High-thermal-conductivity insulating double-dynamic-network polymer material as well as preparation method and application thereof

Abstract

The invention provides a high-thermal-conductivity insulating double-dynamic-network polymer material as well as a preparation method and application thereof. The preparation raw materials of the high-thermal-conductivity insulating double-dynamic-network polymer material comprise the following components: a polymer matrix and a modified inorganic thermal conductive filler, the polymer matrix comprises an epoxy vanillin monomer and a dithio curing agent; the modified inorganic heat-conducting filler comprises a first heat-conducting filler subjected to amination modification and a second heat-conducting filler subjected to amination modification; and the D50 particle size of the first heat-conducting filler is larger than that of the second heat-conducting filler. The high-thermal-conductivity insulating double-dynamic-network polymer material provided by the invention has high thermal conductivity, high insulativity and reprocessing and recycling performance, and the raw materials with bio-based sources are more in line with the green and environment-friendly development concept.

Description

Technical Field

[0001] The present invention belongs to the technical field of bio-based composite materials, and particularly relates to a highly thermally conductive and insulating double-dynamic network polymer material, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of modern electronic communication technologies, especially under the accelerated promotion of the 5G era, electronic packaging materials are facing higher performance requirements, particularly in terms of thermal conductivity and insulation. In order to meet the heat dissipation requirements of high-speed and high-integration electronic devices, packaging materials not only need to have excellent electrical insulation properties, but also need to have high thermal conductivity and low thermal expansion coefficient, which makes polymer-based composite materials reinforced with inorganic fillers become the current key research and application direction.

[0003] CN107459775A discloses an epoxy resin insulating and thermally conductive composite material and a preparation method thereof. The epoxy resin insulating and thermally conductive composite material includes an epoxy resin matrix, graphene-modified diamond filled in the epoxy resin matrix, and a curing agent. The mass ratio range of the epoxy resin to the graphene-modified diamond is 1:0.5 to 1:2, and the mass ratio range of the epoxy resin to the curing agent is 1:0.2 to 1:0.5; the graphene-modified diamond is diamond particles with graphene nanosheets grown on the surface. The epoxy resin insulating and thermally conductive composite material prepared by this technical solution has a thermal conductivity of up to 1.4 W / mK, but the thermal conductivity still needs to be further improved and cannot meet the high thermal conductivity requirements.

[0004] CN110157156A discloses an insulating and highly thermally conductive epoxy resin composition and a preparation method thereof. The insulating and highly thermally conductive epoxy resin composition includes the following raw material components in mass fractions: epoxy resin mixture 3.6% - 6.4%; aniline curing agent 1.3% - 1.6%; defoaming agent 0.01% - 0.03%; carbon black 0.005% - 0.015%; surface-modified alumina 92% - 95%; the epoxy resin mixture is a mixture of bisphenol epoxy resin and halogen-free modified epoxy resin in a mass ratio of 1:1. This technical solution can make each component evenly mixed by adding a high content of surface-modified alumina in components such as the epoxy resin mixture, so that the final product has a high thermal conductivity (above 5 W / m·K), but the mechanical properties are poor.

[0005] In the prior art, to improve the thermal conductivity of polymer-based composites, a large amount of high-thermal-conductivity inorganic fillers, such as alumina, silicon nitride, boron nitride, etc., are usually added. However, with the increase in the proportion of high-thermal-conductivity inorganic fillers, the material system also faces a series of challenges. On the one hand, high-thermal-conductivity inorganic fillers are prone to agglomeration in polymers at high contents, resulting in uneven dispersion, which in turn affects the overall mechanical properties of polymer-based composites; on the other hand, traditional polymer-based composites are discarded or incinerated after service, which will cause environmental pollution.

[0006] Therefore, it is necessary to develop a polymer-based composite material that can improve mechanical properties, thermal conductivity and recyclability, and at the same time meet the characteristics of green environmental protection. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a high-thermal-conductivity insulating double-dynamic network polymer material and its preparation method and application. The high-thermal-conductivity insulating double-dynamic network polymer material has high mechanical properties, high thermal conductivity, high insulation and reprocessing and recycling properties. At the same time, the use of raw materials from bio-based sources is more in line with the development concept of green environmental protection.

