A high thermal conductivity aluminum-based copper clad laminate and its preparation method

Abstract

This application relates to the technical field of the preparation of copper clad laminates, and specifically discloses a high thermal conductivity aluminum-based copper clad laminate and a preparation method thereof, including an aluminum-based bottom plate and a prepreg. The prepreg is prepared by thermally curing a thermally conductive adhesive solution and copper foil. The thermally conductive adhesive solution added in this application contains functional components and modified thermally conductive fillers. The functional components contain a microcrystalline cellulose structure, a ricinoleic acid ester structure, and a pyridyl group. The presence of the microcrystalline cellulose structure, on the one hand, exerts its own high crystallinity and orientation, and on the other hand, it can form a hydrogen bond interaction with the modified thermally conductive filler. The ricinoleic acid ester structure has orderliness, and the pyridyl group can produce a π-π interaction with the benzene ring on the modified thermally conductive filler. The presence of the modified thermally conductive filler, on the one hand, exerts the good thermal conductivity of boron nitride, and on the other hand, the octenyl succinic anhydride grafted on the modified thermally conductive filler can undergo chemical bonding with the mercapto group on the functional component. Through the synergistic action of each structure, the thermal conductivity and insulation performance of the aluminum-based copper clad laminate are improved.

Description

Technical Field

[0001] The present application relates to the technical field of preparation of copper clad laminates, and more specifically, to a high thermal conductivity aluminum-based copper clad laminate and a preparation method thereof. Background Art

[0002] An aluminum-based copper clad laminate is a plate-like material made by impregnating an electronic glass fiber cloth or other reinforcing materials with a resin, a single resin, etc. as an insulating adhesive layer, and covering one or both sides with a copper foil and then hot pressing. It has good heat dissipation performance, mechanical strength and electrical performance, and is an ideal material for manufacturing high-performance PCBs.

[0003] As the substrate material of a printed circuit board, the copper clad laminate must have a certain thermal conductivity to meet the requirements of electronic products. Conventional copper clad laminates are composed of an insulating base layer, a metal base layer, a copper foil, etc. Among them, the metal base layer and the copper foil generally have good thermal conductivity. To achieve the thermal conductivity of the copper clad laminate, it is necessary to start from improving the thermal conductivity of the insulating base layer. In the prior art, to increase the thermal conductivity of the insulating base layer, the amount of thermal conductive particles is often increased. However, the modified thermal conductive filler has a small molecular weight and cannot participate in the curing reaction, and is easy to migrate and precipitate, which makes the processing of the insulating base layer difficult, and the mechanical properties and bonding properties of the prepared insulating base layer are reduced, ultimately affecting the insulation performance of the copper clad laminate. Therefore, providing an aluminum-based copper clad laminate with good thermal conductivity and good insulation performance at the same time is a technical problem that needs to be solved at present. Summary of the Invention

[0004] To solve the problems mentioned in the above background art, the present application provides a high thermal conductivity aluminum-based copper clad laminate and a preparation method thereof.

[0005] A high thermal conductivity aluminum-based copper clad laminate includes an aluminum-based bottom plate and a prepreg, and the prepreg is obtained by thermally curing a thermal conductive adhesive solution and a copper foil.

[0006] The preparation method of the high thermal conductivity aluminum-based copper clad laminate includes the following steps:

[0007] Step S1: Coat the thermal conductive adhesive solution on the copper foil, control the upper glue line speed to be 12 - 20 m / min, control the coating thickness to be 75 - 95 μm, and perform heat treatment at 230 - 260 °C for 2 - 4 min to obtain a prepreg;

[0008] Step S2: Cut the prepreg and laminate it with the aluminum-based bottom plate, and perform hot pressing at 20 - 25 MPa and 280 - 320 °C for 1.8 - 2.2 h, and then cool to obtain the high thermal conductivity aluminum-based copper clad laminate.

[0009] Preferably, the preparation method of the thermal conductive adhesive solution includes the following steps:

[0010] Step 1: Prepare the following raw materials in parts by weight: 64 - 132 parts of bisphenol A epoxy resin, 16 - 30 parts of functional component, 8 - 18 parts of modified thermal conductive filler, 20 - 40 parts of organic solvent, 0.1 - 0.2 parts of photoinitiator, 25 - 30 parts of curing agent, and 1 - 5 parts of curing accelerator;

[0011] Step 2: Add the functional component, modified thermal conductive filler, and photoinitiator into the organic solvent, stir evenly, irradiate with ultraviolet light for 10 - 20 min, control the irradiation temperature at 50 - 56 °C, cool down to 25 - 30 °C, then sequentially add bisphenol A epoxy resin, curing agent, and curing accelerator, emulsify for 1.6 - 2.8 h, and stand for 5 - 7 h to obtain the thermal conductive adhesive liquid.

[0012] Preferably, the photoinitiator is benzoin dimethyl ether.

[0013] Preferably, the organic solvent is one or more of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone mixed in any proportion.

[0014] Preferably, the curing agent is epoxy resin curing agent T31.

[0015] Preferably, the curing accelerator is one or more of 1 - benzylbenzene - 2 - ethylimidazole, 2 - ethyl - 4 - methylimidazole, and 1 - cyanoethylimidazole mixed in any proportion.

