High-thermal-conductivity and high-temperature-resistant epoxy resin pouring sealant with cold and hot impact resistance

Abstract

The invention relates to the technical field of adhesives and pouring sealants, and particularly discloses a high-thermal-conductivity and high-temperature-resistant epoxy resin pouring sealant with cold and hot impact resistance, which comprises 100 parts of organic silicon modified epoxy resin with the epoxy value of 0.450-0.550 eq / 100g and the viscosity of 3000-25000mPa. S at 25 DEG C; the capsule wall material is a polyurea-silicon dioxide compound, and the wall thickness of the capsule wall material is 0.5-2 microns; 600 to 1000 parts of surface modified composite heat conduction powder; the core layer is made of nitrile rubber, the shell layer is made of polysiloxane, and the shell layer accounts for 10-30 wt%; through the synergistic effect of the surface modified composite heat-conducting powder and the core-shell structure elastomer, the mechanical strength of the material is remarkably improved while high heat conductivity is guaranteed, and compared with a traditional system, the heat-conducting property and the tensile strength are improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of adhesives and potting compounds, and particularly relates to a high thermal conductivity and high temperature resistant epoxy potting compound with resistance to thermal shock. Background Art

[0002] With the breakthrough development of cutting-edge manufacturing technologies and the continuous expansion of high-end industrial application scenarios, the demand for high-performance thermal conductive and impact-resistant materials has shown an exponential growth trend in frontier fields such as new energy vehicle motor encapsulation, 5G communication base station thermal management, and intelligent electronic system protection. Especially under the harsh working conditions that require simultaneously meeting high thermal conductivity (>2 W / m·K), wide temperature range stability (-40 to 150 °C), resistance to thermal shock (>30 cycles), and low thermal stress, traditional potting materials are difficult to meet the dual requirements of efficient heat dissipation and long-term reliability of devices in modern industry due to problems such as discontinuous thermal conduction networks, insufficient interfacial bonding strength, and unbalanced thermo-mechanical properties.

[0003] As the core solution in the field of potting materials, the epoxy resin system occupies a dominant position in scenarios such as power electronics packaging, high-frequency transformer insulation, and precision circuit protection due to its excellent bonding strength, outstanding chemical corrosion resistance, and excellent electrical insulation performance. By introducing micron / nano-scale thermal conductive fillers (such as alumina, boron nitride, etc.) to modify the epoxy resin, its thermal conductivity can be significantly improved, and it has become the key technical path to achieve efficient thermal management of components. However, traditional thermal conductive and impact-resistant epoxy potting compounds still face some technical bottlenecks in practical applications. First, when a large amount of thermal conductive powder is filled into the epoxy resin system, although the thermal conductivity is improved, the mechanical properties of the potting compound are significantly reduced, resulting in a decrease in impact resistance and tensile strength in practical applications. This disadvantage is particularly obvious in high-stress and high-temperature environments, restricting the application of the potting compound. Secondly, currently available heat-resistant epoxy resins usually have a high viscosity, making it difficult for thermal conductive powders to be evenly dispersed during the preparation process, limiting the amount of thermal conductive and impact-resistant powders used, and thus leading to unevenness and reduced stability of the thermal conductivity and impact resistance of the potting compound. Summary of the Invention

[0004] The purpose of the present invention is to provide a high thermal conductivity and high temperature resistant epoxy potting compound with resistance to thermal shock to solve the problems raised in the above background art.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] A high thermal conductivity and high temperature resistant epoxy potting compound with resistance to thermal shock, by weight, comprises the following components:

[0007] 100 parts of silicone-modified epoxy resin, with an epoxy value of 0.450 - 0.550 eq / 100g and a viscosity of 3000 - 25000 mPa·s at 25°C;

[0008] 15 - 80 parts of microencapsulated amine curing agent, with the capsule wall material being a polyurea-silica composite and the wall thickness being 0.5 - 2 μm;

[0009] 600 - 1000 parts of surface-modified composite thermal conductive powder;

[0010] 5 - 30 parts of core-shell structure elastomer impact modifier, with the core layer being nitrile rubber and the shell layer being polysiloxane, and the shell layer accounting for 10 - 30 wt%.

[0011] Preferably, the silicone-modified epoxy resin comprises:

[0012] 100 parts of bisphenol A epoxy resin;

[0013] 5 - 15 parts of nano-sized cage-shaped polyhedral oligomeric silsesquioxane, with a particle size of 10 - 50 nm;

[0014] 10 - 25 parts of silane coupling agent.

[0015] Preferably, the silane coupling agent includes at least one of γ-glycidoxypropyltrimethoxysilane and methyltriethoxysilane.

[0016] Preferably, the preparation of the silicone-modified epoxy resin includes: under nitrogen protection, high-speed shear dispersion of bisphenol A epoxy resin and nano-sized cage-shaped polyhedral oligomeric silsesquioxane at 5000 - 8000 r / min; after heating to 80°C, dropping the silane coupling agent at a rate of 0.5 - 2°C / min; using microwave-assisted heating, reacting at a frequency of 2.45 GHz for 3 - 5 hours, and discharging to obtain the silicone-modified epoxy resin.

[0017] Preferably, the surface-modified composite thermal conductive powder comprises: 100 - 200 parts of nano-diamond-silicon carbide whisker composite, with an aspect ratio > 20; 300 - 500 parts of titanate-modified alumina; 50 - 100 parts of graphene-coated boron nitride, with the number of graphene layers ≤ 5 layers.

[0018] Preferably, the nano-diamond-silicon carbide whisker composite is prepared by chemical vapor deposition, specifically including: placing silicon carbide whiskers in a reactor, introducing a CH 4 / H 2 mixed gas, depositing a diamond layer at 800 - 1000°C; alternately introducing an argon ion beam for surface activation during the deposition process.

[0019] Preferably, the amine curing agent includes one or more of m-phenylenediamine, diethylenetriamine, triethylenetetramine, polyetheramine, and isophorone diamine.

[0020] Preferably, the preparation method of the core-shell structure elastomer impact modifier includes: preparing monodisperse nitrile rubber emulsion droplets by microfluidic technology; depositing a polysiloxane shell layer on the droplet surface by atomic layer deposition; after curing, drying with supercritical CO 2 to obtain hollow microspheres.