[0008] To achieve the purpose of this invention, the following technical solutions are adopted in the present invention:

[0009] In the first aspect, the present invention provides a high-thermal-conductivity insulating double-dynamic network polymer material. The preparation raw materials of the high-thermal-conductivity insulating double-dynamic network polymer material include the following components: a polymer matrix and a modified inorganic thermal conductive filler; the polymer matrix includes an epoxy vanillin monomer and a dithio curing agent;

[0010] The structural formula of the epoxy vanillin monomer is as follows:

[0011]

[0012] The modified inorganic thermal conductive filler includes a first thermal conductive filler modified by amination and a second thermal conductive filler modified by amination; the D50 particle size of the first thermal conductive filler > and the D50 particle size of the second thermal conductive filler.

[0013] In the present invention, a recyclable highly thermally conductive insulating dual-dynamic network polymer material is prepared by ring-opening addition and amine-aldehyde condensation of an epoxy vanillin monomer synthesized from a bio-based raw material, a dithio curing agent, and a modified inorganic thermal conductive filler. The highly thermally conductive insulating dual-dynamic network polymer material contains dynamic Schiff base bonds (C=N) and dynamic disulfide bonds (S-S), and can achieve reshaping processing and recycling. The modified inorganic thermal conductive filler is aminated with a first thermal conductive filler and a second thermal conductive filler having different D50 particle sizes. Filling small-particle-size thermal conductive fillers between large-particle-size thermal conductive fillers in the highly thermally conductive insulating dual-dynamic network polymer material can achieve filling in a state close to the densest packing, form a more complete thermal conduction path, thereby improving thermal conductivity, avoiding easy agglomeration of inorganic thermal conductive fillers in the polymer at high contents, and improving mechanical properties. The highly thermally conductive insulating dual-dynamic network polymer material not only solves the problem of dispersion of thermal conductive fillers, but also has reprocessing and recycling performance. At the same time, the raw material epoxy vanillin monomer from a bio-based source can replace traditional bisphenol A epoxy resin, which is safer and more environmentally friendly.

[0014] Preferably, the raw materials for preparing the epoxy vanillin monomer include vanillin and epichlorohydrin.

[0015] In the present invention, the reaction formula for the reaction of vanillin and epichlorohydrin to generate the epoxy vanillin monomer is as follows:

[0016]

[0017] Preferably, the molar ratio of vanillin to epichlorohydrin is 1:(5-10), such as 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9 or 1:9.5, etc.

[0018] Preferably, the dithio curing agent includes 4,4'-dithiobisbenzeneamine and / or 2,2'-dithiobisbenzeneamine.

[0019] Preferably, the mass ratio of the epoxy vanillin monomer to the dithio curing agent is 1:(0.5-2), such as 1:0.7, 1:0.9, 1:1.1, 1:1.3, 1:1.5, 1:1.7 or 1:1.9, etc.

[0020] Preferably, the D50 particle size of the first thermal conductive filler is 20-50 μm, such as 23 μm, 26 μm, 29 μm, 32 μm, 35 μm, 38 μm, 41 μm, 44 μm or 47 μm, etc.

[0021] Preferably, the D50 particle size of the second thermal conductive filler is 0.5-3 μm, such as 0.8 μm, 1.1 μm, 1.4 μm, 1.7 μm, 2.0 μm, 2.3 μm, 2.6 μm or 2.9 μm, etc.

[0022] Preferably, the first heat-conducting filler and the second heat-conducting filler each independently comprise any one or a combination of at least two of boron nitride (BN), aluminum nitride (AlN), aluminum oxide, diamond, or aluminum hydroxide.

[0023] Preferably, the amino-modified first heat-conducting filler and the amino-modified second heat-conducting filler are prepared by modifying the first heat-conducting filler and the second heat-conducting filler with an amino-terminated silane coupling agent.

[0024] Preferably, the amino-modified first heat-conducting filler and the amino-modified second heat-conducting filler are prepared by the following method: mixing the first heat-conducting filler, the second heat-conducting filler, and an ethanol solution of the amino-terminated silane coupling agent, heating for reaction, filtering, and drying to obtain the amino-modified first heat-conducting filler and the amino-modified second heat-conducting filler.