[0016] Preferably, the preparation method of the functional component includes the following steps:

[0017] Step A1: Mix microcrystalline cellulose and saturated sodium hydroxide solution evenly, then add epichlorohydrin, heat up to 58 - 64 °C, continue stirring for 5.2 - 6.4 h, filter, and then add the mixed solution a of castor oil acid, pyridine, and anhydrous DMF dropwise, control the dropping to be completed within 30 min, heat up to 76 - 82 °C, continue reacting for 4 - 6 h, after the reaction ends, filter, wash, and dry to obtain the hydroxyl monomer. Among them, the mass ratio of microcrystalline cellulose, saturated sodium hydroxide solution, epichlorohydrin, and mixed solution a is 0.6 - 1.0:64 - 76:2.4 - 3.0:32 - 34. In the mixed solution a, the mass ratio of castor oil acid, pyridine, and anhydrous DMF is 4:0.03 - 0.05:28 - 30. In the above reaction process, under alkaline conditions, the hydroxyl groups on the surface of microcrystalline cellulose react with epichlorohydrin by substitution reaction, and the epoxy groups on the surface of the substituted microcrystalline cellulose continue to react with castor oil acid by ring - opening esterification reaction under the catalysis of pyridine to obtain the hydroxyl monomer;

[0018] Step A2: Add the hydroxyl monomer, 2-mercaptonicotinic acid, and phosphotungstic acid into anhydrous DMF, stir evenly. Under nitrogen protection, heat up to 74 - 80 °C, and stir for reaction for 9 - 12 h. After the reaction ends, carry out suction filtration, washing, and drying to obtain the functional component. The mass ratio of the hydroxyl monomer, 2-mercaptonicotinic acid, phosphotungstic acid, and anhydrous DMF is 1.6 - 2.2: 0.4 - 0.6: 0.01 - 0.02: 40 - 60. During the above reaction process, using anhydrous DMF as the solvent and phosphotungstic acid as the catalyst, the hydroxyl monomer and 2-mercaptonicotinic acid undergo an esterification reaction to obtain the functional component. During the above reaction process, control the amount of the hydroxyl monomer slightly higher than that of 2-mercaptonicotinic acid so that after the reaction ends, there are still remaining hydroxyls that can participate in the subsequent preparation process.

[0019] Preferably, the modified thermal conductive filler is prepared by the following steps:

[0020] Step B1: Under nitrogen protection, add nano-hexagonal boron nitride into the alkali solution, heat up to 106 - 112 °C, and stir for reaction for 36 - 42 h. After the reaction ends, carry out precipitation, washing, and drying to obtain hydroxyl boron nitride, where the mass ratio of nano-hexagonal boron nitride and the alkali solution is 3 - 5: 600 - 700;

[0021] Step B2: Add hydroxyl boron nitride, 3,5-diaminobenzoic acid, and p-toluenesulfonic acid into anhydrous DMF, stir evenly. Under nitrogen protection, heat up to 78 - 84 °C, and stir for reaction for 12 - 16 h. After the reaction ends, carry out suction filtration, washing, and drying to obtain the amino monomer. The mass ratio of hydroxyl boron nitride, 3,5-diaminobenzoic acid, p-toluenesulfonic acid, and anhydrous DMF is 2.2 - 2.6: 15.2 - 18.4: 0.14 - 0.20: 70 - 78. During the above reaction process, using anhydrous DMF as the solvent and p-toluenesulfonic acid as the catalyst, hydroxyl boron nitride and 3,5-diaminobenzoic acid undergo an esterification reaction to obtain the amino monomer. During the above reaction process, control the amount of hydroxyl boron nitride slightly higher than that of 3,5-diaminobenzoic acid so that after the reaction ends, there are still remaining hydroxyls that can participate in the subsequent preparation process;

[0022] Step B3: Add the amino monomer into anhydrous DMF, stir evenly, adjust the pH value to 8 - 9, dropwise add the mixed solution b of octenyl succinic anhydride and isopropanol, control to finish dropping within 10 min. After dropping, heat up to 72 - 76 °C, continue to stir for reaction for 6 - 12 h, then adjust the pH value to 6.4 - 6.8, wash, and dry to obtain the modified thermal conductive filler. The mass ratio of the amino monomer, anhydrous DMF, and the mixed solution b is 3 - 5: 62 - 66: 32 - 36. In the mixed solution b, the mass ratio of octenyl succinic anhydride and isopropanol is 4 - 6.8: 28. During the above reaction process, using anhydrous DMF as the solvent, the active amino group on the amino monomer and the acid anhydride on octenyl succinic anhydride undergo a ring-opening esterification reaction to obtain the modified thermal conductive filler.

[0023] Preferably, in the step B1, the alkaline solution is an aqueous sodium hydroxide solution with a mass fraction of 30-40%.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] In order to improve the thermal conductivity and insulation of the aluminum-based copper clad laminate, this application starts from two aspects. One is to add functional components during the preparation of the thermal conductive adhesive. The functional components contain microcrystalline cellulose structure, ricinoleic acid ester structure and pyridyl group. The presence of the microcrystalline cellulose structure, on the one hand, exerts its own high crystallinity and orientation, improving the thermal conductivity and insulation of the aluminum-based copper clad laminate. On the other hand, it can form hydrogen bond interactions with the active carboxyl groups on the modified thermal conductive filler, improving the dispersibility of the modified thermal conductive filler and further enhancing the thermal conductivity of the aluminum-based copper clad laminate. The ricinoleic acid ester structure has orderliness, improving the thermal conductivity and insulation of the aluminum-based copper clad laminate. The presence of the pyridyl group can produce π-π interactions with the benzene ring on the modified thermal conductive filler, realizing the loading of the functional components on the surface of the modified thermal conductive filler and further improving the thermal conductivity and insulation of the aluminum-based copper clad laminate. The second is to add modified thermal conductive fillers. On the one hand, it exerts the good thermal conductivity of boron nitride itself. On the other hand, the octenyl succinic anhydride grafted on the surface of the modified thermal conductive filler contains unsaturated double bonds, which can chemically bond with the mercapto groups on the functional components and introduce them into the thermal conductive adhesive, enabling them to work synergistically with the functional components to jointly improve the thermal conductivity and insulation performance of the aluminum-based copper clad laminate. Specific Embodiments

[0026] To make the embodiments of this application easier to understand, the following will specifically describe this application with reference to specific examples. These examples are only illustrative and are not limited to the application scope of this application.