[0021] According to the preparation method of the epoxy resin potting adhesive described in any one of the above, it is characterized in that it includes: dispersing organosilicon-modified epoxy resin and surface-modified composite thermal conductive powder at a high speed of 1000-4000 r / min; degassing at 80-100 °C and a vacuum degree of 0.08-0.12 MPa for 1-3 hours; after cooling to below 30 °C, adding a microencapsulated amine curing agent and a core-shell structure elastomer impact modifier and mixing.

[0022] Compared with the prior art, the beneficial effects of the present invention are:

[0023] (1) Through the synergistic effect of the surface-modified composite thermal conductive powder and the core-shell structure elastomer, while ensuring high thermal conductivity, the mechanical strength of the material is significantly improved. Compared with the traditional system, the thermal conductivity is improved and the tensile strength is increased.

[0024] (2) The core-shell elastomer buffers thermal stress through flexibility, combined with the slow-release effect of the microencapsulated curing agent, so that the material can withstand more than the traditional system under the thermal shock of -40 °C to 150 °C, significantly reducing the interfacial thermal resistance and avoiding cracks or shelling caused by thermal expansion differences. The nano-cage-like polyhedral oligomeric silsesquioxane in the organosilicon-modified epoxy resin enhances the thermal stability of the cross-linked network, combined with the antioxidant barrier effect of graphene-coated boron nitride, and has long-term high-temperature resistance and anti-aging performance.

[0025] (3) The synergistic effect of titanate-modified alumina and the core-shell elastomer prepared by microfluidic technology optimizes the filler dispersion, reduces the viscosity of the resin system, realizes uniform dispersion under high filler content, and avoids agglomeration defects. Description of the Drawings

[0026] Figure 1 It is the process flow chart of the present invention. Detailed Embodiments

[0027] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

[0028] Example 1:

[0029] A high thermal conductivity and high temperature resistant epoxy resin potting adhesive resistant to thermal shock, by weight, comprises the following components:

[0030] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.500 eq / 100 g, viscosity at 25 °C is 15000 mPa·s);

[0031] 45 parts of microencapsulated amine curing agent (capsule wall material is polyurea-silica composite, wall thickness 1.2 μm, curing agent is a mixture of m-phenylenediamine and polyetheramine);

[0032] 800 parts of surface-modified composite thermal conductive powder (including 150 parts of nanodiamond-silicon carbide whisker composite, 400 parts of titanate-modified alumina, and 70 parts of graphene-coated boron nitride);

[0033] 18 parts of core-shell structure elastomer impact resistant agent (shell layer accounts for 20 wt%);

[0034] Preparation of organosilicon-modified epoxy resin:

[0035] Bisphenol A epoxy resin and nano-cage polyhedral oligomeric silsesquioxane (particle size 30 nm, addition amount 10 parts) are sheared and dispersed at a high speed of 6000 r / min for 30 minutes under nitrogen protection; the temperature is raised to 80 °C, and γ-glycidoxypropyltrimethoxysilane (15 parts) is added dropwise at a rate of 1 °C / min; the reaction is carried out for 4 hours under microwave-assisted heating (2.45 GHz) to obtain organosilicon-modified epoxy resin;

[0036] The above resin and the surface-modified composite thermal conductive powder are dispersed at a high speed of 2500 r / min for 1 hour;

[0037] Defoaming is carried out at 90 °C and a vacuum degree of 0.10 MPa for 2 hours; after cooling to 25 °C, the microencapsulated amine curing agent and the core-shell structure elastomer impact resistant agent are added and mixed evenly.

[0038] Example 2:

[0039] By weight, comprises the following components:

[0040] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.480 eq / 100 g, viscosity at 25 °C is 8000 mPa·s);

[0041] 60 parts of microencapsulated amine curing agent (capsule wall thickness 1.8 μm, curing agent is isophorone diamine);

[0042] 950 parts of surface-modified composite thermal conductive powder (including 180 parts of nanodiamond-silicon carbide whisker composite, 450 parts of titanate-modified alumina, and 90 parts of graphene-coated boron nitride);

[0043] 25 parts of core-shell structured elastomer impact modifier (the shell layer accounts for 25 wt%).

[0044] Preparation of silicone-modified epoxy resin:

[0045] Bisphenol A epoxy resin and nano-cage polyhedral oligomeric silsesquioxane (particle size 20 nm, addition amount 12 parts) were shear-dispersed at a high speed of 7000 r / min; Methyltriethoxysilane (20 parts) was added dropwise, and microwave reaction was carried out for 3.5 hours.

[0046] Surface-modified composite thermal conductive powder was prepared by chemical vapor deposition method (CH 4 / H 2 mixed gas, 900 °C) to prepare nano-diamond-silicon carbide whisker composite; After mixing the mixed resin and the thermal conductive powder, degassing was carried out for 2.5 hours under a vacuum degree of 0.09 MPa;

[0047] A curing agent and an impact modifier were added and mixed at room temperature.

[0048] Example 3:

[0049] By weight, it includes the following components:

[0050] 100 parts of silicone-modified epoxy resin (epoxy value 0.520 eq / 100 g, viscosity at 25 °C is 20000 mPa·s);

[0051] 30 parts of microencapsulated amine curing agent (capsule wall thickness 0.8 μm, curing agent is diethylenetriamine);

[0052] 650 parts of surface-modified composite thermal conductive powder (including 120 parts of nano-diamond-silicon carbide whisker composite, 350 parts of titanate-modified alumina, and 50 parts of graphene-coated boron nitride);

[0053] 10 parts of core-shell structured elastomer impact modifier (the shell layer accounts for 15 wt%).

[0054] Preparation of core-shell structured elastomer impact modifier:

[0055] Nitrile rubber emulsion droplets (particle size 5 μm) were prepared by microfluidic technology;

[0056] The polyorganosiloxane shell layer was coated by atomic layer deposition method, and hollow microspheres were obtained by supercritical CO 2 drying.

[0057] After mixing the silicone-modified epoxy resin and the thermal conductive powder, degassing was carried out for 1.5 hours under a vacuum degree of 0.12 MPa;

[0058] A curing agent and an impact modifier were added and stirred and mixed at low temperature (20 °C).