[0025] Preferably, the amino-terminated silane coupling agent comprises any one or a combination of at least two of 3-aminopropyltriethoxysilane (KH-550), 3-aminopropyltrimethoxysilane (KH-540), or [3-(2-aminoethyl)aminopropyl]trimethoxysilane (KH-792).

[0026] Preferably, the mass percentage concentration of the ethanol solution of the amino-terminated silane coupling agent is 3% to 10%, such as 4%, 5%, 6%, 7%, 8%, or 9%, etc.

[0027] Preferably, the mass of the amino-terminated silane coupling agent is 0.5% to 1.5% of the total mass of the first heat-conducting filler and the second heat-conducting filler, such as 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, or 1.4%, etc.

[0028] Preferably, the mass ratio of the first heat-conducting filler to the second heat-conducting filler is (1.5 to 9):1, such as 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, or 8:1, etc.

[0029] Preferably, the raw materials for preparing the high heat-conducting and insulating double-dynamic network polymer material further include an organic solvent.

[0030] Preferably, the organic solvent comprises any one or a combination of at least two of dichloromethane, acetone, methyl ethyl ketone, toluene, dimethylformamide (DMF), or dimethylacetamide (DMAc).

[0031] Preferably, the raw materials for preparing the high thermal conductivity insulating dual-dynamic network polymer material include the following components in parts by weight: 10 parts of polymer matrix, 70-90 parts of modified inorganic thermal conductive filler (such as 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts, 84 parts, 86 parts or 88 parts, etc.), and 10-50 parts of organic solvent (such as 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 45 parts, etc.).

[0032] In a second aspect, the present invention provides a method for preparing the high thermal conductivity insulating dual-dynamic network polymer material as described in the first aspect. The preparation method includes the following steps: mixing the polymer matrix, the modified inorganic thermal conductive filler and optionally the organic solvent, and curing to obtain the high thermal conductivity insulating dual-dynamic network polymer material.

[0033] Preferably, the temperature of the curing is 60-100 °C, such as 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C or 95 °C, etc.

[0034] Preferably, the time of the curing is 2-12 h, such as 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h or 11 h, etc.

[0035] In a third aspect, the present invention provides an application of the high thermal conductivity insulating dual-dynamic network polymer material as described in the first aspect in electronic packaging materials.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] The present invention uses an epoxy vanillin monomer synthesized from bio-based raw materials, adds a dithio curing agent and a modified inorganic thermal conductive filler, and prepares a recyclable high thermal conductivity insulating dual-dynamic network polymer material through ring-opening addition and amine-aldehyde condensation. The high thermal conductivity insulating dual-dynamic network polymer material contains dynamic Schiff base bonds and dynamic disulfide bonds, which can realize reshaping processing and recycling; the first thermal conductive filler and the second thermal conductive filler with different D50 particle sizes are used to fill small particle size thermal conductive fillers between large particle size thermal conductive fillers, and can be filled in a state close to the closest packing, thereby improving the thermal conductivity. It not only solves the dispersion problem of the thermal conductive filler, but also the polymer has reprocessing and recycling performance. At the same time, the bio-based raw material epoxy vanillin monomer can replace the traditional bisphenol A epoxy resin harmful to the human body, which is safer, greener and more environmentally friendly. The tensile strength of the high thermal conductivity insulating dual-dynamic network polymer material is ≥59.3 MPa, the elongation at break is ≥6.1%, the thermal conductivity is ≥3.9 W / mK, the insulation strength is ≥42 kV / mm. After 3 times of recycled hot pressing and molding, the tensile strength decrease rate is ≤3%, the elongation at break is ≤9%, the thermal conductivity decrease rate is ≤5%, and the insulation strength decrease rate is ≤7%. Description of the Drawings

[0038] Figure 1 1H NMR spectrum of the epoxy vanillin monomer prepared in Preparation Example 1;

[0039] Figure 2 HRMS spectrum of the epoxy vanillin monomer prepared in Preparation Example 1. Detailed implementation manners

[0040] The technical solution of the present invention will be further described below through specific implementation manners. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0041] Preparation Example 1

