TWI292413B - The composition and synthetic method of nano-dispersed clay vinylester resin - Google Patents

Description

1292413 IX. Description of the invention: [Technical field to which the invention pertains] The present invention particularly relates to a nano-dispersed clay vinyl ester resin and a synthetic method 'mainly based on a method for synthesizing vinyl ester to obtain a nano-clay vinyl ester tree. It is known in the present invention that a reactive diluent such as (Styrene) can be used to form a liquid nano-dispersed bismuth silicate layer which is uniformly dispersed in a vinyl ester substrate to enhance the compatibility of the inorganic phase with the organic phase. In addition to the role of filler, layered clay also provides the role of synthetic reaction and catalytic synthesis, and changes the morphology of the resin molecular chain in the nano-clay vinyl ester resin, so that the resin is hardened under the reaction conditions with hardener and accelerator. The obtained nano-composite composite material and physical properties are deeply affected by the reaction process, the composition of each composition, the ratio, the reaction temperature, and the intercalating agent. Only a nano-composite material with simultaneous improvement of mechanical strength and hardness can be obtained. The obtained bismuth-containing layer clay can be regarded as a nano-organic resin. The vinyl ester resin can be regarded as a new type of organic/inorganic hybrid resin. Increase its added value. [First-hand technology] According to the traditional organic composite material, the material is a combination of two or more materials, because of its light weight, high strength, high degree of freedom, and weather resistance and corrosion resistance. Such excellent performance, in the aerospace, ship, wheel transport, rail, building materials, electronic mobilization, leisure industry and public works materials, etc. φ - has become one of the thick grade of organic materials. The organic polymer is added with inorganic materials such as glass fiber, bismuth glass beads and talc powder, etc., and the type of compound _ and the inorganic phase are taken from the organic phase to form a two-phase material, because the inorganic material cannot be extremely fine in 1292413. The reinforcing effect of combining the two has a certain limit reduced to 100 nm, and the complementary effect is complementary to form a mixed material, that is, one of the fields, if it can be present in the substrate, and has excellent machine separation characteristics. Dispersion (1 to 100 nm) and the composite material is easy to break. Therefore, the inorganic strong effect will be improved and perfected. Nanocrystallization is a current state in which the related nano-sized clay tends to be homogeneous, and the mechanical properties, thermal properties, and phase separation are easily formed, which further increases the particle size of the chain between the two. If it is redispersed to l〇〇nm to disperse clay in the polymer, it is important to disperse the composite (1~100 nm) in the polymerization. The transparency of the composite is low, and the coefficient of gas is low. The problem of existence, how to develop an innovative structure that can be more ideal and practical, is waiting for the relevant industry to think about the goals and directions of breakthrough. In view of this, the inventor has been engaged in the manufacturing development and design experience of related products for many years. After detailed design and careful evaluation of the above objectives, the inventor has finally obtained the practical invention. [Description of the Invention] The present invention relates to a nano-dispersed clay vinyl ester resin and a synthetic method thereof, which are mainly hardened by a resin by a hardener to form a thermosetting nano composite material. The resin is based on (1)· Saturated monocarboxylic acid. (2) · Epoxy resin. (3). The combination of the organic layered clay and the reaction catalyst and the chain extender is 5 Å. 〇~150 C at the reaction temperature, the square nano-clay vinyl ester, this resin can be prepared into a liquid resin by using an alkenyl-containing reactive diluent, and can be applied to various composite materials on 1292413, with hardener and promotion. The agent forms a novel thermoset nano-dispersed clay composite in vinyl ester. [Embodiment] Therefore, the present invention intends to use a sandwiching agent having a cationic functional group to modify a layered clay, synthesizing a vinyl ester in a vinyl ester front conductor composition to be synthesized, and further comprising an alkenyl group-containing single The above-mentioned reaction product is released into a novel nano-dispersed clay/vinyl ester resin composite material. Natural cationic clay is a mineral that is abundant in nature and is an inexpensive material. Its layered structure has excellent hydrophilicity, and hinders the compatibility between clay and polymer. It must be modified to make the surface of clay minerals It is lipophilic or hydrophobic, and is easily dispersed in an organic solvent and increases the affinity of the clay to the polymer. This is the use of a sandwiching agent to improve the clay interface and increase the layer spacing of the clay layer, which increases the chance of the polymer monomer or polymer itself entering the silicate layer, making each citrate layer and polymer of the clay The effective contact area, and due to the presence of organic polymer molecules and the ionic chain of the citrate layer, the thermal properties, mechanical properties, and flame resistance of the nanocomposite can be improved, offsetting the traditional inorganic filling. When the polymer forms a composite material, the mechanical strength and impact resistance of the composite material are sacrificed. At present, among these nanocomposites, Nyl〇n6/ciay nanocomposites are the most thoroughly studied and commercialized, from A.0kada et al.