[0027] The following further elaborates on this application with reference to examples and comparative examples.

[0028] Preparation Examples 1-3 and Comparative Preparation Examples 1-2 provide the preparation methods of the functional components.

[0029] Preparation Example 1

[0030] This preparation example provides a preparation method of a functional component. The preparation method of this functional component includes the following steps:

[0031] Step A1: Stir microcrystalline cellulose and saturated sodium hydroxide solution at a speed of 500 rpm for 16 min until homogeneous. Then add epichlorohydrin, raise the temperature to 58 °C, keep the rotation speed unchanged, and continue stirring for 5.2 h. Filter, and then add mixture a of castor oil acid, pyridine and anhydrous DMF dropwise, control to finish dropping within 30 min. After dropping, raise the temperature to 76 °C and continue the reaction for 4 h. After the reaction ends, filter, wash with anhydrous ethanol and deionized water three times in sequence, and dry at 60 °C to constant weight to obtain a hydroxyl monomer. Among them, the mass ratio of microcrystalline cellulose, saturated sodium hydroxide solution, epichlorohydrin and mixture a is 0.6:64:2.4:32. In mixture a, the mass ratio of castor oil acid, pyridine and anhydrous DMF is 4:0.03:28;

[0032] Step A2: Add the hydroxyl monomer, 2-mercaptonicotinic acid and phosphotungstic acid into anhydrous DMF, stir at a speed of 650 rpm for 18 min until homogeneous. Under nitrogen protection, raise the temperature to 74 °C and stir for reaction for 9 h. After the reaction ends, carry out suction filtration, wash with anhydrous ethanol and deionized water three times in sequence, and dry at 68 °C to constant weight to obtain a functional component. Among them, the mass ratio of the hydroxyl monomer, 2-mercaptonicotinic acid, phosphotungstic acid and anhydrous DMF is 1.6:0.4:0.01:40.

[0033] Preparation Example 2

[0034] This preparation example provides a preparation method of a functional component. The preparation method of this functional component includes the following steps:

[0035] Step A1: Stir microcrystalline cellulose and saturated sodium hydroxide solution at a speed of 550 rpm for 20 min until homogeneous. Then add epichlorohydrin, raise the temperature to 61 °C, and continue stirring for 5.8 h. Filter, and then add mixture a of castor oil acid, pyridine and anhydrous DMF dropwise, control to finish dropping within 30 min. After dropping, raise the temperature to 79 °C and continue the reaction for 5 h. After the reaction ends, filter, wash with anhydrous ethanol and deionized water four times in sequence, and dry at 64 °C to constant weight to obtain a hydroxyl monomer. Among them, the mass ratio of microcrystalline cellulose, saturated sodium hydroxide solution, epichlorohydrin and mixture a is 0.8:70:2.7:33. In mixture a, the mass ratio of castor oil acid, pyridine and anhydrous DMF is 4:0.04:29;

[0036] Step A2: Add the hydroxyl monomer, 2-mercaptonicotinic acid and phosphotungstic acid into anhydrous DMF, stir at a speed of 700 rpm for 22 min until homogeneous. Under nitrogen protection, raise the temperature to 77 °C, keep the rotation speed unchanged, and stir for reaction for 10.5 h. After the reaction ends, carry out suction filtration, wash with anhydrous ethanol and deionized water four times in sequence, and dry at 72 °C to constant weight to obtain a functional component. Among them, the mass ratio of the hydroxyl monomer, 2-mercaptonicotinic acid, phosphotungstic acid and anhydrous DMF is 1.9:0.5:0.015:50.

[0037] Preparation Example 3

[0038] This preparation example provides a method for preparing a functional component. The method for preparing the functional component includes the following steps:

[0039] Step A1: Stir microcrystalline cellulose and saturated sodium hydroxide solution at a rotation speed of 600 rpm for 24 min until uniform, then add epichlorohydrin, raise the temperature to 64 °C, maintain the rotation speed unchanged, continue stirring for 6.4 h, filter, and then add a mixed solution a of castor oil acid, pyridine, and anhydrous DMF. Control the dropping within 30 min. After dropping, raise the temperature to 82 °C and continue the reaction for 6 h. After the reaction ends, filter, wash 5 times with anhydrous ethanol and deionized water in sequence, and dry at 68 °C to constant weight to obtain a hydroxyl monomer. Among them, the mass ratio of microcrystalline cellulose, saturated sodium hydroxide solution, epichlorohydrin, and mixed solution a is 1.0:76:3.0:34. In the mixed solution a, the mass ratio of castor oil acid, pyridine, and anhydrous DMF is 4:0.05:30;

[0040] Step A2: Add the hydroxyl monomer, 2-mercaptonicotinic acid, and phosphotungstic acid to anhydrous DMF, stir at a rotation speed of 750 rpm for 26 min until uniform, under nitrogen protection, raise the temperature to 80 °C, stir and react for 12 h. After the reaction ends, carry out suction filtration, wash 5 times with anhydrous ethanol and deionized water in sequence, and dry at 76 °C to constant weight to obtain the functional component. Among them, the mass ratio of the hydroxyl monomer, 2-mercaptonicotinic acid, phosphotungstic acid, and anhydrous DMF is 2.2:0.6:0.02:60.