[0042] An epoxy vanillin monomer, and the preparation method of the epoxy vanillin monomer is as follows: Add 15.2 g of vanillin (0.1 mol), 46.3 g of epichlorohydrin (0.5 mol) and 1.13 g of benzyltriethylammonium chloride (0.005 mol) into a 250 mL three-necked flask equipped with a mechanical stirrer and a condenser, react at 90 °C for 3 h, then cool to room temperature, rotary evaporate to remove the excessive epichlorohydrin, then add the NaOH aqueous solution (4.4 g of NaOH dissolved in 25 g of deionized water) into the flask, and continue to stir and react at 30 °C for 30 min, then add ethyl acetate and deionized water and stir to mix, the mixture is extracted three times with ethyl acetate, the organic phase is collected, the organic phase is rinsed three times with saturated brine, then dried overnight over anhydrous MgSO4, and the ethyl acetate is rotary evaporated to obtain a yellow solid product, epoxy vanillin monomer, and the yield is about 80 wt%.

[0043] The 1H NMR spectrum of the prepared epoxy vanillin monomer is as shown in Figure 1 shown, and the HRMS spectrum is as shown in Figure 2 shown;

[0044] HRMS (m / z): The measured value is 209.08062 g / mol. (The theoretical value is 208.07 g / mol);

[0045] 1H NMR (400 MHz, DMSO-d6) 9.99 - 9.69 (m, 1H), 7.81 - 7.03 (m, 3H), 4.56 - 4.23 (m, 1H), 3.94 (d, 4H), 3.50 - 3.22 (m, 3H), 2.79 (d, 2H).

[0046] Example 1

[0047] This embodiment provides a high thermal conductivity and insulating dual-dynamic network polymer material and a preparation method thereof. The high thermal conductivity and insulating dual-dynamic network polymer material comprises the following components in parts by weight: 10 parts of a polymer matrix, 80 parts of a modified inorganic thermal conductive filler, and 30 parts of an organic solvent (dimethylformamide).

[0048] The polymer matrix comprises an epoxy vanillin monomer (the epoxy vanillin monomer provided in Preparation Example 1) and a dithio curing agent (4,4'-dithiobisbenzeneamine), and the mass ratio of the epoxy vanillin monomer to the dithio curing agent is 1:0.67.

[0049] The modified inorganic thermal conductive filler comprises a first thermally conductive filler modified by amination and a second thermally conductive filler modified by amination, and is prepared by the following method: adding a first thermally conductive filler (aluminum nitride, D50 particle size of 30 μm) and a second thermally conductive filler (aluminum nitride, D50 particle size of 1.1 μm) with a mass ratio of 7:3 into an ethanol solution of an aminoalkylsilane coupling agent (the aminoalkylsilane coupling agent is 3-aminopropyltriethoxysilane, with a mass percentage concentration of 5 wt%), and the mass of the aminoalkylsilane coupling agent in the ethanol solution of the aminoalkylsilane coupling agent is 1% of the total mass of the first thermally conductive filler and the second thermally conductive filler. After heating and stirring at 60 °C for 8 hours, filtration and drying are carried out to obtain the first thermally conductive filler modified by amination and the second thermally conductive filler modified by amination.

[0050] The preparation method of the high thermal conductivity and insulating dual-dynamic network polymer material is as follows: ultrasonically mixing the polymer matrix, the modified inorganic thermal conductive filler and the organic solvent uniformly, pouring them into a polytetrafluoroethylene mold, drying at 80 °C until the solvent is completely volatilized, and then curing at 100 °C for 6 h to obtain the high thermal conductivity and insulating dual-dynamic network polymer material.

[0051] Example 2

[0052] This embodiment provides a high thermal conductivity and insulating dual-dynamic network polymer material and a preparation method thereof. The high thermal conductivity and insulating dual-dynamic network polymer material comprises the following components in parts by weight: 10 parts of a polymer matrix, 90 parts of a modified inorganic thermal conductive filler, and 40 parts of an organic solvent (dimethylacetamide).

[0053] The polymer matrix comprises an epoxy vanillin monomer (the epoxy vanillin monomer provided in Preparation Example 1) and a dithio curing agent (2,2'-dithiobisbenzeneamine), and the mass ratio of the epoxy vanillin monomer to the dithio curing agent is 1:0.52.