And Y. Kojima et al., in Acs Symp Series, 1995, 585, 55 and J. Αρρ· P 〇lym. Su, 1995, 52. 576, know that the addition of 5wt% clay and 3〇% glass fiber is similar to the reinforcing effect. This is unmatched by conventional composite materials. They also reported the addition of 4wt% clay to form nanocomb 1292413 in Nyl〇n6, which has a tensile strength increase of 55 %, a tensile modulus of about 90%, and a heat acceptability of 〇〇1〇〇. C 'Therefore, Nylon6/clay nanocomposites are now commercialized, and Nylon6/clay nanocomposites have been used by T〇y〇ta, & timepiece belt cover covers and gas barriers. (gas bairies films) There are many patents related to polymer/clay nanocomposites that have Epoxy/clay, Rubber/clay, PEO/day, Pol yolef in/clay, PCL/clay and other nanocomposites. The natural clay mineral structure is composed of tetrahedrons and octahedrons in different stacking manners. The layered natural clay is composed of tetrahedral/octahedron=proportion layered tannic acid layer, with cations such as Na+ between layers. Therefore, the layered tantalate layer has a certain cation exchange equivalent. This exchange is the best 'in the day (four) ion layer when the natural clay used in the selection of 80~15〇meg/l〇〇g (referring to the cation exchange in the 100g clay) is the best in the nano-clay composite. The clay is further used in this mixed material with Na+_Montena stone being the most common and inexpensive, and the present invention is of course applied to the study of the embodiment using the natural clay, but the scope of the invention is not limited thereto. From the dicerate sheet structure, when there is water in the salt layer, the electrostatic repulsion increases and the interlayer distance increases, causing the layered clay to expand due to water. If: = ion, the cation will neutralize the negative of some of the sheet structure. The swellability of the layered clay is limited in the liquid environment. ... and the porosity between the layers, the exchange of ions to change the layer of soil. As for the organic property of the rod (four), that is, the organic cation type inclusion agent formed by the levitation of the right u sub-exchange is compatible with the polymer monomer or the polymer. (9) Literature studies have shown that it affects the organic viscosity. In the case of the reactivity of the 'money molecule', the 1294213 bulk, thermal and mechanical properties, it is also the focus of the present invention to select an appropriate ammonium ion organic molecule to form the organoclay as a binder. The layered clay is a 5L crucible formed by a layer formed between layers, and can be classified into two kinds of finely dispersed nanocomposites, ie (a) sandwiched nai In the case of a rice composite material, the polymer chain which is elongated alone is sandwiched into the strong bismuth acid layer, resulting in a neatly arranged reproducible nanometer-distance multilayer structure, and the layered (four) salt layered inorganic material retains a layered shape. Reproducibility, but the inclusion of macromolecules in its citrate layer still forms a strong inorganic chain. (b) a delaminated nanocomposite, the phthalate layer is delaminated and dispersed in a polymer substrate, and the layered arrangement is any-direction, and then X-ray is wound: 10 gauge analysis at (10)^ There is no diffraction peak in the direction. At this time, the distance between the layers of the silicate layer has reached 44A (20 < 2), and the nano-dispersed clay is obtained in the vinyl eucalyptus. The above two kinds of nano-materials have the highest compatibility of the two phases in the delaminated hybrid composite. The σ' nano-clay composite has the following advantages: (1) Low linear expansion coefficient. (2) Reducing the water absorption of the nano-clay composite material. (3) When the content of low inorganic clay is low, it can improve its mechanical properties, and has the advantages of high gloss, no warping, no floating fiber and the like. (4) Because clay has a length-to-thickness ratio from the sub-chain direction, a small amount of clay can greatly improve the mechanical properties of the nanocomposite, but it is still affected by a small amount of intercalating agent. Physical and thermal properties. Although nano-clay composites have the above advantages, they are affected by synthetic properties, preparation conditions, inclusion agent selection, clay content and different polymer systems, and are not necessarily <================ The above conditions are entered =:: The development of the relevant example. 1292413 The thermosetting vinyl ester resin to be carried out according to the present invention is synthesized by reacting an epoxy resin with an unsaturated monocarboxylic acid, and then diluted with a reactive dilute monomer to have an unsaturated double The reactive resin of the bond is called a vinyl ester resin (Vinylester); wherein the vinyl ester resin means containing ·· ', R, 0