[0041] Comparative Preparation Example 1

[0042] This comparative preparation example provides a method for preparing a functional component. The method for preparing the functional component includes the following steps:

[0043] Step A1: Stir microcrystalline cellulose and saturated sodium hydroxide solution at a rotation speed of 500 rpm for 16 min until uniform, then add epichlorohydrin, raise the temperature to 58 °C, maintain the rotation speed unchanged, continue stirring for 5.2 h, filter, and then add a mixed solution a of caprylic acid, pyridine, and anhydrous DMF. Control the dropping within 30 min. After dropping, raise the temperature to 76 °C and continue the reaction for 4 h. After the reaction ends, filter, wash 3 times with anhydrous ethanol and deionized water in sequence, and dry at 60 °C to constant weight to obtain a hydroxyl monomer. Among them, the mass ratio of microcrystalline cellulose, saturated sodium hydroxide solution, epichlorohydrin, and mixed solution a is 0.6:64:2.4:32. In the mixed solution a, the mass ratio of caprylic acid, pyridine, and anhydrous DMF is 4:0.03:28;

[0044] Step A2: Add the hydroxyl monomer, 2-mercaptonicotinic acid, and phosphotungstic acid into anhydrous DMF, stir at 650 rpm for 18 min until homogeneous, under nitrogen protection, heat up to 74 °C, stir and react for 9 h. After the reaction is completed, perform suction filtration, wash 3 times successively with anhydrous ethanol and deionized water, and dry at 68 °C to constant weight to obtain the functional component, where the mass ratio of the hydroxyl monomer, 2-mercaptonicotinic acid, phosphotungstic acid, and anhydrous DMF is 1.6:0.4:0.01:40.

[0045] Comparative Preparation Example 2

[0046] This comparative preparation example provides a method for preparing a functional component. The method for preparing the functional component includes the following steps:

[0047] Step A1: Stir microcrystalline cellulose and saturated sodium hydroxide solution at 500 rpm for 16 min until homogeneous, then add epichlorohydrin, heat up to 58 °C, keep the rotation speed unchanged, continue to stir for 5.2 h, filter, and then add and dropwise add the mixed solution a of castor oil acid, pyridine, and anhydrous DMF, control to finish dropping within 30 min. After dropping, heat up to 76 °C and continue to react for 4 h. After the reaction is completed, filter, wash 3 times successively with anhydrous ethanol and deionized water, and dry at 60 °C to constant weight to obtain the hydroxyl monomer, where the mass ratio of microcrystalline cellulose, saturated sodium hydroxide solution, epichlorohydrin, and mixed solution a is 0.6:64:2.4:32, and in the mixed solution a, the mass ratio of castor oil acid, pyridine, and anhydrous DMF is 4:0.03:28;

[0048] Step A2: Add the hydroxyl monomer, 3-mercaptopropionic acid, and phosphotungstic acid into anhydrous DMF, stir at 650 rpm for 18 min until homogeneous, under nitrogen protection, heat up to 74 °C, stir and react for 9 h. After the reaction is completed, perform suction filtration, wash 3 times successively with anhydrous ethanol and deionized water, and dry at 68 °C to constant weight to obtain the functional component, where the mass ratio of the hydroxyl monomer, 3-mercaptopropionic acid, phosphotungstic acid, and anhydrous DMF is 1.6:0.4:0.01:40.

[0049] Preparation Examples 4 - 6 and Comparative Preparation Examples 3 - 4 provide methods for preparing modified heat-conducting fillers.

[0050] Preparation Example 4

[0051] This preparation example provides a modified heat-conducting filler, which is prepared by the following steps:

[0052] Step B1: Under nitrogen protection, add nano - hexagonal boron nitride into an aqueous sodium hydroxide solution with a mass fraction of 30%, heat up to 106 °C, control the rotation speed at 400 rpm, stir and react for 36 h. After the reaction, precipitate, wash with anhydrous methanol 3 times, and dry at 60 °C to constant weight to obtain hydroxy - boron nitride. Among them, the mass ratio of nano - hexagonal boron nitride to the sodium hydroxide solution is 3:600;

[0053] Step B2: Add hydroxy - boron nitride, 3,5 - diamino - benzoic acid, and p - toluenesulfonic acid into anhydrous DMF, control the rotation speed at 600 rpm, stir for 26 min until homogeneous. Under nitrogen protection, heat up to 78 °C, maintain the rotation speed unchanged, and continue to stir and react for 12 h. After the reaction, perform suction filtration, and then wash with anhydrous ethanol and deionized water 3 times, and dry at 65 °C to constant weight to obtain the amino monomer. Among them, the mass ratio of hydroxy - boron nitride, 3,5 - diamino - benzoic acid, p - toluenesulfonic acid, and anhydrous DMF is 2.2:15.2:0.14:70;

[0054] Step B3: Add the amino monomer into anhydrous DMF, stir at a rotation speed of 700 rpm for 22 min until homogeneous, adjust the pH value to 8 with a 0.6 M aqueous sodium hydroxide solution, dropwise add a mixed solution b of octenyl succinic anhydride and isopropanol, control to finish dropping within 10 min. After dropping, heat up to 72 °C, maintain the rotation speed unchanged, and continue to stir and react for 6 h. Then adjust the pH value to 6.4 with a 0.4 M hydrochloric acid solution, and then wash with anhydrous ethanol and deionized water 3 times, and dry at 68 °C to constant weight to obtain the modified thermal conductivity filler. Among them, the mass ratio of the amino monomer, anhydrous DMF, and the mixed solution b is 3:62:32. In the mixed solution b, the mass ratio of octenyl succinic anhydride to isopropanol is 4:28.