[0054] The modified inorganic heat-conducting filler includes a first heat-conducting filler modified by amination and a second heat-conducting filler modified by amination, which are prepared by the following method: Add a first heat-conducting filler (aluminum nitride, D50 particle size is 50 μm) and a second heat-conducting filler (aluminum nitride, D50 particle size is 3 μm) with a mass ratio of 2:1 into an ethanol solution of an amino-terminated silane coupling agent (the amino-terminated silane coupling agent is 3-aminopropyltriethoxysilane, mass percentage concentration is 5 wt%). The mass of the amino-terminated silane coupling agent in the ethanol solution of the amino-terminated silane coupling agent is 1.5% of the total mass of the first heat-conducting filler and the second heat-conducting filler. After heating and stirring at 60 °C for 8 hours, filter and dry to obtain the first heat-conducting filler modified by amination and the second heat-conducting filler modified by amination.

[0055] The preparation method of the high heat-conducting and insulating double-dynamic network polymer material is as follows: Ultrasonically mix the polymer matrix, the modified inorganic heat-conducting filler and the organic solvent evenly, pour them into a polytetrafluoroethylene mold, dry at 80 °C to completely volatilize the solvent, and then cure at 90 °C for 12 h to obtain the high heat-conducting and insulating double-dynamic network polymer material.

[0056] Example 3

[0057] This example provides a high heat-conducting and insulating double-dynamic network polymer material and its preparation method. The high heat-conducting and insulating double-dynamic network polymer material includes the following components by weight: 10 parts of polymer matrix, 70 parts of modified inorganic heat-conducting filler, and 20 parts of organic solvent (acetone).

[0058] The polymer matrix includes an epoxy vanillin monomer (the epoxy vanillin monomer provided in Preparation Example 1) and a dithio curing agent (4,4'-dithiobis(aniline)), and the mass ratio of the epoxy vanillin monomer to the dithio curing agent is 1:1.94.

[0059] The modified inorganic heat-conducting filler includes a first heat-conducting filler modified by amination and a second heat-conducting filler modified by amination, which are prepared by the following method: Add a first heat-conducting filler (aluminum nitride, D50 particle size is 20 μm) and a second heat-conducting filler (aluminum nitride, D50 particle size is 0.5 μm) with a mass ratio of 9:1 into an ethanol solution of an amino-terminated silane coupling agent (the amino-terminated silane coupling agent is 3-aminopropyltriethoxysilane, mass percentage concentration is 5 wt%). The mass of the amino-terminated silane coupling agent in the ethanol solution of the amino-terminated silane coupling agent is 0.5% of the total mass of the first heat-conducting filler and the second heat-conducting filler. After heating and stirring at 60 °C for 8 hours, filter and dry to obtain the first heat-conducting filler modified by amination and the second heat-conducting filler modified by amination.

[0060] The preparation method of the high thermal conductivity insulating double-dynamic network polymer material is as follows: The polymer matrix, modified inorganic thermal conductive filler, and organic solvent are ultrasonically mixed evenly, poured into a polytetrafluoroethylene mold, dried at 80 °C until the solvent completely volatilizes, and then cured at 100 °C for 10 h to obtain the high thermal conductivity insulating double-dynamic network polymer material.

[0061] Example 4

[0062] This example provides a high thermal conductivity insulating double-dynamic network polymer material and its preparation method. The difference from Example 1 is only that the first thermal conductive filler (aluminum nitride, D50 particle size of 30 μm) is replaced with the same mass of the first thermal conductive filler (boron nitride, D50 particle size of 30 μm), and the second thermal conductive filler (aluminum nitride, D50 particle size of 1.1 μm) is replaced with the same mass of the second thermal conductive filler (boron nitride, D50 particle size of 1.1 μm), and other conditions are the same as those in Example 1.

[0063] Example 5

[0064] This example provides a high thermal conductivity insulating double-dynamic network polymer material and its preparation method. The difference from Example 1 is only that the first thermal conductive filler (aluminum nitride, D50 particle size of 30 μm) is replaced with the same mass of the first thermal conductive filler (diamond, D50 particle size of 30 μm), and the second thermal conductive filler (aluminum nitride, D50 particle size of 1.1 μm) is replaced with the same mass of the second thermal conductive filler (diamond, D50 particle size of 1.1 μm), and other conditions are the same as those in Example 1.