I II H2C II C-R-C - O-CH2-CH-CH2-R,,-

I

The main structure of the 0H functional group; it is formed by a ring-opening reaction of an epoxy resin with an unsaturated monocarboxylic acid. Among them, epoxy resin is bisphenol A type, bisphenol type, bisphenol S type, bisphenol F type, novolak type, biphenyl type, naphthalene type, decanoic acid type, hexahydrofurfuric acid type, benzoic acid type , diglycidyl ether, epoxy resin such as ethylene glycol type or diglycidyl ether or modified shell resin having two or more epoxy groups. The commonly used unsaturated monocarboxylic acid (m〇n〇unsaturated m〇n〇c arboxylic acid) is acrylic acid, methacrylic acid, crotonic acid, phenylacrylic acid, crotonic acid, phenylpropene, mountain acid, Methyl propylene carboxyethyl ester, maleic acid salt, propylene dilute ethyl ester, dicyclopentadiene dichloride, cis-butyl dicarbonate, etc., generally using methacrylic acid, methacrylic acid hydroxy group excellent in alkali resistance A carboxylic acid of a mercaptoacrylic acid type such as an ester, a maleate or a hydroxypropyl methacrylate is preferred, and as the present invention, a diluent is used as a reactive monomer having an unsaturated bond such as styrene or methylbenzene. Ethylene, vinyl acetate, methyl methacrylate, divinyl benzene or a reactive monomer having an unsaturated group or two or more functional acryl monomers. The hardening agent of the other ethyl ester hardening has dimercapto-peroxy 10 1292413 compound, _ peroxide, hydrogen ~ ~, a ^ witch? sheep L compound: 虱 '% _ class, alkyl over the purpose class And organic peroxygen such as peroxycarbonic acid, such as, for example, benzamidine peroxide, methyl ethyl ketone peroxide, moon-based peroxide, dicumyl peroxide, cumene hydrogen Peroxide, etc., can be used as a benzoic acid peroxide J. A photoinitiator can also be added to initiate a free radical reaction by bubbling or other light irradiation to harden the ethylene. The promoter of the present invention may be a third-order aryl group having a m group in a nitrogen substituent, for example, N,N-dipropyl-p-toluidine, N-phenyldiethanolamine, N-p-benzene. Preferably, N,N-dipropyl propyl-p-tolylamine is preferred as a small amount of an effective N-ethanolamine, N,N-dihydroxybutyl-p-toluidine or the like. And it can be added as needed in the vinyl styrene resin, 6 is a coloring agent pigment, an external absorbent, a filling material, a bismuth change agent, a plasticizer or a coupling agent, etc. The thermosetting ethylene S resin formed by the combination of the above formulas is One of the best materials for the application of anti-rice engineering or paint or flooring or SMC/BMC composites. The advantages of vinyl ester resin, and the corrosion resistance of the 2000s. , 'To improve this material type nano-sized clay, Beneficial clay, B-rare earth layered tantalate layer', known nano-fossils, current 'thermosetting, good processing characteristics, low cost, high temperature resistance, high strength material industry The new darling, but as time comes, the global standard of living is also expanding. Based on this nature, the invention is developed with new materials. This new machine/inorganic resin is found in this urethane resin. At present, it has a wide range of advantages, and it has the adhesive advantage of good epoxy resin. It has been reinforced and compounded. The performance of the composite material in this era of shrinkage, brittleness and its olefin resin and its composite ester resin can be For a new one with nanocrystallization and evenly dispersed in the acid salt layer in the polymer of the 11 1192413 method (1) directly with appropriate solvent and pre-precursor and organic clay dispersion nanocrystallization, (2) added The reactive functional organic clay is polymerized with an organic monomer or a compound to form a nano composite. (3) The melting method allows the polymer molecules to directly enter the clay citrate layer. The invention combines a reactive functional group intercalating agent with a vinyl ester lead to form an ethylene ester and then dilutes it into a liquid nanocrystalline ceric acid layer with a diluent, and is combined with a hardening agent. The accelerator or coupler forms a nano-clay vinyl acetate composite. The patents or other literatures related to domestic and foreign nano-clay vinyl ester resins have not been published. The related ones are Giannilis et al., 1996, Sept 1〇, the US patent 'n〇555467〇's Yinqing nan〇c〇 The case of ap (10) te, which is a composition of a vinyl ester resin which is the main purpose of the present invention, is a hardening reaction of an acid anhydride type hardener, an epoxy resin and an organic clay to form a nano-clay epoxy resin composite material. The most preferred method of the present invention. Is to provide a kind of nano-dispersed clay, which is based on synthetic nano-dispersed clay.