[0055] Preparation Example 5

[0056] This preparation example provides a modified thermal conductivity filler, which is prepared by the following steps:

[0057] Step B1: Under nitrogen protection, add nano - hexagonal boron nitride into an aqueous sodium hydroxide solution with a mass fraction of 35%, heat up to 109 °C, control the rotation speed at 450 rpm, stir and react for 39 h. After the reaction, precipitate, wash with anhydrous methanol 4 times, and dry at 60 °C to constant weight to obtain hydroxy - boron nitride. Among them, the mass ratio of nano - hexagonal boron nitride to the sodium hydroxide solution is 4:650;

[0058] Step B2: Add hydroxyboron nitride, 3,5-diaminobenzoic acid, and p-toluenesulfonic acid into anhydrous DMF, control the rotation speed at 650 rpm, stir for 28 min until uniform, under nitrogen protection, heat up to 81 °C, stir and react for 14 h. After the reaction is completed, perform suction filtration, and then wash with anhydrous ethanol and deionized water 4 times each, and dry at 70 °C to constant weight to obtain the amino monomer. Among them, the mass ratio of hydroxyboron nitride, 3,5-diaminobenzoic acid, p-toluenesulfonic acid, and anhydrous DMF is 2.4:16.8:0.17:74;

[0059] Step B3: Add the amino monomer into anhydrous DMF, stir at a rotation speed of 720 rpm for 24 min until uniform, adjust the pH value to 8.5 with 0.8 M aqueous sodium hydroxide solution, dropwise add the mixed solution b of octenyl succinic anhydride and isopropanol, control to finish dropping within 10 min. After dropping, heat up to 74 °C, maintain the rotation speed unchanged, continue to stir and react for 9 h, then adjust the pH value to 6.6 with 0.4 M hydrochloric acid solution, and then wash with anhydrous ethanol and deionized water 4 times each, and dry at 72 °C to constant weight to obtain the modified thermal conductive filler. Among them, the mass ratio of the amino monomer, anhydrous DMF, and the mixed solution b is 4:64:34. In the mixed solution b, the mass ratio of octenyl succinic anhydride and isopropanol is 4.9:28.

[0060] Preparation Example 6

[0061] This preparation example provides a modified thermal conductive filler, which is prepared by the following steps:

[0062] Step B1: Under nitrogen protection, add nano-hexagonal boron nitride into an aqueous sodium hydroxide solution with a mass fraction of 40%, heat up to 112 °C, control the rotation speed at 500 rpm, stir and react for 42 h. After the reaction is completed, precipitate, wash with anhydrous methanol 5 times, and dry at 65 °C to constant weight to obtain hydroxyboron nitride. Among them, the mass ratio of nano-hexagonal boron nitride and sodium hydroxide solution is 5:700;

[0063] Step B2: Add hydroxyboron nitride, 3,5-diaminobenzoic acid, and p-toluenesulfonic acid into anhydrous DMF, control the rotation speed at 650 rpm, stir for 30 min until uniform, under nitrogen protection, heat up to 84 °C, stir and react for 16 h. After the reaction is completed, perform suction filtration, and then wash with anhydrous ethanol and deionized water 5 times each, and dry at 75 °C to constant weight to obtain the amino monomer. Among them, the mass ratio of hydroxyboron nitride, 3,5-diaminobenzoic acid, p-toluenesulfonic acid, and anhydrous DMF is 2.6:18.4:0.20:78;

[0064] Step B3: Add the amino monomer into anhydrous DMF, stir for 26 min at a rotation speed of 740 rpm until homogeneous, adjust the pH value to 9, dropwise add the mixed solution b of octenyl succinic anhydride and isopropanol, control the dropping to be completed within 10 min. After dropping, raise the temperature to 76 °C, continue stirring and reacting for 12 h, then adjust the pH value to 6.8, wash 5 times successively with anhydrous ethanol and deionized water, and dry at 76 °C to constant weight to obtain the modified thermal conductive filler. Among them, the mass ratio of the amino monomer, anhydrous DMF and the mixed solution b is 5:66:36, and in the mixed solution b, the mass ratio of octenyl succinic anhydride and isopropanol is 6.8:28.

[0065] Comparative Preparation Example 3

[0066] This comparative preparation example provides a modified thermal conductive filler, which is prepared by the following steps:

[0067] Step B1: Under nitrogen protection, add nano hexagonal boron nitride into an aqueous sodium hydroxide solution with a mass fraction of 30%, raise the temperature to 106 °C, control the rotation speed to be 400 rpm, stir and react for 36 h. After the reaction, precipitate, wash 3 times with anhydrous methanol, and dry at 60 °C to constant weight to obtain hydroxy boron nitride. Among them, the mass ratio of nano hexagonal boron nitride and the sodium hydroxide solution is 3:600;

[0068] Step B2: Add hydroxy boron nitride, L-cysteine and p-toluenesulfonic acid into anhydrous DMF, control the rotation speed to be 600 rpm, stir for 26 min until homogeneous. Under nitrogen protection, raise the temperature to 78 °C, maintain the rotation speed unchanged, and continue stirring and reacting for 12 h. After the reaction, perform suction filtration, then wash 3 times with anhydrous ethanol and deionized water, and dry at 65 °C to constant weight to obtain the amino monomer. Among them, the mass ratio of hydroxy boron nitride, L-cysteine, p-toluenesulfonic acid and anhydrous DMF is 2.2:15.2:0.14:70;

[0069] Step B3: Add the amino monomer into anhydrous DMF, stir for 22 min at a rotation speed of 700 rpm until homogeneous, adjust the pH value to 8 with a 0.6 M aqueous sodium hydroxide solution, dropwise add the mixed solution b of octenyl succinic anhydride and isopropanol, control the dropping to be completed within 10 min. After dropping, raise the temperature to 72 °C, maintain the rotation speed unchanged, continue stirring and reacting for 6 h, then adjust the pH value to 6.4 with a 0.4 M hydrochloric acid solution, wash 3 times successively with anhydrous ethanol and deionized water, and dry at 68 °C to constant weight to obtain the modified thermal conductive filler. Among them, the mass ratio of the amino monomer, anhydrous DMF and the mixed solution b is 3:62:32, and in the mixed solution b, the mass ratio of octenyl succinic anhydride and isopropanol is 4:28.

