 1284138 that the addition of AMO/MMT is better than the effect of adding D_2000/MMT, especially the invention only needs to add 〇. A 5wt% AMO/MMT nanosheet can be used to obtain a nanocomposite with excellent hardness and transparency. 5 (3) Comparison of thermal expansion coefficients:

In Table 1, compared with Comparative Example 1, the thermal expansion coefficient of the coating film produced in Examples 1-4 of the present invention showed a tendency to decrease remarkably, and the reduction ratio was about 30% to 50%. This is because when the delaminated AMO/MMT nanosheet is added to the organic polymer, the H 〇 activity space of the organic polymer segment is restricted, and the volume shrinkage problem of the organic polymer system itself is improved. . In summary, the present invention prepares a nanosheet/organic polymer nanocomposite by adding a nanosheet which is delaminated and dispersed by an AMO intercalation agent to an organic polymer. In particular, the nanosheet of the present invention is added in an amount of only 5 〇.5 wt% to obtain a nanocomposite having excellent mechanical properties, transparency and thermal properties. Moreover, it is worth mentioning that the quaternary ammonium cation formed by acidification of the amine group at the end of the amyl intercalation agent can be used as a positive β ion initiator to promote the nano bismuth tablet. The cross-linking reaction between the organic polymer further enables the nano-ruthenium sheet to reach a degree of dispersion of the nano-meter scale in the organic polymer, and further improve 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 is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention as a simple equivalent change according to the scope of the invention and the contents of the description of the invention. And modifications are still within the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a TEM image of a coating film made of a nanosheet/organic polymer nanocomposite containing 3 wt% of AMO/MMT naphthalene 5 m wafer according to Example 3 of the present invention. . [Description of main components of the figure] (none) 23

Claims (1)

1284138 Pickup, patent application scope:, rice bran sheet / organic polymer nano composite material, comprising: an organic polymer; and ^ no rice stone Xi's film is an intercalant and oxygen layer with the following chemical formula (1) The product obtained by the reaction of the inorganic clay in an acidic environment is 0H HaN-POp.HNl^c^^^cHaNH pop NHi^ (1) wherein POP is a divalent moiety having the following chemical formula (π); RR-CHCHg+OCHgCHj· ^ (||) and R is (^~(:4), and n is an integer between 1 and (10), and m is an integer between 1〇 and 1〇〇. The patent range is the nanometer stone tablets/organic polymer nano composites t 2 , wherein the organic polymer is selected from the group consisting of the following groups: Oxygen erythraea, polyamine, polystyrene ( Ps), polypropylene (pp), polyaminomethine (pu), poly(pET), polymethyl methacrylate (PMMA), and combinations of these. 3. The nanometer Ishikawa organic polymer nano composite material according to the second item of the patent application scope, wherein the organic polymer is an epoxy resin. The application of the patent scope of the project of nano-stone tablets / organic polymer nanocomposite 24 1284138: only two of which, in the chemical formula (1) ..., η is an integer between 丨 to 10 0. The nanosecond piece of the first item/organic polymer nanocomposite Π The intercalating agent of the chemical formula (1) is a reaction product of (iv) diamine, p-cresol and formaldehyde. 6·nr circumference item 1 (n) Sheet/organic polymer nanocomposite crucible," oxygen layered inorganic clay is selected from the group consisting of: montmorillonite (also known as rillonite), kaolin (k〇iin), mica (mica) , talc powder (talc), and the combination of the above-mentioned 7 _ ^ patent patent scope 1 of the nano-stone tablets / organic nano-composite, the cation exchange equivalent of the stone-like layered inorganic clay (CEC The system is between 50 and 200 meq/1〇〇g. 8. The nano-polymer nano-composite of nano-shixi tablets, according to item 7 of the patent application scope, wherein the stone-like layered inorganic clay The cation exchange equivalent (CEC) is between 1 〇〇 and 15 〇 meq / 1 〇〇 g. The nanometer stone slab/with the smashing polymer nano composite material 'where' the total weight of the nano composite material, the content of the nano slab in the nano composite material is 〇1~7〇 Ww%. 1〇.If applying for the full-length ninth section of the nano-section/organic polymer nanocomposite, the nano-stone composite is used in the nano composite according to the total weight of the nano composite. The content of the medium is less than U. The nano-stone film/organic polymer nano composite material according to the tenth item of the patent application scope, wherein the nano-side film is in the nanometer based on the total weight of the nano composite material The content of the rice composite towel is not more than 5% by weight. 25 1284138 12. 13. 14. 15. 16. If the patent application is not included in the first or third paragraph of the patent, the bismuth/organic polymer nanocomposite material further comprises a curing agent. For example, in the case of claim 12, the curing agent is a phenol type curing agent, which is a phenol type curing agent. For example, the nano-composite material of the patent application No. 1335, 1 towel ^. The monthly/organic 鬲 molecule is not recovered, and contains an organic high score of 0.1:1 to 1:1 5. In the case of the curing agent, for example, the material of the third item of the patent application, the child/, the eve film/organic polymer nano composite _ ^ eight series is used for the manufacture of the coating. A film for hardness coating, which is a series of nano-slices/right sputum, claiming patent range 1 or 3, and then applying 敎 子 纳米 nano composite material coated onto the substrate It is prepared by a long time. 26