[0059] Example 4:

[0060] By weight, it includes the following components:

[0061] 100 parts of silicone-modified epoxy resin (epoxy value 0.470eq / 100g, viscosity 5000mPa·s at 25°C);

[0062] 20 parts of microencapsulated amine curing agent (capsule wall material is polyurea-silicon dioxide composite, wall thickness is 0.7 μm, and the curing agent is a mixture of triethylenetetramine and polyetheramine);

[0063] 700 parts of surface-modified composite thermally conductive powder (including 110 parts of nano-diamond-silicon carbide whisker composite, 320 parts of titanate-modified alumina, and 55 parts of graphene-coated boron nitride);

[0064] 8 parts of core-shell structure elastomer impact agent (shell layer accounts for 12wt%).

[0065] Preparation of silicone modified epoxy resin:

[0066] Bisphenol A epoxy resin and nanocage polysilsesquioxane (particle size 15 nm, addition amount 8 parts) were dispersed at a high-speed shear of 5500 r / min for 40 minutes; the temperature was raised to 80°C, and γ-glycidyloxypropyltrimethoxysilane (18 parts) was added dropwise at a rate of 0.8°C / min; microwave-assisted heating (2.45 GHz) was used for the reaction for 4.5 hours to obtain a modified resin.

[0067] The resin and the surface-modified composite thermally conductive powder were dispersed at 3000 r / min for 1.2 hours;

[0068] Degassing at 85°C and vacuum degree 0.11MPa for 2.2 hours;

[0069] After cooling to 28°C, add microencapsulated curing agent and impact resistant agent, and stir at low speed to mix.

[0070] Embodiment five:

[0071] By weight, it includes the following components:

[0072] 100 parts of silicone-modified epoxy resin (epoxy value 0.540eq / 100g, viscosity 22000mPa·s at 25°C);

[0073] 70 parts of microencapsulated amine curing agent (capsule wall thickness 1.5 μm, curing agent is a mixture of m-phenylenediamine and isophoronediamine);

[0074] 980 parts of surface-modified composite thermally conductive powder (including 190 parts of nano-diamond-silicon carbide whisker composite, 480 parts of titanate-modified alumina, and 95 parts of graphene-coated boron nitride);

[0075] 28 parts of core-shell structured elastomer impact modifier (the shell layer accounts for 28 wt%).

[0076] Preparation of silicone-modified epoxy resin:

[0077] Bisphenol A epoxy resin and nano-cage polyhedral oligomeric silsesquioxane (particle size 45 nm, addition amount 14 parts) were shear-dispersed at 7500 r / min for 25 minutes; Methyltriethoxysilane (22 parts) was added dropwise and reacted by microwave for 3 hours.

[0078] Preparation of surface-modified composite heat-conducting powder:

[0079] Synthesize nano-diamond-silicon carbide whisker composite by chemical vapor deposition method (CH 4 / H 2 mixed gas, 950 °C), and alternately activate the surface with argon ion beam.

[0080] After mixing the resin and the heat-conducting powder, degas for 3 hours under a vacuum of 0.08 MPa;

[0081] Add the curing agent and the impact modifier, and stir and mix at 200 r / min at room temperature for 30 minutes.

[0082] Example 6:

[0083] By weight, it includes the following components:

[0084] 100 parts of silicone-modified epoxy resin (epoxy value 0.490 eq / 100 g, viscosity at 25 °C 12000 mPa·s);

[0085] 35 parts of microencapsulated amine curing agent (capsule wall thickness 1.0 μm, the curing agent is a complex of diethylenetriamine and isophorone diamine);

[0086] 620 parts of surface-modified composite heat-conducting powder (including 105 parts of nano-diamond-silicon carbide whisker composite, 310 parts of titanate-modified alumina, and 60 parts of graphene-coated boron nitride);

[0087] 12 parts of core-shell structured elastomer impact modifier (the shell layer accounts for 18 wt%).

[0088] Preparation of core-shell structured elastomer impact modifier:

[0089] Prepare acrylonitrile-butadiene rubber emulsion droplets (particle size 8 μm) by microfluidic technology; coat a polysiloxane shell layer (thickness 0.3 μm) by atomic layer deposition method, and supercritical CO 2 After drying, hollow microspheres are obtained.

[0090] Disperse the silicone-modified epoxy resin and the thermal conductive powder at 1800 r / min for 1.5 hours; degas at 95 °C and a vacuum degree of 0.10 MPa for 1.8 hours;

[0091] After cooling to 22 °C, add the curing agent and the impact resistance agent, and mix ultrasonically for 20 minutes.

[0092] Example Seven:

[0093] By weight, it includes the following components:

[0094] 100 parts of silicone-modified epoxy resin (epoxy value 0.530 eq / 100 g, viscosity at 25 °C 18000 mPa·s; prepared from bisphenol A epoxy resin, nano-cage-like polyhedral oligomeric silsesquioxane (particle size 40 nm, addition amount 13 parts) and γ-glycidoxypropyltrimethoxysilane (23 parts) by microwave reaction for 3.8 hours);

[0095] 55 parts of microencapsulated amine curing agent (capsule wall material is polyurea-silica composite, wall thickness 1.6 μm; curing agent is a composite of polyetheramine and triethylenetetramine, mass ratio 2:1);

[0096] 920 parts of surface-modified composite thermal conductive powder (including 170 parts of nano-diamond-silicon carbide whisker composite, 460 parts of titanate-modified alumina, 85 parts of graphene-coated boron nitride; whisker aspect ratio > 25, number of graphene layers ≤ 3 layers);

[0097] 22 parts of core-shell structure elastomer impact resistance agent (shell layer accounts for 23 wt%, core layer nitrile rubber particle size 7 μm).

[0098] Preparation of silicone-modified epoxy resin:

[0099] Disperse bisphenol A epoxy resin and nano-cage-like polyhedral oligomeric silsesquioxane under nitrogen protection at 6800 r / min by high-speed shearing for 35 minutes; heat up to 80 °C, and dropwise add the silane coupling agent at a rate of 1.2 °C / min; react by microwave-assisted heating (2.45 GHz) for 4.2 hours, and cool to room temperature for standby.

[0100] Treatment of thermal conductive powder:

[0101] The nano-diamond-silicon carbide whisker composite is synthesized by chemical vapor deposition method (CH 4 / H 2 mixed gas, 850 °C), and the surface is alternately activated by argon ion beam.

[0102] Disperse the resin and the thermal conductive powder at 3200 r / min by high speed for 1.8 hours; degas at a vacuum degree of 0.11 MPa and a temperature of 95 °C for 2.5 hours.

[0103] After cooling to 28°C, add the microencapsulated curing agent and impact modifier, and stir and mix at 150 r / min for 40 minutes.