[0070] Comparative Preparation Example 4

[0071] This comparative preparation example provides a modified thermal conductive filler, which is prepared by the following steps:

[0072] A preparation method of a modified thermal conductive filler, which is prepared by the following steps:

[0073] Step B1: Under nitrogen protection, add nano-hexagonal boron nitride into an aqueous sodium hydroxide solution with a mass fraction of 30%, heat up to 106 °C, control the rotation speed at 400 rpm, stir and react for 36 h. After the reaction, precipitate, wash with anhydrous methanol 3 times, and dry at 60 °C to constant weight to obtain hydroxy boron nitride. Among them, the mass ratio of nano-hexagonal boron nitride to the sodium hydroxide solution is 3:600;

[0074] Step B2: Add hydroxy boron nitride, 3,5-diaminobenzoic acid, and p-toluenesulfonic acid into anhydrous DMF, control the rotation speed at 600 rpm, stir for 26 min until uniform, under nitrogen protection, heat up to 78 °C, maintain the rotation speed unchanged, and continue to stir and react for 12 h. After the reaction, filter by suction, and then wash with anhydrous ethanol and deionized water 3 times, and dry at 65 °C to constant weight to obtain the amino monomer. Among them, the mass ratio of hydroxy boron nitride, 3,5-diaminobenzoic acid, p-toluenesulfonic acid, and anhydrous DMF is 2.2:15.2:0.14:70;

[0075] Step B3: Add the amino monomer into anhydrous DMF, stir at a rotation speed of 700 rpm for 22 min until uniform, adjust the pH value to 8 with a 0.6 M aqueous sodium hydroxide solution, dropwise add a mixed solution b of n-octyl succinic anhydride and isopropanol, control the dropping within 10 min. After dropping, heat up to 72 °C, maintain the rotation speed unchanged, and continue to stir and react for 6 h. Then adjust the pH value to 6.4 with a 0.4 M hydrochloric acid solution, and then wash with anhydrous ethanol and deionized water 3 times, and dry at 68 °C to constant weight to obtain the modified thermal conductive filler. Among them, the mass ratio of the amino monomer, anhydrous DMF, and the mixed solution b is 3:62:32. In the mixed solution b, the mass ratio of n-octyl succinic anhydride to isopropanol is 4:28.

[0076] Preparation Examples 7-9 and Comparative Preparation Examples 5-8 provide a preparation method of a thermal conductive adhesive liquid.

[0077] Preparation Example 7

[0078] This preparation example provides a preparation method of a thermal conductive adhesive liquid. The preparation method of this thermal conductive adhesive liquid includes the following steps:

[0079] First step: Prepare the following raw materials in parts by weight: 64 parts of bisphenol A epoxy resin, 16 parts of the functional component prepared in Preparation Example 1, 8 parts of the modified thermal conductive filler prepared in Preparation Example 4, 20 parts of propylene glycol methyl ether, 0.1 part of benzoin dimethyl ether, 25 parts of epoxy resin curing agent T31, and 1 part of 1-benzylbenzene-2-ethylimidazole;

[0080] Step 2: Add the functional component, the modified thermal conductive filler, and benzoin dimethyl ether into propylene glycol methyl ether, stir at a speed of 600 rpm for 25 min until homogeneous, keep the speed unchanged, irradiate with ultraviolet light while stirring for 10 min, control the irradiation temperature at 50 °C, cool down to 25 °C, then sequentially add bisphenol A epoxy resin, epoxy resin curing agent T31, and 1-benzylbenzene-2-ethylimidazole, and carry out an emulsification reaction at a speed of 1000 rpm for 1.6 h, and let stand for 5 h to obtain the thermal conductive adhesive liquid.

[0081] Preparation Example 8

[0082] This preparation example provides a method for preparing a thermal conductive adhesive liquid. The method for preparing the thermal conductive adhesive liquid includes the following steps:

[0083] Step 1: Prepare the following raw materials in parts by weight: 98 parts of bisphenol A epoxy resin, 23 parts of the functional component prepared in Preparation Example 2, 13 parts of the modified thermal conductive filler prepared in Preparation Example 5, 30 parts of propylene glycol methyl ether acetate, 0.15 parts of benzoin dimethyl ether, 27.5 parts of epoxy resin curing agent T31, and 3 parts of 2-ethyl-4-methylimidazole;

[0084] Step 2: Add the functional component, the modified thermal conductive filler, and benzoin dimethyl ether into propylene glycol methyl ether acetate, stir at a speed of 640 rpm for 28 min until homogeneous, keep the speed unchanged, irradiate with ultraviolet light while stirring for 12.5 min, control the irradiation temperature at 53 °C, cool down to 28 °C, then sequentially add bisphenol A epoxy resin, epoxy resin curing agent T31, and 2-ethyl-4-methylimidazole, and carry out emulsification for 2.2 h at a speed of 1100 rpm, and let stand for 6 h to obtain the thermal conductive adhesive liquid.

[0085] Preparation Example 9

[0086] This preparation example provides a method for preparing a thermal conductive adhesive liquid. The method for preparing the thermal conductive adhesive liquid includes the following steps:

[0087] Step 1: Prepare the following raw materials in parts by weight: 132 parts of bisphenol A epoxy resin, 30 parts of the functional component prepared in Preparation Example 3, 18 parts of the modified thermal conductive filler prepared in Preparation Example 6, 40 parts of cyclohexanone, 0.2 parts of benzoin dimethyl ether, 30 parts of epoxy resin curing agent T31, and 5 parts of 1-cyanoethylimidazole;

[0088] Step 2: Add the functional component, modified thermal conductive filler, and dimethyl benzoin ether into cyclohexanone, stir at a rotation speed of 680 rpm for 31 min until homogeneous, keep the rotation speed unchanged, irradiate with ultraviolet light while stirring for 15 min, control the irradiation temperature at 56 °C, cool down to 30 °C, then successively add bisphenol A epoxy resin, epoxy resin curing agent T31, and 1-cyanoethyl imidazole, emulsify at a rotation speed of 1200 rpm for 2.8 h, and let stand for 7 h to obtain the thermal conductive adhesive liquid.

