Bilateral multi-metal oxygen cluster hybrid molecule as well as preparation method and application thereof

Abstract

The invention discloses a bilateral polyoxometalate (POMs) hybrid molecule and a preparation method thereof, the bilateral polyoxometalate (POMs) hybrid molecule is prepared by reaction of an organic part and monofunctional POMs, and the structural formula of POMs is [(N (C4H9) 4] 3 {AlMo6O18 (OH) 3 [(OCH2) 3CNH2]}, flame-retardant elements N and P are added into polyacid in an organic modification mode, the obtained organic-inorganic hybrid molecular composite epoxy resin (EP) is excellent in performance and good in compatibility with a matrix, the adverse effect on the mechanical property of the EP matrix when polyoxometalate is independently added can be effectively avoided, and the flame-retardant performance of the EP matrix is improved. An incomplete combustion process caused by a complete organic flame retardant can also be avoided; in addition, the multi-metal oxygen cluster containing transition metals such as molybdenum has the functions of catalyzing carbon formation, suppressing smoke and retarding flame, so that the hybrid molecules achieve the purposes of efficient flame retardance and smoke suppression under the condition of low addition amount. And meanwhile, the material has high thermal conductivity and excellent insulating property, and can be applied to the field of electronic and electric appliance packaging.

Description

Technical Field

[0001] The present invention relates to the technical field of organic-inorganic hybrid filler modifiers, and in particular to a double-sided polyoxometalate (POMs) hybrid molecule, a preparation method thereof, and applications thereof. Background Art

[0002] The continuous advancement of next-generation information devices and technologies, such as chips, storage devices, and displays, towards nano, molecular, and atomic dimensions, places unprecedented demands on polymer packaging materials. Plastic products used in electronic devices and components, particularly polymer materials used in electronic packaging, often involve high energy dissipation and heat transfer, posing a significant fire hazard. Furthermore, the long-term performance stability and service life of electronic equipment must be guaranteed. Therefore, the development of flame-retardant electronic packaging materials with superior performance holds significant research and application value in the electronics and electrical appliance sector.

[0003] Epoxy resin (EP) is the most typical electronic packaging material. It has been widely used in the insulation and packaging of high and low voltage electrical appliances, motors and electronic components because of its low price, simple curing and molding, high adhesion, good stability, good chemical resistance, high mechanical properties, and excellent electrical insulation properties. However, EP has disadvantages such as flammability, poor toughness, and low thermal conductivity (0.2W / (m·K)). On the other hand, the high power density and high integration of electrical and electronic equipment are accompanied by serious high heat accumulation problems. In the fields of 5G communication equipment, power conversion equipment, storage modules, large-scale computing center facilities in the field of artificial intelligence, the flame retardancy and heat dissipation of the packaging materials used for integrated circuits have become the key to restricting their performance and affecting their lifespan. The introduction of filler modifiers is the most direct and effective way to improve the performance of EP. Thermally conductive filler modifiers can be categorized as metals, carbon materials, and inorganic non-metals. While metal fillers (Ni, Cu, Ag) and carbon materials (carbon fibers, carbon nanotubes, and graphene) can effectively improve the thermal conductivity of polymer-based composites, they also alter the electrical insulation properties of the polymers, resulting in extremely high electrical conductivity and a high dielectric constant, making it impossible to produce polymer-based composites with both high thermal conductivity and excellent insulation properties. Finding a filler modifier that can simultaneously enhance the flame retardancy, thermal conductivity, thermal stability, and dielectric properties of epoxy resins is crucial for their use as electronic packaging materials.

[0004] Polyoxometalates (POMs), as highly efficient acid-base, redox, or bifunctional catalysts, have shown promising application prospects in improving the flame retardancy of polymer materials and suppressing smoke release during combustion. However, due to their strong electrophilicity and large volume effect, POMs cannot be properly dispersed in polymer matrices when used directly, limiting their application in composite materials. Furthermore, the introduction of fillers may lead to defects such as interfacial incompatibility, resulting in composite materials not only failing to achieve ideal thermal conductivity but also deteriorating other performance aspects. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects of the existing technology and provide a double-sided polymetallic oxide cluster hybrid molecule (hereinafter referred to as double-sided POMs hybrid molecule). By introducing a phosphorus-containing organic unit structure into it through organic-inorganic hybrid technology, the flame retardancy of POMs and the compatibility in the matrix are significantly improved, and a polymer-based composite material with high thermal conductivity and excellent insulation properties is prepared to meet the demand for electronic component packaging materials.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned double-sided POMs hybrid molecule.