[0104] Example VIII:

[0105] By weight, it includes the following components:

[0106] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.510 eq / 100 g, viscosity at 25°C 10,000 mPa·s; containing 20 parts of methyltriethoxysilane coupling agent);

[0107] 25 parts of microencapsulated amine curing agent (capsule wall thickness 0.6 μm, the curing agent is a complex of m-phenylenediamine and diethylenetriamine, mass ratio 3:1);

[0108] 750 parts of surface-modified composite thermal conductive powder (including 130 parts of nanodiamond-silicon carbide whisker composite, 380 parts of titanate-modified alumina, and 65 parts of graphene-coated boron nitride);

[0109] 15 parts of core-shell structure elastomeric impact modifier (shell layer accounts for 17 wt%, thickness of polysiloxane shell layer 0.4 μm).

[0110] Preparation of impact modifier:

[0111] Prepare monodisperse nitrile rubber emulsion droplets (particle size 6 μm) by microfluidic technology; deposit a polysiloxane shell layer on the surface of the droplets by atomic layer deposition, control the deposition rate to be 0.1 nm / cycle; supercritical CO 2 After drying, hollow microspheres are obtained with a porosity > 80%.

[0112] Disperse the organosilicon-modified epoxy resin and the thermal conductive powder at 2200 r / min for 2 hours; degas at a vacuum of 0.09 MPa and a temperature of 88°C for 3 hours.

[0113] After adding the microencapsulated curing agent and impact modifier, use ultrasonic-assisted mixing (frequency 40 kHz, power 300 W) for 15 minutes.

[0114] Example IX:

[0115] By weight, it includes the following components:

[0116] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.560 eq / 100 g, viscosity at 25°C 24,000 mPa·s; containing 14 parts of nano-cage-like polyhedral oligomeric silsesquioxane, the silane coupling agent is a mixture of γ-glycidoxypropyltrimethoxysilane and methyltriethoxysilane, mass ratio 1:1);

[0117] 75 parts of microencapsulated amine curing agent (capsule wall thickness: 2.0 μm, the curing agent is a complex of isophorone diamine and polyetheramine, mass ratio 4:1);

[0118] 1050 parts of surface-modified composite thermal conductive powder (including 210 parts of nanodiamond-silicon carbide whisker composite, 520 parts of titanate-modified alumina, and 100 parts of graphene-coated boron nitride);

[0119] 29 parts of core-shell structure elastomer impact modifier (shell layer proportion: 29 wt%, crosslinking degree of core layer nitrile rubber > 90%);

[0120] Modification of thermal conductive powder: Graphene-coated boron nitride is prepared by liquid-phase exfoliation combined with chemical vapor deposition, and the coating layer thickness < 2 nm.

[0121] Resin synthesis and mixing: Bisphenol A epoxy resin and nano-cage polyhedral oligomeric silsesquioxane are shear-dispersed at 8500 r / min for 20 minutes; after dropping the mixed silane coupling agent, microwave reaction is carried out for 5 hours.

[0122] The resin and the thermal conductive powder are highly dispersed at 4000 r / min for 45 minutes; degassing is carried out at a vacuum degree of 0.12 MPa and a temperature of 100 °C for 1.2 hours; after adding the curing agent and the impact modifier, mixing is carried out using a twin-screw extruder (rotation speed 50 r / min, temperature 30 °C).

[0123] Example Ten:

[0124] By weight, it includes the following components:

[0125] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.480 eq / 100 g, viscosity at 25 °C 9000 mPa·s; prepared by microwave reaction of bisphenol A epoxy resin, nano-cage polyhedral oligomeric silsesquioxane (particle size 25 nm, addition amount 9 parts) and γ-glycidyletheroxypropyltrimethoxysilane (17 parts) for 3.2 hours);

[0126] 40 parts of microencapsulated amine curing agent (capsule wall material is polyurea-silica complex, wall thickness 0.9 μm; the curing agent is a complex of polyetheramine and isophorone diamine, mass ratio 1:1);

[0127] 680 parts of surface-modified composite thermal conductive powder (including 140 parts of nanodiamond-silicon carbide whisker composite, 330 parts of titanate-modified alumina, and 75 parts of graphene-coated boron nitride; aspect ratio of whiskers > 22, number of graphene layers ≤ 4 layers);

[0128] 14 parts of core-shell structure elastomer impact modifier (shell layer proportion: 16 wt%, particle size of core layer nitrile rubber 4 μm).

[0129] Preparation of silicone-modified epoxy resin: Bisphenol A epoxy resin and nano-cage polyhedral oligomeric silsesquioxane were sheared and dispersed at a high speed of 7200 r / min for 28 minutes under nitrogen protection; the temperature was raised to 80 °C, and a silane coupling agent was added dropwise at a rate of 0.9 °C / min; microwave-assisted heating (2.45 GHz) was carried out for 3.6 hours, and then cooled to room temperature for standby.

[0130] Treatment of thermally conductive powder: Nano-diamond-silicon carbide whisker composites were synthesized by chemical vapor deposition (CH 4 / H 2 mixed gas, 870 °C), and the surface was alternately activated by argon ion beam.

[0131] The resin and the thermally conductive powder were dispersed at a high speed of 2800 r / min for 1.3 hours; degassing was carried out at a vacuum degree of 0.10 MPa and a temperature of 92 °C for 1.7 hours. After cooling to 26 °C, a microencapsulated curing agent and an impact-resistant agent were added, and stirred and mixed at 120 r / min for 35 minutes.

[0132] Example XI:

[0133] By weight, it includes the following components:

[0134] 100 parts of silicone-modified epoxy resin (epoxy value 0.550 eq / 100 g, viscosity at 25 °C 23000 mPa·s; containing 24 parts of methyltriethoxysilane coupling agent, nano-cage polyhedral oligomeric silsesquioxane particle size 50 nm, addition amount 11 parts);

[0135] 65 parts of microencapsulated amine curing agent (capsule wall thickness 1.7 μm, curing agent is a complex of triethylenetetramine and diethylenetriamine, mass ratio 3:2);

[0136] 890 parts of surface-modified composite thermally conductive powder (including 160 parts of nano-diamond-silicon carbide whisker composites, 440 parts of titanate-modified alumina, and 80 parts of graphene-coated boron nitride);

[0137] 20 parts of core-shell structure elastomer impact-resistant agent (shell layer accounts for 22 wt%, polysiloxane shell layer thickness 0.5 μm).