[0065] Example 6

[0066] This example provides a high thermal conductivity insulating double-dynamic network polymer material and its preparation method. The difference from Example 1 is only that the first thermal conductive filler (aluminum nitride, D50 particle size of 30 μm) is replaced with the same mass of the first thermal conductive filler (aluminum oxide, D50 particle size of 30 μm), and the second thermal conductive filler (aluminum nitride, D50 particle size of 1.1 μm) is replaced with the same mass of the second thermal conductive filler (aluminum oxide, D50 particle size of 1.1 μm), and other conditions are the same as those in Example 1.

[0067] Example 7

[0068] This example provides a high thermal conductivity insulating double-dynamic network polymer material and its preparation method. The difference from Example 1 is only that the first thermal conductive filler (aluminum nitride, D50 particle size of 30 μm) is replaced with the same mass of the first thermal conductive filler (aluminum hydroxide, D50 particle size of 30 μm), and the second thermal conductive filler (aluminum nitride, D50 particle size of 1.1 μm) is replaced with the same mass of the second thermal conductive filler (aluminum oxide, D50 particle size of 1.1 μm), and other conditions are the same as those in Example 1.

[0069] Example 8

[0070] This example provides a highly thermally conductive insulating dual-dynamic network polymer material and its preparation method. The difference from Example 1 is only that 3-aminopropyltriethoxysilane is replaced with the same mass of 3-aminopropyltrimethoxysilane, and other conditions are the same as those in Example 1.

[0071] Example 9

[0072] This example provides a highly thermally conductive insulating dual-dynamic network polymer material and its preparation method. The difference from Example 1 is only that 3-aminopropyltriethoxysilane is replaced with the same mass of [3-(2-aminoethyl)aminopropyl]trimethoxysilane, and other conditions are the same as those in Example 1.

[0073] Example 10

[0074] This example provides a highly thermally conductive insulating dual-dynamic network polymer material and its preparation method. The difference from Example 1 is only that the second thermally conductive filler (aluminum nitride, D50 particle size is 1.1 μm) is replaced with the same mass of the second thermally conductive filler (aluminum oxide, D50 particle size is 0.3 μm), and other conditions are the same as those in Example 1.

[0075] Example 11

[0076] This example provides a highly thermally conductive insulating dual-dynamic network polymer material and its preparation method. The difference from Example 1 is only that the second thermally conductive filler (aluminum nitride, D50 particle size is 1.1 μm) is replaced with the same mass of the second thermally conductive filler (aluminum oxide, D50 particle size is 10 μm), and other conditions are the same as those in Example 1.

[0077] Comparative Example 1

[0078] This comparative example provides a polymer-based composite material. The difference from Example 1 is only that the epoxy vanillin monomer is replaced with the same mass of bisphenol A diglycidyl ether (DGEBA), and other conditions are the same as those in Example 1.

[0079] Comparative Example 2

[0080] This comparative example provides a polymer-based composite material. The difference from Example 1 is only that the second thermally conductive filler (aluminum nitride, D50 particle size is 1.1 μm) is not added, and the addition amount of the first thermally conductive filler (aluminum nitride, D50 particle size is 30 μm) is increased so that the weight fraction of the modified inorganic thermally conductive filler remains unchanged, and other conditions are the same as those in Example 1.

[0081] Comparative Example 3

[0082] This comparative example provides a polymer-based composite material, which is only different from Example 1 in that the ethanol solution of the terminal amino silane coupling agent (the terminal amino silane coupling agent is 3-aminopropyltriethoxysilane, and the mass percentage concentration is 5 wt%) is replaced with an ethanol solution of a silane coupling agent containing double bonds of the same mass (the silane coupling agent containing double bonds is γ-methacryloxypropyltrimethoxysilane, and the mass percentage concentration is 5 wt%), and other conditions are the same as those in Example 1.

[0083] Comparative Example 4

[0084] This comparative example provides a polymer-based composite material, which is only different from Example 1 in that the disulfide curing agent (2,2'-dithiobisbenzeneamine) is replaced with 4,4'-diaminodiphenylmethane of the same mass, and other conditions are the same as those in Example 1.

[0085] The initial performance tests were carried out on the high thermal conductivity and insulating double dynamic network polymer materials provided in the above Examples 1 to 11 and the polymer-based composite materials provided in Comparative Examples 1 to 4 as follows:

[0086] Tensile strength and elongation at break: Tested according to the method of GB / T 1040.1-2018.