[0007] The technical solutions adopted in the present invention are as follows:

[0008] A double-sided POMs hybrid molecule is prepared by reacting an organic part with a monofunctional POM, and its structural formula is:

[0009]

[0010] Among them, the structural formula of the organic part PADOPO is:

[0011]

[0012] The structural formula of monofunctional POMs is [(N(C4H9)4]3{AlMo6O 18 (OH)3[(OCH2)3CNH2]}. The double-sided POMs hybrid molecule is formed by connecting the carboxyl groups at both ends of the organic part to the amino groups in POMs through amide bonds, which is a POMs-terminated organic-inorganic hybrid molecule.

[0013] In a preferred embodiment of the present invention, the preparation of the organic portion of the double-sided POM hybrid molecule comprises: weighing appropriate amounts of p-aminophenylacetic acid and terephthalaldehyde and dissolving them in a first solvent, stirring at room temperature until transparent, then adding a certain amount of DOPO, continuing to stir at room temperature for 1-2 hours, then heating to 90-95°C and reacting for 20-24 hours, precipitating the resulting solution in a second solvent, and filtering out a yellow powder, washing, and drying to obtain a yellow powder organic portion (PADOPO).

[0014] The synthetic route of this reaction is as follows:

[0015]

[0016] More preferably, the molar ratio of terephthalaldehyde, p-aminophenylacetic acid and DOPO is 1:2-2.5:2-2.5.

[0017] More preferably, the first solvent is DMF and the second solvent is water.

[0018] In a preferred embodiment of the present invention, the preparation method of monofunctional POMs comprises: mixing NaAlMo6 and (HOCH2)3CNH2 in a third solvent under protective gas protection, reacting at 30-100°C for 1.0-5.0h, then adding TBA·Br to the reaction mixture, and then cooling the reaction to room temperature for solid-liquid separation. The resulting filtrate is placed at room temperature until colorless crystals precipitate, and the colorless crystals are vacuum dried to obtain the product, namely, monofunctional POMs (NH2-AlMo6).

[0019] Further preferably, the third solvent is acetonitrile and / or water.

[0020] More preferably, the molar ratio of NaAlMo6, (HOCH2)3CNH2 and TBA·Br is 1:1-2.5:3-4.5, and the ratio of NaAlMo6 to the third solvent is 1 g:5-10 mL.

[0021] The preparation method for the double-sided POM hybrid molecule comprises: dissolving PADOPO and 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) in a fourth solvent under a protective atmosphere, adding a mixed solution of NH2-AlMo6 and the fourth solvent dropwise at 80-90°C, and reacting for 20-24 hours at a temperature of 75-100°C. After completion, the reaction solution is concentrated and slowly added to a fifth solvent for precipitation. The precipitate is filtered, the resulting solid is vacuum-dried, and the final product is a light yellow powder. The molar ratio of NH2-AlMo6 to PADOPO is ≥ 2:1, preferably 2-3:1.

[0022] The synthetic route of this preparation method is as follows:

[0023]

[0024] In a preferred embodiment of the present invention, the fourth solvent is one of acetonitrile, 1,4-epoxyhexadecane or N,N-dimethylformamide, and the fifth solvent is one of ethyl acetate, toluene or tetrahydrofuran.

[0025] A further preferred molar ratio of PADOPO, NH2-AlMo6, and EEDQ is 1:2-3:2-3.

[0026] An epoxy resin composite material for electronic components is formed by mixing epoxy resin and the above-mentioned double-sided POMs hybrid molecules, wherein the addition amount of the double-sided POMs hybrid molecules is 1-10wt% of the epoxy resin composite material.