Resin composite. The result obtained by the above purpose

The non-ricized clay citrate layer can be uniformly dispersed in the vinyl ester liquid to shake the J fat ingredients, and then the Γ:: organic, inorganic mixed soil-accelerator, hardener or coupling agent to form the rice, and then know m This nano-clay is used in r, and the material is improved. In addition to 佯拄K ^ t 隹 酉曰 酉曰 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 保持 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在To increase the scope of application, gp is mainly composed of vinyl-containing early-, bad-lactating resins, catalysts and inclusions with cationic functional groups. The organic clay is mainly used for ring-opening reaction and the organic clay (4) salt layer is used. The synthetic reaction of dispersing forms a new resin for the purpose of ethylene δ. The vinyl acid precursor is mainly composed of acrylic acid, and the epoxy resin has a system (仏 〇 A A A A , , , , , system) Ep〇xy), η ovolac system epoxy, or their different systems of mixed epoxy resin, etc., the cationic functional group of the cationic organic clay has an acid group, a clothing base "vinyl The main 'clay' is mainly layered clay. The synthesized nano-clayed vinyl, the composition of the resin is the same as described in the method. The obtained nano-sized clay is prepared by using an alkenyl-containing reactive diluent. Liquid resin: this resin is separately used as a hardener, plus The agent or the coupling agent together form a nano-clayed ethylene ester composite material. In order to make the above and other objects, features and advantages of the present invention more apparent, several preferred embodiments and comparative examples are described herein. With reference to the drawings, the following detailed description is as follows: The embeddable material used in the present invention is a combination of a citrate layer which can be mixed with an ammonium ion-containing intercalating agent and a cation-containing crucible which is soluble or insoluble in water. The acid salt layer is formed into an organic clay, and the inclusion agent includes a small molecule monomer and a macromolecular prepolymer, etc., and the choice of the cooling agent must have an ammonium ion, and an epoxy group and an acid. Base, vinyl, alcohol group, etc. are beneficial for the functional group of the synthetic nano-clay vinyl ester resin. The interlayer cation of the layered tantalate layer is Na+, ca+2, K+, Mg+2, with 4 + and similar, including mixtures thereof. Cation exchange can be carried out and the formation of the mixture 13 1292413 delamination CEC value (100 g clay can replace the exchange equivalent value) about 70~1 50meg / 100g, each citrate The layer is made up of 2: 丨 tetrahedral / octahedron ratio It is made of 'Montear, Hectorite, saponite, nontron ite, beidellitei, Volkonskoite, saponite, sanconite, sobockite, sterensite, svinfordite, vermiculite, etc., and other systems such as mica, illite, ledikite, etc. Thick at about i 0