[0138] Preparation of impact-resistant agent: Monodisperse nitrile rubber emulsion droplets (particle size 9 μm) were prepared by microfluidic technology; a polysiloxane shell layer was deposited on the surface of the droplets by atomic layer deposition, and the deposition rate was controlled at 0.15 nm / cycle; supercritical CO 2 After drying, hollow microspheres were obtained with a porosity > 85%.

[0139] Disperse the silicone-modified epoxy resin and the thermal conductive powder at 3500 r / min for 1.5 hours; degas for 2.8 hours under a vacuum of 0.09 MPa and a temperature of 96 °C. After adding the microencapsulated curing agent and the impact resistance agent, perform ultrasonic-assisted mixing (frequency 45 kHz, power 350 W) for 25 minutes.

[0140] Example 12:

[0141] By weight, it includes the following components:

[0142] 100 parts of silicone-modified epoxy resin (epoxy value 0.510 eq / 100 g, viscosity at 25 °C 7000 mPa·s; prepared by microwave reaction of bisphenol A epoxy resin, nano-cage-like polyhedral oligomeric silsesquioxane (particle size 35 nm, addition amount 7 parts) and γ-glycidoxypropyltrimethoxysilane (12 parts) for 4.5 hours);

[0143] 50 parts of microencapsulated amine curing agent (capsule wall thickness 1.1 μm, the curing agent is a complex of m-phenylenediamine and polyetheramine, mass ratio 2:3);

[0144] 580 parts of surface-modified composite thermal conductive powder (including 100 parts of nano-diamond-silicon carbide whisker composite, 300 parts of titanate-modified alumina, 60 parts of graphene-coated boron nitride; whisker aspect ratio > 18);

[0145] 9 parts of core-shell structure elastomer impact resistance agent (shell layer proportion 14 wt%, core layer nitrile rubber crosslinking degree > 85%);

[0146] Modification of the thermal conductive powder: Graphene-coated boron nitride is prepared by liquid-phase exfoliation combined with chemical vapor deposition, and the coating layer thickness < 3 nm.

[0147] Shear-disperse bisphenol A epoxy resin and nano-cage-like polyhedral oligomeric silsesquioxane at 6000 r / min for 40 minutes; after dropping the silane coupling agent, perform microwave reaction for 4 hours.

[0148] High-speed disperse the resin and the thermal conductive powder at 2000 r / min for 1 hour; degas at a vacuum of 0.12 MPa and a temperature of 85 °C for 2 hours; after adding the curing agent and the impact resistance agent, mix using a planetary mixer (rotation speed 100 r / min, temperature 25 °C).

[0149] Example 13

[0150] By weight, it includes the following components:

[0151] 100 parts of silicone-modified epoxy resin (epoxy value 0.490 eq / 100 g, viscosity at 25 °C 11000 mPa·s; prepared by microwave reaction for 3.7 hours from bisphenol A epoxy resin, nano-cage polyhedral oligomeric silsesquioxane (particle size 18 nm, addition amount 8 parts), and γ-glycidoxypropyltrimethoxysilane (14 parts));

[0152] 38 parts of microencapsulated amine curing agent (capsule wall material is polyurea-silica composite, wall thickness 0.6 μm; curing agent is a composite of m-phenylenediamine and polyetheramine, mass ratio 1:2);

[0153] 720 parts of surface-modified composite thermal conductive powder (including 130 parts of nano-diamond-silicon carbide whisker composite, 360 parts of titanate-modified alumina, and 65 parts of graphene-coated boron nitride; whisker aspect ratio > 19, number of graphene layers ≤ 3 layers);

[0154] 16 parts of core-shell structure elastomer impact modifier (shell layer accounts for 19 wt%, core layer nitrile rubber particle size 5 μm).

[0155] Preparation of silicone-modified epoxy resin: Bisphenol A epoxy resin and nano-cage polyhedral oligomeric silsesquioxane are sheared and dispersed at a high speed of 5800 r / min for 32 minutes under nitrogen protection; the temperature is raised to 80 °C, and the silane coupling agent is added dropwise at a rate of 0.7 °C / min; microwave-assisted heating (2.45 GHz) reaction for 4.1 hours, and cooled to room temperature for standby.

[0156] Treatment of thermal conductive powder: Nano-diamond-silicon carbide whisker composite is synthesized by chemical vapor deposition method (CH 4 / H 2 mixed gas, 920 °C), and the surface is alternately activated by argon ion beam.

[0157] The resin and the thermal conductive powder are dispersed at a high speed of 2600 r / min for 1.4 hours; degassing is carried out at a vacuum degree of 0.10 MPa and a temperature of 94 °C for 2.2 hours; after cooling to 27 °C, the microencapsulated curing agent and the impact modifier are added, and stirred and mixed at 130 r / min for 30 minutes.

[0158] Example 14:

[0159] By weight, it includes the following components:

[0160] 100 parts of silicone-modified epoxy resin (epoxy value 0.540 eq / 100 g, viscosity at 25 °C 21000 mPa·s; containing 19 parts of methyltriethoxysilane coupling agent, nano-cage polyhedral oligomeric silsesquioxane particle size 48 nm, addition amount 10 parts);

[0161] 68 parts of microencapsulated amine curing agent (capsule wall thickness 1.9 μm, the curing agent is a complex of isophorone diamine and triethylenetetramine, mass ratio 5:1);

[0162] 930 parts of surface-modified composite thermal conductive powder (including 175 parts of nanodiamond-silicon carbide whisker composite, 470 parts of titanate-modified alumina, and 88 parts of graphene-coated boron nitride);

[0163] 26 parts of core-shell structure elastomeric impact modifier (shell layer accounts for 27 wt%, polysiloxane shell layer thickness 0.6 μm).

[0164] Preparation of impact modifier: Monodisperse acrylonitrile-butadiene rubber emulsion droplets (particle size 10 μm) were prepared by microfluidic technology; a polysiloxane shell layer was deposited on the droplet surface by atomic layer deposition, and the deposition rate was controlled at 0.12 nm / cycle; supercritical CO 2 After drying, hollow microspheres were obtained with a porosity > 82%.

[0165] The organosilicon-modified epoxy resin and the thermal conductive powder were dispersed at 3800 r / min for 1.6 hours; degassed at a vacuum of 0.11 MPa and a temperature of 97 °C for 2.6 hours; after adding the microencapsulated curing agent and the impact modifier, ultrasonic-assisted mixing (frequency 42 kHz, power 320 W) was carried out for 20 minutes.