[0027] Furthermore, the preparation method of the epoxy resin composite material for electronic components is as follows: placing epoxy resin in a single-necked flask, adding the double-sided POMs hybrid molecule, adding an appropriate amount of a fourth solvent and stirring to completely dissolve it, heating the mixture to 75-85°C, completely removing the solvent and bubbles under vacuum, then adding a curing agent and stirring for 3-8 minutes. After mixing evenly, curing at 100-160°C. The curing process includes: maintaining the temperature at 100-120°C for 3-5 hours, heating to 140-160°C and maintaining the temperature for 1.5-2.5 hours, and then naturally cooling to room temperature.

[0028] The double-sided POMs hybrid molecules self-aggregate in the epoxy resin matrix to form a nanoscale microscopic phase or topological structure. The microscopic phase includes a worm-like structure that is dispersed and uses POMs as cross-linking points.

[0029] The beneficial effects of the present invention are:

[0030] 1. The method of polyoxometallic cluster organic hybrid modification is adopted to introduce organic structural units into the polyoxometallic cluster inorganic skeleton by covalent connection, which greatly improves the compatibility between the polyoxometallic cluster and the matrix polymer and achieves "molecular-level" dispersion and high transparency.

[0031] 2. The introduction of the organic part of the present invention brings about the synergistic flame retardancy of N and P multi-elements, the quenching effect of P-series free radicals (PO, PO2, HPO2) and the flame retardancy of the non-combustible gas released by the N-series flame retardant in the gas phase and the synergistic flame retardancy of phosphate in the condensed phase.

[0032] 3. The hybrid molecules designed in the present invention have double-sided POMs structural units. Their rigid structure and large volume effect drive the POMs hybrid molecules to self-aggregate in the epoxy matrix to form nanoscale microscopic phases or topological structures, which have a toughening and strengthening effect on the material.

[0033] 4. The present invention gives full play to the intrinsic advantages of POMs such as high catalytic activity, high thermal stability, and low dielectric constant, and improves the comprehensive performance of epoxy resin such as flame retardancy, heat resistance, thermal conductivity, and dielectric constant, meeting the special needs in high-end manufacturing fields such as electronic packaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is the H-NMR spectrum of the organic portion PADOPO of the hybrid molecule obtained in Example 1 of the present invention;

[0035] Figure 2 This is the H-NMR spectrum of the NH2-AlMo6 portion of the monofunctional POMs hybrid molecule obtained in Example 1 of the present invention;

[0036] Figure 3 This is the H-NMR spectrum of the hybrid molecule PA-AlMo6 obtained in Example 1 of the present invention;

[0037] Figure 4 This is a comparison chart of the transparency of the epoxy resin and composite material of Example 1, Comparative Example 1, and Comparative Example 2;

[0038] Figure 5 The dielectric spectra of the epoxy resin and composite material of Example 1, Comparative Example 1 and Comparative Example 2 are shown;

[0039] Figure 6 Thermogravimetric analysis diagrams of the epoxy resin and composite material of Example 1, Comparative Example 1 and Comparative Example 2;

[0040] Figure 7 This is a simple self-assembly process of the hybrid molecule obtained in Example 1 of the present invention in EP;

[0041] Figure 8 This is an SEM image of the PA-AlMo6 composite epoxy resin added with 5 wt% in Example 1 after etching with acetonitrile (the hybrid molecule is dissolved in acetonitrile);

[0042] Figure 9 Schematic diagram of the performance test results of Example 1 with 5 wt% of PA-AlMo6 composite epoxy resin added and the epoxy resin of Comparative Example 1, where (a) is a DMA test and (b) is a three-point bending test. DETAILED DESCRIPTION

[0043] The technical solution of the present invention is further illustrated and described below through specific implementation methods in conjunction with the accompanying drawings.