There is an interlayer bonding force between the 0A' layer and the layer. The entrainment agent improves the lipophilicity of the layered material of the sulphate, which not only enhances the lipophilicity of the clay, but also increases the distance between the layers by more than 5A, and increases the ability of the reaction monomer and the intercalating agent during synthesis to enhance The dispersing ability of the citrate layer. The main technology of the present invention is a reaction monomer formed by forming a nano-clay vinyl ester resin and a synthetic method, including unsaturated monoweilic acid (including a dilute acid monomer), a coupling agent, an accelerator, etc., wherein the unsaturated single Carboxylic acid (including alkenyl acid monomer), a variety of systems, including olefinic acids, acrylic acid, etc.; in the epoxy resin, there are bisphenol A (BisphenolA), phenolic (n (alac) system, bisphenol F (BiphenylF) system, Silicone (Silicone), second official

Base systems, tetrafunctional groups, etc., or catalysts such as epoxy resins in their mixed systems, such as organophosphorus compounds, tertiary amine salts, organic gold, and couplings, such as titanols, decanes, etc. . The invention mainly comprises the synthesis of vinyl esters and epoxy resins to form vinyl esters while forming eight buckets: single ' Τ ^ σ , and knife-distributing organic: Ϊ 示 示 米 矽 矽 矽 在 在 在 在 在Resin-like resin, 曰τ 'to achieve the purpose of β delamination and rice, as for the coupling agent can improve the compatibility of the organic phase with I, further enhance the physical properties of the resin and the application of additional generation, 'The synthesis of the new resin is then formed with a reactive diluent such as styrene (styreneg value - state resin, the above undiluted and diluted thermosetting tree ne), used in coating 3 14 1292413, adhesives, composite materials, etc. Aspect ± 'Formation - organic / inorganic nano-dispersion mixed material. The hardening reaction of the above resin can be used as a hardening agent, such as methyl ethyl ketone peroxide, metal salt promoter, accelerator or coupling agent, etc. Clay thermoset composite. Comparative Example 1 Equivalent molar number of bisphenol A epoxy resin and methacrylic acid were placed in a reaction tank and heated to 80 C to mix evenly, adding 4% Tpp (Tripheny) 1 phosphine) reaction catalyst starts at 100 t Should, until the epoxy equivalent is greater than 10000, start to cool down, while diluting styrene into liquid vinyl ester resin (the styrene weight ratio is 45%), the synthesized resin is added 6% cobalt octoate: 0 · 4phr, NN Nonylaniline: 〇· 〇3phr, 55% MEKP0: lphr is hardened at room temperature and hardened at 105 r, 2 hr. Its tensile strength (test method ASTM D790) is 973 kgf/cm2. Barcol hardness reached 38. Comparative Example 2 The above-mentioned formulated ethylene vinegar resin was directly added to ADA (Aminododecanoic Ac id) 4 wt% organic clay (containing H2N(CH2)uC00H as a sandwiching agent) to form clay/tree 曰The composite material 'is analyzed by XRD as '^ non-nano-dispersed composite material (the figure of No. 1 in Fig. 1 is still present in the peak of 2 0 equal to 4 °), and its tensile strength Q ?lexrual strength) is 9 46 kg / cm, Barcol hardness is 40. Comparative Example 3 15 1292413 The vinyl ester resin of Comparative Example 1 is directly added to the CV clay containing double-stranded modification (including double-bond ammonium salt modification) Nitrate soil) 2wt%, then the same hardener and accelerator shape Clay-containing thermosetting composites, known as X-rayed by XRD analysis (Fig. 1 of Figure 1), is a composite material showing CV clay with double-stranded modification (including double-bonded ammonium) The salt-modified nano-soil) participates in the hardening reaction to form a thermosetting resin into a nano-composite composite, but has a Flexrual strength of only 561 kg/cm and a Barcol hardness of 