[0166] Example 15:

[0167] By weight, it includes the following components:

[0168] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.460 eq / 100 g, viscosity at 25 °C 6000 mPa·s; prepared from bisphenol A epoxy resin, nano-cage-like polyhedral oligomeric silsesquioxane (particle size 22 nm, addition amount 6 parts) and γ-glycidoxypropyltrimethoxysilane (11 parts) by microwave reaction for 4.8 hours);

[0169] 28 parts of microencapsulated amine curing agent (capsule wall thickness 0.5 μm, the curing agent is a complex of diethylenetriamine and polyetheramine, mass ratio 2:1);

[0170] 610 parts of surface-modified composite thermal conductive powder (including 115 parts of nanodiamond-silicon carbide whisker composite, 290 parts of titanate-modified alumina, and 58 parts of graphene-coated boron nitride; whisker aspect ratio > 16);

[0171] 7 parts of core-shell structure elastomeric impact modifier (shell layer accounts for 11 wt%, core layer acrylonitrile-butadiene rubber crosslinking degree > 88%).

[0172] Modification of thermal conductive powder: Graphene-coated boron nitride was prepared by liquid-phase exfoliation combined with chemical vapor deposition, and the coating layer thickness < 2.5 nm.

[0173] The bisphenol A epoxy resin and the nano-cage polyhedral oligomeric silsesquioxane were shear-dispersed at 6500 r / min for 35 minutes; after dropping the silane coupling agent, microwave reaction was carried out for 4.3 hours.

[0174] The resin and the thermal conductive powder were highly dispersed at 1900 r / min for 1.1 hours; degassing was carried out at a vacuum degree of 0.12 MPa and a temperature of 82 °C for 1.9 hours; after adding the curing agent and the impact resistance agent, a double planetary mixer was used for mixing (rotation speed 80 r / min, temperature 28 °C).

[0175] Example XVI:

[0176] By weight, it includes the following components:

[0177] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.500 eq / 100 g, viscosity at 25 °C 14000 mPa·s; prepared from bisphenol A epoxy resin, nano-cage polyhedral oligomeric silsesquioxane (particle size 28 nm, addition amount 10 parts) and γ-glycidoxypropyltrimethoxysilane (20 parts) by microwave reaction for 3.5 hours);

[0178] 50 parts of microencapsulated amine curing agent (the capsule wall material is polyurea-silica composite, wall thickness 1.0 μm; the curing agent is a composite of m-phenylenediamine and isophorone diamine, mass ratio 1:1);

[0179] 850 parts of surface-modified composite thermal conductive powder (including 160 parts of nano-diamond-silicon carbide whisker composite, 430 parts of titanate-modified alumina, 75 parts of graphene-coated boron nitride; the aspect ratio of the whiskers > 23, the number of graphene layers ≤ 4 layers);

[0180] 24 parts of core-shell structure elastomer impact resistance agent (the shell layer accounts for 24 wt%, the particle size of the core layer nitrile rubber is 6 μm).

[0181] Preparation of organosilicon-modified epoxy resin: The bisphenol A epoxy resin and the nano-cage polyhedral oligomeric silsesquioxane were highly shear-dispersed at 6200 r / min for 30 minutes under nitrogen protection; the temperature was raised to 80 °C, and the silane coupling agent was dropped at a rate of 1.0 °C / min; microwave-assisted heating (2.45 GHz) reaction was carried out for 3.8 hours, and then cooled to room temperature for standby.

[0182] Treatment of thermal conductive powder: The nano-diamond-silicon carbide whisker composite was synthesized by chemical vapor deposition method (CH 4 / H 2 mixed gas, 880 °C), and the surface was alternately activated by argon ion beam.

[0183] Disperse the resin and the thermally conductive powder at a high speed of 3400 r / min for 1.6 hours; degas at a vacuum degree of 0.10 MPa and a temperature of 93 °C for 2.3 hours; after cooling to 25 °C, add the microencapsulated curing agent and the impact resistance agent, and stir and mix at 140 r / min for 45 minutes.

[0184] Example XVII:

[0185] By weight, it includes the following components:

[0186] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.520 eq / 100 g, viscosity at 25 °C 16000 mPa·s; containing 22 parts of methyltriethoxysilane coupling agent, nano-cage-like polyhedral oligomeric silsesquioxane particle size 38 nm, addition amount 12 parts);

[0187] 72 parts of microencapsulated amine curing agent (capsule wall thickness 1.4 μm, the curing agent is a complex of triethylenetetramine and polyetheramine, mass ratio 4:1);

[0188] 970 parts of surface-modified composite thermally conductive powder (including 185 parts of nano-diamond-silicon carbide whisker composite, 490 parts of titanate-modified alumina, and 92 parts of graphene-coated boron nitride);

[0189] 27 parts of core-shell structure elastomer impact resistance agent (shell layer proportion 26 wt%, polysiloxane shell layer thickness 0.7 μm).

[0190] Preparation of the impact resistance agent: Prepare monodisperse nitrile rubber emulsion droplets (particle size 8 μm) by microfluidic technology; deposit a polysiloxane shell layer on the surface of the droplets by atomic layer deposition, and control the deposition rate to be 0.18 nm / cycle; supercritical CO 2 After drying, hollow microspheres are obtained, and the porosity > 87%.

[0191] Disperse the organosilicon-modified epoxy resin and the thermally conductive powder at 3900 r / min for 1.7 hours; degas at a vacuum degree of 0.11 MPa and a temperature of 98 °C for 2.7 hours; after adding the microencapsulated curing agent and the impact resistance agent, carry out ultrasonic-assisted mixing (frequency 48 kHz, power 380 W) for 18 minutes.

[0192] Example XVIII:

[0193] By weight, it includes the following components:

[0194] 100 parts of organosilicon-modified epoxy resin (epoxy value 0.470 eq / 100 g, viscosity at 25 °C 7500 mPa·s; prepared by microwave reaction of bisphenol A epoxy resin, nano-cage-like polyhedral oligomeric silsesquioxane (particle size 20 nm, addition amount 7 parts) and γ-glycidyletheroxypropyltrimethoxysilane (13 parts) for 4.2 hours);

[0195] 32 parts of microencapsulated amine curing agent (capsule wall thickness: 0.8 μm, the curing agent is a complex of diethylenetriamine and isophorone diamine, mass ratio 1:3);

[0196] 640 parts of surface-modified composite thermal conductive powder (including 125 parts of nano-diamond-silicon carbide whisker composite, 310 parts of titanate-modified alumina, and 62 parts of graphene-coated boron nitride; whisker aspect ratio > 17);

[0197] 11 parts of core-shell structure elastomer impact modifier (shell layer accounts for 13 wt%, crosslinking degree of core layer nitrile rubber > 86%).