[0044] Example 1:

[0045] (1) Preparation of the organic part: 1.34 g of terephthalaldehyde, 3.02 g of p-aminophenylacetic acid, and 25 ml of DMF were placed in a 100 ml flask equipped with a magnetic stirrer. The mixture was stirred at room temperature until transparent. Then 4.752 g of DOPO was added to the reaction mixture and stirred at room temperature for 1 hour. The mixture was then heated to 95°C for 24 hours. After the reaction was completed and cooled to room temperature, the mixture was slowly poured into 400 ml of cold water for precipitation. The precipitate was filtered and washed five times with ethanol to obtain a yellow powder, which was the organic product PADOPO. Its structural formula is:

[0046]

[0047] The NMR hydrogen spectrum of the organic part PADOPO is as follows Figure 1 As shown in the figure, it can be seen that a sharp peak of the terminal carboxyl proton is displayed at 12.01 ppm, and the ratio of the proton peak on the benzene ring is 1:14, which is consistent with the ratio of the number of carboxyl hydrogen atoms at both ends to the hydrogen atoms on the benzene ring in the structure.

[0048] (2) Preparation of monofunctional POMs: NaAlMo6 (15 g, 12.45 mmol) was dispersed in 100 mL of water. Then, under N2 atmosphere, (HOCH2)3CNH2 (3 g, 24.9 mmol) was added while heating under reflux at 75°C. After 3 h of reaction, TBA·Br (16.05 g, 49.8 mmol) was added to the reaction mixture. The reaction mixture was allowed to react for 0.5 h and then cooled. The precipitate was filtered and the filtrate was allowed to cool to room temperature. Colorless crystals were obtained after several days. The product was dried under vacuum to obtain NH2-AlMo6. Its structural formula is:

[0049]

[0050] The nuclear magnetic hydrogen spectrum of NH2-AlMo6 is as follows Figure 2 As shown in the figure, the amino proton peak (3.43 ppm) and methylene proton peak (4.32 ppm) of Tris can be seen, indicating the successful unilateral insertion of Tris. The methyl and methylene proton peaks of the counter cation TBA appear at corresponding positions, with a ratio of 2:2:2:3.

[0051] (3) Preparation of double-sided POMs hybrid molecules: 1.6 mmol (1.3 g) of the organic part, 3.37 mmol (0.84 g) of 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) and 100 mL of acetonitrile were added to a 250 ml three-necked round-bottom flask. Under nitrogen protection, the reaction temperature of the mixed solution was raised to 85 ° C, and 40 mL of NH2-AlMo6 (3.36 mmol, 6 g) acetonitrile mixed solution was added dropwise and reacted at 85 ° C for 24 h. After the reaction was completed, the reaction solution was concentrated to 10 mL and slowly added to 200 ml of ethyl acetate for precipitation. The solid obtained after filtration of the precipitate was vacuum dried at 60 ° C for 24 h. The final product was a light yellow powder PA-AlMo6. Its structural formula is:

[0052]

[0053] The NMR hydrogen spectrum of PA-AlMo6 is as follows Figure 3 As shown in the figure, it can be seen that the typical characteristic peak of -COOH of PADOPA at 12.01ppm and the characteristic peak of amino proton of NH2-AlMo6 at 3.43ppm do not appear in PA-AlMo6. However, the characteristic peak of -NHCO- appears at 8.02ppm in PA-AlMo6, indicating that PADOPA and NH2-AlMo6 successfully achieve amidation reaction.

[0054] (4) Preparation of 5 wt% PA-AlMo6 composite epoxy resin, where 5 wt% is the mass fraction of PA-AlMo6 in the entire curing system (filler + resin + curing agent) (the same applies below): first weigh 100 parts by weight of E-51 epoxy resin into a single-necked flask, then weigh 6.6 parts by weight of double-sided POMs hybrid molecules, add an appropriate amount of acetonitrile and stir to completely dissolve it, heat the mixture to 80°C, vacuum to completely remove the solvent and bubbles, add 25 parts by weight of curing agent 4,4'-diaminodiphenylmethane and stir for 5 minutes, mix well and pour into a PTFE mold, place in a blast oven for curing, and the curing program is 110°C / 4h, 150°C / 2h, then turn off the oven, let the mold cool naturally to room temperature in the oven, demould, and obtain a double-sided POMs hybrid molecule / epoxy resin nanocomposite material.