[0087] Thermal conductivity: Tested according to the method of ASTM D5470-17(2024).

[0088] Insulation strength: The insulation strength was tested using a Chroma 19073 withstand voltage insulation tester from Taiwan, China.

[0089] The initial performance test results are shown in Table 1 below.

[0090] The recyclability tests were carried out on the high thermal conductivity and insulating double dynamic network polymer materials provided in the above Examples 1 to 11 and the polymer-based composite materials provided in Comparative Examples 1 to 4. The specific test method is as follows: The samples were cut into particles with an average particle size of 500 μm, and then hot-pressed at 180 °C and a pressure of 5 MPa for 30 min again to complete the hot-pressing molding. The above steps of cutting and hot-pressing molding were repeated 3 times, and the samples prepared for the 3rd time were re-tested for the above tensile strength, elongation at break, thermal conductivity and insulation strength.

[0091] The test results of the recycling performance are shown in Table 2 below.

[0092] Table 1

[0093] Tensile strength (MPa) Elongation at break (%) Thermal conductivity (W / mK) Dielectric strength (kV / mm) Example 1 65.3 6.7 6.3 46 Example 2 63.2 6.4 6.1 44 Example 3 59.3 7.1 6.2 42 Example 4 66.2 6.5 6.2 50 Example 5 66.7 6.4 8.2 49 Example 6 65.9 6.5 4.3 45 Example 7 65.8 6.7 3.9 46 Example 8 65.2 6.6 6.3 45 Example 9 64.9 6.5 6.3 44 Example 10 64.6 6.3 6.2 45 Example 11 64.7 6.1 6.2 43 Comparative Example 1 65.3 5.4 5.4 42 Comparative Example 2 65.2 4.9 4.5 38 Comparative Example 3 60.3 5.2 5.2 36 Comparative Example 4 63.5 5.9 5.8 44

[0094] Table 2

[0095]

[0096] As can be seen from the content of Table 1, the tensile strength of the highly thermally conductive and insulating dual-dynamic network polymer materials provided in Examples 1 to 11 is ≥59.3 MPa, the elongation at break is ≥6.1%, the thermal conductivity is ≥3.9 W / mK, the insulation strength is ≥42 kV / mm. After 3 times of recycled hot pressing and molding, the tensile strength decrease rate is ≤3%, the elongation at break is ≤9%, the thermal conductivity decrease rate is ≤5%, and the insulation strength decrease rate is ≤7%.

[0097] Compared with Example 1, if the D50 particle size of the second thermal conductive filler is too small (Example 10), the thermal conductivity of the prepared highly thermally conductive and insulating dual-dynamic network polymer material will decrease. If the D50 particle size of the second thermal conductive filler is too large (Example 11), the thermal conductivity of the prepared highly thermally conductive and insulating dual-dynamic network polymer material will decrease, and the insulation strength decrease rate after recycling becomes higher. Thus, it can be seen that the performance of the highly thermally conductive and insulating dual-dynamic network polymer material prepared by controlling the D50 particle size of the second thermal conductive filler within a specific range is better.

[0098] Compared with Example 1, if vanillin epoxy monomer is replaced with the same mass of bisphenol A diglycidyl ether (Comparative Example 1), the recyclability of the prepared polymer matrix composite material becomes worse. The reason is that the polymer matrix composite material prepared with bisphenol A diglycidyl ether does not contain dynamic Schiff base bonds (C=N), and the density of dynamic bonds in the polymer matrix composite material becomes lower.

[0099] Compared with Example 1, if the second thermal conductive filler is not added (Comparative Example 2), the thermal conduction network is discontinuous, and there are large voids between the thermal conductive fillers, then the thermal conductivity of the prepared polymer matrix composite material becomes worse, and the recyclability becomes worse.

[0100] Compared with Example 1, if the amino-terminated silane coupling agent is replaced with a double-bond-containing silane coupling agent (Comparative Example 3), the recyclability of the prepared polymer matrix composite material becomes worse. The reason is that the double-bond-terminated silane coupling agent cannot undergo an amino-aldol condensation reaction with the aldehyde group of vanillin epoxy. In the polymer matrix composite material, not only the density of dynamic bonds becomes lower, but also the thermal conductive fillers are prone to agglomeration, which affects the thermal conductivity.