35. Example 1 First, an epoxy resin and MAA (Meth-Acrylic Acid) were added to the same reaction procedure and conditions as in Comparative Example 1, and 1 wt% and 2 wt were added simultaneously with the reaction. %, 3wt% and 4wt% ADA (Amin ododecanoic Acid modified nano-soil) organic clay (containing H2N(CH2)iiC00 Η) was subjected to ethylene esterification reaction, and the obtained resin was diluted with styrene to a ratio of 55/45 containing clay/ The vinyl ester resin, the thermosetting composite obtained by the hardening reaction of the same Comparative Example 1 was analyzed by XRD (numbers 2, 3, and 5 in Figure 1 represent 1%, 2%, and 4%, respectively). Thermosetting nano-composites, different amounts of ADA (Aminododecanoic Acid modified nano-soil), the tensile strength and Barco hardness are shown in Table 1. The relationship between the addition reaction time and the flexural strength and Barcol hardness in 2 wt% ADA (Aminododecanoic Acid modified nano soil) is shown in Table 2. It is resistant to 5 in the constant temperature water tank (TC benzene test and Comparative Example 1 and the weight increase change and hardness reduction ratio are shown in Table 3. 16 1292413 Synthesis of nano-clay vinyl ester composite material and comparative examples 丨 and 2 impact resistance characteristics For comparison, see Table 4. From the above Comparative Examples 1 and 2 and Example 1, the nanosolidified clay resin thermosetting composite material of the present invention is obtained by thermosetting, mechanical strength and toughness in mechanical properties. The composite materials can be simultaneously increased, and the barrier property and chemical resistance of the chemical solvent are improved. It shows that the nano-silicate dispersion of the citrate layer can make the advantages of the organic phase and the inorganic phase simultaneously. In the composite material, the multiplication effect is seen. As for the hardness and the (4) special performance, the former shows that the former is added by the inorganic phase, and the latter is the distribution and size of the organic clay added to change the molecular chain of the organic polymer, so that the toughness is improved. The analysis of the differential thermal analyzer (DSC) and the thermal deformation moisture tester (HDT) showed that the glass transition temperature and the heat distortion temperature showed a decreasing trend. Epoxy resin (epoxyresin) and MAA (methacrylic acid monomer Meth rylic Acid) and TPP (triphenyl sulfonate 邮 邮 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The (7) clay containing double-stranded modified (nano-soil modified with double-bonded ammonium salt) is subjected to a synthesis reaction. After the synthesis, the same method of Comparative Example 1 and the composition of the composition are hardened to form a thermosetting nano-clayed vinyl ethylene. Composite material, its tensile strength (f lexural strength), glass transition temperature (Tg) value and Barco (Barc0:l) value and comparison example 3, see Table 5 0. The above results show the characteristics of the sandwich agent, the deep process of the synthesis process Affects the properties of this thermoset nanocomposite composite. However, the nano-dispersed bismuth citrate in the vinyl ester tree 17 1292413 is the smooth completion & 'physical properties, then the system table shows better conditions. To re-adjust the combination formula can The present invention has been specifically described by the above-mentioned households, and the present invention is described by specific terms, and the scope of the invention cannot be limited thereto; those skilled in the art can understand this Spirit of invention After changing the principle of its modifications and equivalents of the purpose, and this and other changes and modifications are intended to be included in the range of chatter as the scope of the patent application of the predetermined boundary.