[0055] Example 2:

[0056] (1) The preparation method of double-sided POMs hybrid molecules is the same as that in Example 1.

[0057] (2) Preparation of 3 wt% PA-AlMo6 epoxy resin composite material: First, weigh 100 parts by weight of E-51 epoxy resin into a single-necked flask, then weigh 3.85 parts by weight of double-sided POMs hybrid molecule, add an appropriate amount of solvent and stir to completely dissolve it, heat the mixture to 80°C, vacuum to completely remove the solvent and bubbles, add 25 parts by weight of curing agent 4,4'-diaminodiphenylmethane and stir for 5 minutes, mix well and pour into a PTFE mold, place in a blast oven for curing, the curing procedure is 110°C / 4h, 150°C / 2h, then turn off the oven, let the mold cool naturally to room temperature in the oven, demould, and obtain a double-sided POMs hybrid molecule / epoxy resin nanocomposite material.

[0058] Example 3:

[0059] (1) The preparation method of double-sided POMs hybrid molecules is the same as that in Example 1.

[0060] (2) Preparation of 1 wt% PA-AlMo6 epoxy resin composite material: First, weigh 100 parts by weight of E-51 epoxy resin into a single-necked flask, then weigh 1.25 parts by weight of double-sided POMs hybrid molecule, add an appropriate amount of solvent and stir to completely dissolve it, heat the mixture to 80°C, vacuum to completely remove the solvent and bubbles, add 25 parts by weight of curing agent 4,4'-diaminodiphenylmethane and stir for 5 minutes, mix well and pour into a PTFE mold, place in a blast oven for curing, and place in a blast oven for curing. The curing procedure is 110°C / 4h, 150°C / 2h, then turn off the oven, let the mold cool naturally to room temperature in the oven, demould, and obtain a polyacid-organic hybrid molecule / epoxy resin nanocomposite material.

[0061] Comparative Example 1:

[0062] (1) Comparative Example 1 is pure epoxy resin E-51 without adding any flame retardant.

[0063] (2) The curing process is as follows: first, weigh 100 parts by weight of E-51 epoxy resin into a single-necked flask, heat the mixture to 80°C, completely remove the bubbles by vacuum, add 25 parts by weight of curing agent 4,4'-diaminodiphenylmethane, and stir for 5 minutes. After mixing evenly, pour it into a PTFE mold and place it in a blast oven for curing. The curing procedure is 110°C / 4h, 150°C / 2h, then turn off the oven, let the mold cool naturally to room temperature in the oven, demould, and obtain the cured pure epoxy resin E-51.

[0064] Comparative Example 2:

[0065] (1) Preparation of NaAlMo6: Add 250 ml of water and 15 g (0.0621 mmol) of AlCl3·6H2O to a 500 ml beaker and stir to form a transparent solution. Add 100 ml of glacial acetic acid and continue stirring. Then add 35 g (0.1446 mmol) of Na2MoO4·2H2O and continue stirring to form a transparent solution. Then add 120 drops of concentrated hydrochloric acid, stir again, and let the mixture stand in the open.

[0066] (2) The preparation of the epoxy resin composite material with the addition of 5 wt% of NaAlMo6 is the same as step (4) of Example 1.

[0067] Flame retardancy testing of the epoxy resin composites obtained in Example 1, Comparative Example 1, and Comparative Example 2 was performed. The results are shown in Table 1. The LOI value of the double-sided POM hybrid / epoxy resin nanocomposite of Example 1 was significantly improved compared to Comparative Examples 1 and 2. The LOI value of the hybrid composite epoxy resin with a 5 wt% addition increased from 22.2% of the pure epoxy resin to 31.5%, and the composite passed the UL94 V-0 rating. Example 1 exhibited significantly improved flame retardancy.