[0089] Comparative Preparation Example 5

[0090] This comparative preparation example provides a method for preparing a thermal conductive adhesive liquid. The method for preparing the thermal conductive adhesive liquid includes the following steps:

[0091] Step 1: Prepare the following raw materials in parts by weight: 64 parts of bisphenol A epoxy resin, 16 parts of the functional component prepared in Comparative Preparation Example 1, 8 parts of the modified thermal conductive filler prepared in Preparation Example 4, 20 parts of propylene glycol methyl ether, 0.1 part of dimethyl benzoin ether, 25 parts of epoxy resin curing agent T31, and 1 part of 1-benzylbenzene-2-ethylimidazole;

[0092] Step 2: Add the functional component, modified thermal conductive filler, and dimethyl benzoin ether into propylene glycol methyl ether, stir at a rotation speed of 600 rpm for 25 min until homogeneous, keep the rotation speed unchanged, irradiate with ultraviolet light while stirring for 10 min, control the irradiation temperature at 50 °C, cool down to 25 °C, then successively add bisphenol A epoxy resin, epoxy resin curing agent T31, and 1-benzylbenzene-2-ethylimidazole, carry out an emulsification reaction at a rotation speed of 1000 rpm for 1.6 h, and let stand for 5 h to obtain the thermal conductive adhesive liquid.

[0093] Comparative Preparation Example 6

[0094] This comparative preparation example provides a method for preparing a thermal conductive adhesive liquid. The method for preparing the thermal conductive adhesive liquid includes the following steps:

[0095] Step 1: Prepare the following raw materials in parts by weight: 64 parts of bisphenol A epoxy resin, 16 parts of the functional component prepared in Comparative Preparation Example 2, 8 parts of the modified thermal conductive filler prepared in Preparation Example 4, 20 parts of propylene glycol methyl ether, 0.1 part of dimethyl benzoin ether, 25 parts of epoxy resin curing agent T31, and 1 part of 1-benzylbenzene-2-ethylimidazole;

[0096] Step 2: Add the functional component, modified thermal conductive filler, and dimethyl benzoin ether into propylene glycol methyl ether, stir at a speed of 600 rpm for 25 min until homogeneous, keep the speed unchanged, irradiate with ultraviolet light for 10 min while stirring, control the irradiation temperature at 50 °C, cool down to 25 °C, then successively add bisphenol A epoxy resin, epoxy resin curing agent T31, and 1-benzylbenzene-2-ethylimidazole, carry out an emulsification reaction at a speed of 1000 rpm for 1.6 h, and let it stand for 5 h to obtain a thermal conductive adhesive liquid.

[0097] Comparative Preparation Example 7

[0098] This comparative preparation example provides a method for preparing a thermal conductive adhesive liquid. The method for preparing the thermal conductive adhesive liquid includes the following steps:

[0099] Step 1: Prepare the following raw materials in parts by weight: 64 parts of bisphenol A epoxy resin, 16 parts of the functional component prepared in Preparation Example 1, 8 parts of the modified thermal conductive filler prepared in Comparative Preparation Example 3, 20 parts of propylene glycol methyl ether, 0.1 part of dimethyl benzoin ether, 25 parts of epoxy resin curing agent T31, and 1 part of 1-benzylbenzene-2-ethylimidazole;

[0100] Step 2: Add the functional component, modified thermal conductive filler, and dimethyl benzoin ether into propylene glycol methyl ether, stir at a speed of 600 rpm for 25 min until homogeneous, keep the speed unchanged, irradiate with ultraviolet light for 10 min while stirring, control the irradiation temperature at 50 °C, cool down to 25 °C, then successively add bisphenol A epoxy resin, epoxy resin curing agent T31, and 1-benzylbenzene-2-ethylimidazole, carry out an emulsification reaction at a speed of 1000 rpm for 1.6 h, and let it stand for 5 h to obtain a thermal conductive adhesive liquid.

[0101] Comparative Preparation Example 8

[0102] This comparative preparation example provides a method for preparing a thermal conductive adhesive liquid. The method for preparing the thermal conductive adhesive liquid includes the following steps:

[0103] Step 1: Prepare the following raw materials in parts by weight: 64 parts of bisphenol A epoxy resin, 16 parts of the functional component prepared in Preparation Example 1, 8 parts of the modified thermal conductive filler prepared in Comparative Preparation Example 4, 20 parts of propylene glycol methyl ether, 0.1 part of dimethyl benzoin ether, 25 parts of epoxy resin curing agent T31, and 1 part of 1-benzylbenzene-2-ethylimidazole;

[0104] Step 2: Add the functional components, modified thermal conductive filler, and dimethyl benzoin ether into propylene glycol methyl ether, stir at a rotation speed of 600 rpm for 25 min until homogeneous, keep the rotation speed unchanged, irradiate with ultraviolet light for 10 min while stirring, control the irradiation temperature at 50 °C, cool down to 25 °C, then sequentially add bisphenol A epoxy resin, epoxy resin curing agent T31, and 1-benzylbenzene-2-ethylimidazole, and carry out an emulsification reaction at a rotation speed of 1000 rpm for 1.6 h, and let it stand for 5 h to obtain a thermal conductive adhesive solution.

[0105] Examples 1-3 and Comparative Examples 1-4 provide a method for preparing a high thermal conductivity aluminum-based copper clad laminate.