[0198] Modification of thermal conductive powder: Graphene-coated boron nitride is prepared by liquid-phase exfoliation combined with chemical vapor deposition, and the coating thickness < 2.8 nm.

[0199] Bisphenol A epoxy resin and nano-cage polyhedral oligomeric silsesquioxane are shear-dispersed at 6700 r / min for 38 minutes; after dropping the silane coupling agent, microwave reaction is carried out for 4.6 hours.

[0200] The resin and the thermal conductive powder are highly dispersed at 2100 r / min for 1.2 hours; degassing is carried out at a vacuum degree of 0.12 MPa and a temperature of 87 °C for 1.8 hours; after adding the curing agent and the impact modifier, planetary stirring is used for mixing (rotation speed 90 r / min, temperature 22 °C).

[0201] Control group 1:

[0202] Components and preparation: Epoxy resin matrix: 100 parts of bisphenol A epoxy resin, and the curing agent is a common amine curing agent (15 parts of diethylenetriamine);

[0203] Filler: 600 parts of unmodified alumina powder (particle size 5 μm, purity > 99%);

[0204] Preparation process: The resin and the filler are mixed at 2000 r / min for 1 hour and cured at 80 °C for 2 hours.

[0205] Control group 2:

[0206] Components and preparation: Epoxy resin matrix: The same as in Example 1;

[0207] Filler: 600 parts of untreated aluminum nitride powder (particle size 2 μm);

[0208] Preparation process: Direct mixing and then curing, without coupling agent treatment.

[0209] Control group 3:

[0210] Components and preparation: Epoxy resin matrix: The same as in Example 1;

[0211] Filler: 600 parts of silica powder (particle size 10 μm, purity > 98%);

[0212] Preparation process: directly mix and then cure.

[0213] Control group 4:

[0214] Components and preparation: Epoxy resin matrix: same as in Example 1;

[0215] Filler: 300 parts of alumina + 300 parts of boron nitride (not surface-treated);

[0216] Preparation process: directly mix and then cure.

[0217] Control group 5:

[0218] Components and preparation: Epoxy resin matrix: same as in Example 1;

[0219] Filler: 300 parts of low grafting rate aluminum nitride (modification degree 30%) + 300 parts of alumina;

[0220] Preparation process: Halve the addition amount of coupling agent (5 parts of silane coupling agent).

[0221] Control group 6:

[0222] Components and preparation: Pure epoxy resin: 100 parts of bisphenol A type epoxy resin, 15 parts of curing agent;

[0223] No filler is added.

[0224] Control group 8:

[0225] Components and preparation: Filler: 600 parts of talc powder (particle size 15 μm);

[0226] Other components and process: same as in Control group 1.

[0227] Experimental example: Thermal shock test method

[0228] Thermal shock equipment: ESPECTSE-12-A

[0229] Thermal shock combined mold A1: Coat the inner wall of metal mold B1 with a diameter of 60 mm and a depth of 20 mm with a release agent, place metal block B2 at the center, wipe the metal block with ethanol, the size of the metal block: length 30 mm, width 30 mm, height 20 mm, the material of the metal block is aluminum, one diagonal of the metal block height is a sharp angle, and the other diagonal is a rounded corner with a radius of 2 mm.

[0230] Curing and forming: Place the combined mold A1 (including the metal block B2) in an oven preheated to 80°C for 20 minutes. Take out the preheated mold, quickly pour 30 ml of potting adhesive into the mold cavity, ensure that the adhesive completely covers the metal block B2, pre-cure at 80°C for 1 hour, then gradually increase the temperature to 120°C and cure for 2 hours, and finally post-cure at 160°C for 3 hours. After cooling to room temperature, gently tap the mold to take out the combined sample block A2 (the cured colloid is tightly combined with the metal block B2).

[0231] Thermal shock test: Put the sample block A2 into the thermal shock equipment ESPECTSE-12-A, set to stay at -40°C for 1 h and at 150°C for 1 h as one cycle, set the number of cycles according to requirements. Observe the state of the sample block during the experiment. When cracking or shelling is found, determine that the material fails, and record the number of experimental cycles as an index to evaluate the thermal shock resistance of the material. The metal block is aluminum, and the number of cycles > 30 times.

[0232] The specific experimental data are as follows:

[0233]

[0234]

[0235] As can be seen from the above:

[0236] (1) In the examples, the surface-modified composite thermal conductive powders (such as nanodiamond-silicon carbide whiskers, graphene-coated boron nitride, etc.) form a three-dimensional continuous thermal conductive network in the resin matrix through high aspect ratio and synergistic effects. Nanodiamond (thermal conductivity > 2000 W / m·K) serves as a thermal conductive "bridge", and silicon carbide whiskers (thermal conductivity > 120 W / m·K) provide longitudinal thermal conductive paths, significantly reducing the interfacial thermal resistance;

[0237] The synergistic effect of titanate-modified alumina and graphene-coated boron nitride inhibits the agglomeration of fillers (the thermal conductivity of the silica powder in control group 3 is only 0.9 W / m·K due to agglomeration), improving the thermal conductivity efficiency;

[0238] The synergistic effect of the core layer of nitrile rubber (high toughness) and the shell layer of polysiloxane (low Tg, flexibility) effectively absorbs the stress generated by the difference in thermal expansion. Example 18 (shell layer accounting for 29 wt%) has no cracking after 68 cycles from -55°C to 215°C, while control group 1 (without elastomer) can only withstand 15 cycles;

[0239] The surface modifier (such as silane coupling agent) reduces the interfacial pores between the filler and the resin through physical anchoring and chemical bonding (obvious peeling is observed at the interface of control group 2 by SEM), improving the interfacial bonding strength;

[0240] The rigid structure of the high thermal conductivity filler (such as silicon carbide whiskers) forms physical interlocking with the resin matrix, enhancing the tensile strength (the tensile strength in Example 16 is 93.2 MPa, while that in Control Group 6 is only 45.1 MPa).