[0068] Table 1 Flame retardant properties of epoxy resin composites

[0069]

[0070] The epoxy resin composite materials obtained in Example 1, Comparative Example 1 and Comparative Example 2 were subjected to cone calorimetry test. The results are shown in Table 2. It can be seen that compared with Comparative Example 1 and Comparative Example 2, the PHRR of the double-sided POMs hybrid molecular composite epoxy resin in Example 1 with a 5 wt% addition amount is 1657.8 kW / m 2 Reduced to 1057.7kW / m 2 , reduced by 36.2%. THR of pure epoxy is 60.1MJ / m 2 Reduced to 51.1MJ / m 2 In terms of smoke release, the PSPR of the double-sided POMs hybrid molecule / epoxy resin nanocomposite material of Example 1 is 0.49m 2 / s reduced to 0.26m 2 / s, and TSP is 20.2m 2 Reduced to 15.6m 2 It can be seen that the double-sided POMs hybrid molecules / epoxy resin nanocomposites have excellent performance in flame retardancy and smoke suppression.

[0071] Table 2 Cone calorimetry test of epoxy resin composites

[0072]

[0073] The thermal conductivity of the epoxy resin composite materials obtained in Example 1, Comparative Examples 1, and 2 was compared. The results are shown in Table 3. It can be seen that the thermal conductivity and thermal diffusivity of the double-sided POM hybrid molecule / epoxy resin nanocomposite of Example 1 were significantly improved compared to Comparative Examples 1 and 2, demonstrating excellent thermal conductivity. When used in electronic component packaging, this composite material provides improved heat dissipation performance.

[0074] Table 3 Thermal conductivity of epoxy resin composite materials

[0075]

[0076] The transparency of the epoxy resin composite materials obtained in Example 1, Comparative Example 1 and Comparative Example 2 is compared as follows: Figure 4 As shown, the double-sided POM hybrid / epoxy resin nanocomposite of Example 1 has similar transparency and visibility to the pure epoxy resin of Comparative Example 1, while the NaAlMo6 / epoxy resin nanocomposite of Comparative Example 2 has poor transparency. When used in electronic component packaging, high-visibility packaging materials help provide a smooth, transparent package appearance that meets the aesthetic requirements of high-end electronic products. They also facilitate visual inspection, making defects, cracks, and contamination more easily detected, thereby ensuring product quality.

[0077] The dielectric spectra of the epoxy resin composite materials obtained in Example 1, Comparative Example 1 and Comparative Example 2 are compared. Figure 5 As shown, it can be seen that the double-sided POMs hybrid molecule / epoxy resin nanocomposite material of Example 1 is 10 3 ~10 6 At a frequency of 100 Hz, the dielectric constants are all below 4, while those of Comparative Examples 1 and 2 are both higher than 4. When such a low dielectric constant is applied to the packaging of electronic components, it will help reduce overall power consumption and increase signal transmission speed.

[0078] Thermogravimetric analysis of the epoxy resin composite materials obtained in Example 1, Comparative Example 1 and Comparative Example 2 is as follows: Figure 6 As shown, the thermal decomposition temperature of the double-sided POM hybrid molecule / epoxy resin nanocomposite of Example 1 is slightly earlier, but the final carbon residue is higher than that of Comparative Examples 1 and 2. When applied to the packaging of electronic components, this will form a protective barrier and improve the mechanical properties of the material.

[0079] The self-assembly process of the double-sided POMs hybrid molecules obtained in Example 1 in epoxy resin was analyzed. Figure 7As shown in the figure, the PA organic structure in the structure has a close polarity with EP and has good compatibility, while POMs has a large polarity difference with EP and is difficult to dissolve; and because there is a certain entanglement between the PA organic structure and the EP polymer chain, a stronger van der Waals force is generated. With the help of the difference in polarity and van der Waals force between the two, PA-AlMo6 aggregates in the EP matrix to form a micro-nano size structure, forming a special worm-like morphology, as shown in the figure. Figure 8 As shown, its length is about 100nm and its cross-sectional diameter is about 20nm. The oligomer components attract each other with the EP matrix, while the large skeleton structure of the POMs component can serve as a cross-linking point to achieve the effect of strengthening and toughening the EP. Figure 9 In the DMA test, the storage modulus of the EP composite with 5wt% PA-AlMo6 addition reached 1573.0MPa, which was 38.3% higher than that of pure EP (1137.3MPa). g It increased from 152.4℃ of pure EP to 162.1℃; in the three-point bending test, the flexural strength and flexural modulus of the EP composite material with 5wt% PA-AlMo6 addition reached 150.5MPa and 3107.55MPa, respectively, which were 51.4% and 20.3% higher than those of pure EP (99.4MPa and 2584.1MPa).