18 1292413 [Simple description of the diagram] Figure 1: X-ray diffraction pattern of composites of different compositions. Table 1: Properties of different layers of ADA (Aminododecanoic Acid modified nano-soil) organic layered clay content of nano-dispersed clay in ethylene ester composites. Table 2: Nano-dispersed vinyl ester resin Adding 2 wt% ADA (Aminododecanoic Acid modified nano-soil) at different time points during synthesis, the physical properties of the composite material obtained at different synthesis time of vinyl ester. Table 3: Test results of the chemical resistance test of Comparative Example 1 and Example 2 and Example 1. Table 4: Physical property analysis of Comparative Example 1 and Example 2 and Example 2. Table 5 · Physical property analysis of Comparative Example 3 and Example 2. [Description of main component symbols] Note: The present invention has no component symbol description.

19

Claims (1)

J2 fine 13 faint. Ben 丨 ', the scope of application for patents: a nano-dispersed clay vinyl ester resin, the composition of which contains · cation cationic agent modified with 50~2 〇〇〇neg / 1 〇〇 g) Cation exchange milliequivalent layered clay, epoxy resin and unsaturated monocarboxylic acid, esterified coal, unsaturated double bond reactive monomer, wherein the esterification catalyst includes phosphorus triphosphonate organic phosphide, tertiary and fourth Any one or two or more of the ammonium salts, wherein the weight ratio is between 2% of the total of the total reactants of the epoxy resin and the unsaturated monocarboxylic acid, and the layered layer of the cationic type inclusion agent The content of clay ranges from 〇·5 to 8 wt%. Ms. No. 4, the nano-dispersed clay vinyl ruthenium resin described in item i of the invention, wherein the primary bond of the sandwiching agent having a cationic functional group has an organic ammonium salt of 4 to 18 carbons. The invention claims the patented nano-dispersed clay ethylene s secret grease according to Item 1, wherein the content of the layered clay containing the cation-carrying agent is between 5 wt%. The village of Shenshen 1 Liweiwei, the nano-disintegrated clay described in Item 1 of the second paragraph: gas two epoxy resin including double ...,, neighboring armor, dust, milk, resin, or 1500 between. Two or more of the epoxy equivalents are as described in the patent application Fan Yuan Di Resin, the above-mentioned nano-dispersed clay vinyl ester acid. The sum and mono-acids include propionic acid or/and methacrylic acid, such as the patent, the resin, the &, the nano-dissolved clay vinyl ester oxygen resin and the ratio of The reaction equivalent is between Mohr and 丄. 20 1292413. The nano-dispersed clay vinyl ester resin according to claim 1, wherein the unsaturated double bond reactive monomer comprises styrene or \ and methyl styrene. A method for synthesizing nano-dispersed clay B-S resin, comprising: cation-clamping agent modified with 50~200 (meg/100g) cationic parent for milliequivalent layered clay, epoxy resin and unsaturated a monocarboxylic acid, a hydrazine, an unsaturated double bond reactive monomer, wherein the esterification catalyst comprises any one or more of a phosphorus triphosphide organic phosphide, a tertiary and a quaternary ammonium salt, and a weight thereof. Between the total weight of the total epoxy resin and the unsaturated monocarboxylic acid reactant (U-2%; the composition is modified with a cationic binder to have a cation exchange milliequivalent layer of 50 to 200 (meg/100g) Clay, epoxy resin and unsaturated monocarboxylic acid are subjected to ring-opening esterification synthesis reaction under the heating temperature of 5〇t ~i5〇I and promoted by esterification. The intercalating agent backbone having a cationic functional group has an organic ammonium salt of 4 to 18 carbons. 10. The method for synthesizing a nano resin as described in claim 8 wherein the cation-containing dispersed clay vinyl ester has a layered clay content of 1 to 5 wt%. The nano-disintegrated clay vinyl ester described in the article includes an epoxy resin including a bisphenol A type and a phenolic grease having an epoxy equivalent of 15〇-15〇〇21 I292413 12 13 14 15 • as claimed in the patent scope 8 households, +, Shishu f into a kilogram of speed nano-distributed land survey B, said Sa resin synthesis method, it does not on vinyl ester and methacrylic acid.巧内坤酸 or / as in the patent application of the eighth item of the resin into the syllabus of the known nano-dissolved clay vinyl ester, the method, the reaction of the epoxy resin and unsaturated monocarboxylic acid equivalent molar ratio Between U and U. ί 反 ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί Ethylene or / and mercaptostyrene. = Please refer to the synthesis method of the nano-dispersed clay, Baked vinegar, and the glutinous glutinous rice described in the scope of S8, and the synthetic method in the bismuth is the epoxy resin and the unsaturated monocarboxylic acid. 5 (H5 〇 heating temperature] under the promotion of esterification catalyst to carry out the % esterification reaction, after a period of reaction, 60 to 150 minutes after the esterification catalyst is added to the reaction, and then add a cationic cationing agent to change The layered clay participates in the reaction, and the reaction of the epoxy resin with the unsaturated monocarboxylic acid is more than 9%, and the monomer is diluted with the unsaturated double bond reactive monomer to obtain a nano-dispersed clay vinyl ester resin.