[0101] Compared with Example 1, if 2,2'-dithiobisbenzeneamine is replaced with 4,4'-diaminodiphenylmethane (Comparative Example 4), the recyclability of the prepared polymer matrix composite material becomes worse. The reason is that 4,4'-diaminodiphenylmethane does not contain dynamic disulfide bonds (S-S), and the density of dynamic bonds in the polymer matrix composite material becomes lower.

[0102] The applicant declares that the present invention illustrates the process method of the present invention through the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of the raw materials selected for the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A highly thermally conductive and insulating dual-dynamic network polymer material, characterized in that, The raw materials for preparing the high thermal conductivity insulating double-dynamic network polymer material include the following components: a polymer matrix and a modified inorganic thermal conductive filler; The polymer matrix includes an epoxy vanillin monomer and a dithio curing agent; The structural formula of the epoxy vanillin monomer is as follows: The modified inorganic thermal conductive filler includes a first thermal conductive filler modified by amination and a second thermal conductive filler modified by amination; The D50 particle size of the first thermal conductive filler > the D50 particle size of the second thermal conductive filler.

2. The highly thermally conductive and insulating dual-dynamic network polymer material according to claim 1, wherein The raw materials for preparing the epoxy vanillin monomer include vanillin and epichlorohydrin; Preferably, the dithio curing agent includes 4,4'-dithiobis(aniline) and / or 2,2'-dithiobis(aniline); Preferably, the mass ratio of the epoxy vanillin monomer to the dithio curing agent is 1:(0.5 - 2).

3. The highly thermally conductive and insulating dual-dynamic network polymer material according to claim 1 or 2, characterized in that, The D50 particle size of the first thermal conductive filler is 20 - 50 μm; Preferably, the D50 particle size of the second thermal conductive filler is 0.5 - 3 μm.

4. The highly thermally conductive insulating dual-dynamic network polymer material according to any one of claims 1 to 3, characterized in that, The first thermal conductive filler and the second thermal conductive filler each independently include any one or a combination of at least two of boron nitride, aluminum nitride, aluminum oxide, diamond, or aluminum hydroxide.

5. The highly thermally conductive insulating dual-dynamic network polymer material according to any one of claims 1 to 4, characterized in that, The first thermal conductive filler modified by amination and the second thermal conductive filler modified by amination are prepared by modifying the first thermal conductive filler and the second thermal conductive filler with an amino-terminated silane coupling agent; Preferably, the amino-terminated silane coupling agent includes any one or a combination of at least two of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, or [3-(2-aminoethyl)aminopropyl]trimethoxysilane.

6. The highly thermally conductive insulating dual-dynamic network polymer material according to claim 5, wherein The mass of the amino-terminated silane coupling agent is 0.5% - 1.5% of the total mass of the first thermal conductive filler and the second thermal conductive filler; Preferably, the mass ratio of the first thermal conductive filler to the second thermal conductive filler is (1.5 - 9):

1.

7. The highly thermally conductive and insulating dual-dynamic network polymer material according to any one of claims 1 to 6, characterized in that The raw materials for preparing the high thermal conductivity insulating double-dynamic network polymer material further include an organic solvent; Preferably, the organic solvent includes any one or a combination of at least two of dichloromethane, acetone, methyl ethyl ketone, toluene, dimethylformamide, or dimethylacetamide; Preferably, the raw materials for preparing the high thermal conductivity insulating double-dynamic network polymer material include the following components in parts by weight: 10 parts of polymer matrix, 70 - 90 parts of modified inorganic thermal conductive filler, and 10 - 50 parts of organic solvent.

8. A method for preparing a highly thermally conductive insulating dual-dynamic network polymer material according to any one of claims 1 to 7, characterized in that, The preparation method includes the following steps: mixing the polymer matrix, the modified inorganic thermal conductive filler, and optionally the organic solvent, and curing to obtain the high thermal conductivity insulating double-dynamic network polymer material.

9. The preparation method according to claim 8, characterized in that, The temperature of the curing is 60 - 100 °C; Preferably, the time of the curing is 2 - 12 h.

10. Use of the high thermal conductivity insulating double-dynamic network polymer material according to any one of claims 1 - 7 in an electronic packaging material.

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