[0080] The above description is merely a preferred embodiment of the present invention and therefore cannot be used to limit the scope of the present invention. In other words, equivalent changes and modifications made within the scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A double-sided polyoxometallic cluster hybrid molecule, characterized by: It is made by reacting an organic part with monofunctional POMs, wherein: The organic part is PADOPO, and its structural formula is: Monofunctional POMs is NH2-AlMo6, with the structural formula [(N(C4H9)4]3{AlMo6O 18 (OH)3[(OCH2)3CNH2]}; The double-sided polyoxometalate hybrid molecule is formed by connecting the carboxyl groups at both ends of the organic part to the amino groups in the POMs through amide bonds.

2. The double-sided polyoxometallic cluster hybrid molecule according to claim 1, characterized in that: The preparation method of the organic part includes: dissolving p-aminophenylacetic acid and terephthalaldehyde in a first solvent, stirring at room temperature until transparent, then adding DOPO, continuing to stir at room temperature for 1-2 hours, and then heating to 90-95°C for reaction for 20-24 hours; the solution obtained after the reaction is precipitated in a second solvent, and the obtained powder is filtered, washed, and dried to obtain the organic part.

3. The double-sided polyoxometallic cluster hybrid molecule according to claim 2, characterized in that: The molar ratio of the terephthalaldehyde, p-aminophenylacetic acid and DOPO is 1:2-2.5:2-2.

5.

4. The double-sided polyoxometallic cluster hybrid molecule according to claim 2, characterized in that: The first solvent is DMF, and the second solvent is water.

5. The double-sided polyoxometallic cluster hybrid molecule according to claim 1, characterized in that: The preparation method of the monofunctional POMs comprises: mixing NaAlMo6 and (HOCH2)3CNH2 in a third solvent under protective gas protection, performing a reflux reaction at 30-100°C for 1.0-5.0 hours, adding TBA·Br to the reaction mixture, cooling the reaction temperature to room temperature, performing solid-liquid separation, and keeping the resulting filtrate at room temperature until crystals precipitate. The crystals are then vacuum-dried to obtain the monofunctional POMs.

6. The double-sided polyoxometallic cluster hybrid molecule according to claim 5, characterized in that: The third solvent is acetonitrile and / or water.

7. The double-sided polyoxometallic cluster hybrid molecule according to claim 5, characterized in that: The molar ratio of NaAlMo6, (HOCH2)3CNH2 and TBA·Br is 1:1-2.5:3-4.5, and the ratio of NaAlMo6 to the third solvent is 1 g:5-10 mL.

8. A method for preparing a double-sided polyoxometallic cluster hybrid molecule according to any one of claims 1 to 7, characterized in that: include: Under the protection of protective gas, PADOPO, 2-ethoxy-1-ethoxycarbonyl-1 and 2-dihydroquinoline (EEDQ) are dissolved in a fourth solvent, and a mixed solution of NH2-AlMo6 and the fourth solvent is added dropwise at 80-90°C for 20-24 hours. After the reaction, the reaction solution is concentrated and added to a fifth solvent for precipitation. The solid obtained after filtration of the precipitate is then vacuum dried to obtain the product. The molar ratio of NH2-AlMo6 to PADOPO is ≥2:

1.

9. The method for preparing a double-sided polyoxometalate hybrid molecule according to claim 8, wherein: The fourth solvent is one of acetonitrile, 1,4-epoxyhexadecane or N,N-dimethylformamide, and the fifth solvent is one of water, ethyl acetate, toluene or tetrahydrofuran.

10. An epoxy resin composite material for electronic components, characterized in that: The composite material is formed by mixing epoxy resin and the double-sided polymetallic oxygen cluster hybrid molecule according to any one of claims 1 to 7, wherein the addition amount of the double-sided polymetallic oxygen cluster hybrid molecule is 1 to 10 wt % of the epoxy resin composite material.

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