[0241] (2) The epoxy groups of γ-glycidoxypropyltrimethoxysilane (KH-560) react with the resin, and after the methoxy groups are hydrolyzed, they condense with the hydroxyl groups on the filler surface to form a covalent bond of "resin-coupling agent-filler" (the characteristic peak of Si-O-Si is detected by FTIR). When there is no coupling in Control Group 4, the interface only relies on physical adsorption and has weak binding force (the tensile strength decreases by 30%); the titanate coupling agent forms a monolayer on the surface of alumina. Its long-chain alkyl groups improve the compatibility with the resin, and at the same time, the titanium atoms coordinate with the hydroxyl groups on the filler surface, enhancing the chemical stability of the interface (the strength retention rate after aging > 90%);

[0242] The polyurea-silica composite wall material (wall thickness 0.5 - 2 μm) gradually ruptures at high temperatures and slowly releases amine curing agents (such as m-phenylenediamine), delaying the curing exothermic peak and reducing internal stress (the thermal shock performance of Control Group 5 decreases due to too fast curing); the introduction of nano-cage-like polyhedral oligomeric silsesquioxane (POSS) enhances the thermal stability of the cross-linked network through Si-O-Si bonds (Tg > 180 °C), while the Tg of the pure resin in Control Group 6 is only 120 °C;

[0243] The graphene layer (≤ 5 layers) forms a dense barrier on the surface of boron nitride, inhibiting the penetration of oxygen and moisture (the strength decreases by 20% after aging when not coated in Control Group 4); the Si-O bond in the organosilicon-modified epoxy resin has a high bond energy (452 kJ / mol), which is more resistant to high-temperature oxidation than the C-C bond (347 kJ / mol), delaying the aging of the material (the tensile strength retention rate after aging in Example 5 > 90%);

[0244] The excellent performance of the examples stems from the synergy of the optimization of the physical structure (continuous thermal conductivity network, core-shell toughening) and chemical modification (interface bonding, slow-release curing, antioxidant barrier). Due to the lack of these designs in the comparative examples, the performance decreases significantly. In Control Group 8 (traditional silicate filler), without chemical modification and thermal conductivity network, the thermal conductivity is only 0.6 W / m·K, while in Example 18, through multi-scale collaborative design, the thermal conductivity reaches 2.9 W / m·K, and the comprehensive performance is improved by nearly 5 times.

[0245] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A high thermal conductivity and high temperature resistant epoxy resin potting glue that is resistant to thermal shock, characterized in that: By weight, it includes the following components: 100 parts of silicone modified epoxy resin, with an epoxy value of 0.450-0.550eq / 100g and a viscosity of 3000-25000mPa·s at 25°C; 15-80 parts of microencapsulated amine curing agent, the capsule wall material is polyurea-silicon dioxide composite, the wall thickness is 0.5-2μm; 600-1000 parts of surface modified composite thermal conductive powder; The core-shell structure elastomer impact-resistant agent is 5-30 parts, the core layer is nitrile rubber, the shell layer is polysiloxane, and the shell layer accounts for 10-30wt%.

2. The high thermal conductivity and high temperature resistant epoxy resin potting adhesive resistant to thermal shock according to claim 1, characterized in that: The organosilicon-modified epoxy resin comprises: 100 parts of bisphenol A epoxy resin; 5-15 parts of nano-scale cage-type polysilsesquioxane, with a particle size of 10-50 nm; Silane coupling agent 10-25 parts.

3. The high thermal conductivity and high temperature resistant epoxy resin potting adhesive according to claim 2, characterized in that: The silane coupling agent includes at least one of γ-glycidyloxypropyltrimethoxysilane and methyltriethoxysilane.

4. The high thermal conductivity and high temperature resistant epoxy resin potting adhesive resistant to thermal shock according to claim 1, characterized in that: The preparation of the organosilicon-modified epoxy resin comprises: dispersing bisphenol A epoxy resin and nano cage-type polysilsesquioxane at a high speed of 5000-8000 r / min under nitrogen protection; adding a silane coupling agent dropwise at a rate of 0.5-2°C / min after heating to 80°C; and reacting for 3-5 hours at a frequency of 2.45 GHz by microwave-assisted heating, discharging the material, and obtaining the organosilicon-modified epoxy resin.

5. The high thermal conductivity and high temperature resistant epoxy resin potting adhesive resistant to thermal shock according to claim 1, characterized in that: The surface modified composite thermal conductive powder comprises: 100-200 parts of a nano diamond-silicon carbide whisker composite material, with an aspect ratio greater than 20; 300-500 parts of titanate modified aluminum oxide; and 50-100 parts of graphene-coated boron nitride, with the number of graphene layers being ≤5.

6. The high thermal conductivity and high temperature resistant epoxy resin potting adhesive resistant to thermal shock according to claim 5, characterized in that: The nano-diamond-silicon carbide whisker composite is prepared by chemical vapor deposition, which specifically includes: placing silicon carbide whiskers in a reactor, introducing CH4 / H2 mixed gas, and depositing a diamond layer at 800-1000° C.; and alternately introducing argon ion beams during the deposition process for surface activation.

7. The high thermal conductivity and high temperature resistant epoxy resin potting adhesive resistant to thermal shock according to claim 1, characterized in that: The amine curing agent includes one or more of m-phenylenediamine, diethylenetriamine, triethylenetetramine, polyetheramine, and isophoronediamine.

8. The high thermal conductivity and high temperature resistant epoxy resin potting adhesive resistant to thermal shock according to claim 1, characterized in that: The method for preparing the core-shell structured elastomer impact resistant agent comprises: preparing monodisperse nitrile rubber latex droplets by adopting microfluidics technology; depositing a polysiloxane shell layer on the surface of the droplets by atomic layer deposition; and obtaining hollow microspheres by supercritical CO2 drying after curing.

9. The method for preparing the epoxy resin potting adhesive according to any one of claims 1 to 6, characterized in that: include: The organosilicon-modified epoxy resin and the surface-modified composite thermal conductive powder are dispersed at a high speed of 1000-4000 r / min; degassing is performed for 1-3 hours at 80-100° C. and a vacuum degree of 0.08-0.12 MPa; after cooling to below 30° C., microencapsulated amine curing agent and core-shell structure elastomer impact-resistant agent are added and mixed.

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