[0106] Example 1

[0107] Step S1: Coat the thermal conductive adhesive solution prepared in Preparation Example 7 on the copper foil, control the coating line speed at 12 m / min, control the coating thickness at 75 μm, and perform heat treatment at 230 °C for 2 min to obtain a prepreg;

[0108] Step S2: Cut the prepreg and laminate it with the aluminum-based bottom plate, perform hot pressing at 20 MPa and 280 °C for 1.8 h, and cool to obtain a high thermal conductivity aluminum-based copper clad laminate.

[0109] Example 2

[0110] This example provides a high thermal conductivity aluminum-based copper clad laminate, including an aluminum-based bottom plate and a prepreg, and the prepreg is prepared by thermally curing the thermal conductive adhesive solution prepared in Preparation Example 8 and the copper foil;

[0111] The preparation method of this high thermal conductivity aluminum-based copper clad laminate includes the following steps:

[0112] Step S1: Coat the thermal conductive adhesive solution prepared in Preparation Example 8 on the copper foil, control the coating line speed at 16 m / min, control the coating thickness at 85 μm, and perform heat treatment at 245 °C for 3 min to obtain a prepreg;

[0113] Step S2: Cut the prepreg and laminate it with the aluminum-based bottom plate, perform hot pressing at 23 MPa and 300 °C for 1.8 - 2.2 h, and cool to obtain a high thermal conductivity aluminum-based copper clad laminate.

[0114] Example 3

[0115] This example provides a high thermal conductivity aluminum-based copper clad laminate, including an aluminum-based bottom plate and a prepreg, and the prepreg is prepared by thermally curing the thermal conductive adhesive solution prepared in Preparation Example 9 and the copper foil;

[0116] The preparation method of this high thermal conductivity aluminum-based copper clad laminate includes the following steps:

[0117] Step S1: Coat the heat-conducting adhesive solution prepared in Preparation Example 9 on a copper foil. Control the wire speed of sizing to 20 m / min, control the coating thickness to 95 μm, and perform heat treatment at 260 °C for 4 min to obtain a prepreg;

[0118] Step S2: Cut the prepreg and laminate it with an aluminum base plate. Perform hot pressing at 25 MPa and 320 °C for 2.2 h, and then cool to obtain a high heat-conducting aluminum-based copper clad laminate.

[0119] Comparative Example 1

[0120] This comparative example provides a high heat-conducting aluminum-based copper clad laminate, which includes an aluminum base plate and a prepreg. The prepreg is obtained by thermosetting the heat-conducting adhesive solution prepared in Comparative Preparation Example 5 and a copper foil;

[0121] The preparation method of the high heat-conducting aluminum-based copper clad laminate includes the following steps:

[0122] Step S1: Coat the heat-conducting adhesive solution prepared in Comparative Preparation Example 5 on a copper foil. Control the wire speed of sizing to 12 m / min, control the coating thickness to 75 μm, and perform heat treatment at 230 °C for 2 min to obtain a prepreg;

[0123] Step S2: Cut the prepreg and laminate it with an aluminum base plate. Perform hot pressing at 20 MPa and 280 °C for 1.8 h, and then cool to obtain a high heat-conducting aluminum-based copper clad laminate.

[0124] Comparative Example 2

[0125] This comparative example provides a high heat-conducting aluminum-based copper clad laminate, which includes an aluminum base plate and a prepreg. The prepreg is obtained by thermosetting the heat-conducting adhesive solution prepared in Comparative Preparation Example 6 and a copper foil;

[0126] The preparation method of the high heat-conducting aluminum-based copper clad laminate includes the following steps:

[0127] Step S1: Coat the heat-conducting adhesive solution prepared in Comparative Preparation Example 6 on a copper foil. Control the wire speed of sizing to 12 m / min, control the coating thickness to 75 μm, and perform heat treatment at 230 °C for 2 min to obtain a prepreg;

[0128] Step S2: Cut the prepreg and laminate it with an aluminum base plate. Perform hot pressing at 20 MPa and 280 °C for 1.8 h, and then cool to obtain a high heat-conducting aluminum-based copper clad laminate.

[0129] Comparative Example 3

[0130] This comparative example provides a high heat-conducting aluminum-based copper clad laminate, which includes an aluminum base plate and a prepreg. The prepreg is obtained by thermosetting the heat-conducting adhesive solution prepared in Comparative Preparation Example 7 and a copper foil;

[0131] The preparation method of the high thermal conductivity aluminum-based copper clad laminate comprises the following steps:

[0132] Step S1: Coating the thermal conductive adhesive solution prepared in Comparative Preparation Example 7 on the copper foil, controlling the coating line speed to be 12 m / min, controlling the coating thickness to be 75 μm, and performing heat treatment at 230 °C for 2 min to obtain a prepreg;

[0133] Step S2: Cutting the prepreg and laminating it with the aluminum-based bottom plate, performing hot pressing at 20 MPa and 280 °C for 1.8 h, and cooling to obtain the high thermal conductivity aluminum-based copper clad laminate.

[0134] Comparative Example 4

[0135] This comparative example provides a high thermal conductivity aluminum-based copper clad laminate, which includes an aluminum-based bottom plate and a prepreg. The prepreg is obtained by thermally curing the thermal conductive adhesive solution prepared in Comparative Preparation Example 8 and the copper foil;

[0136] The preparation method of the high thermal conductivity aluminum-based copper clad laminate comprises the following steps:

[0137] Step S1: Coating the thermal conductive adhesive solution prepared in Comparative Preparation Example 8 on the copper foil, controlling the coating line speed to be 12 m / min, controlling the coating thickness to be 75 μm, and performing heat treatment at 230 °C for 2 min to obtain a prepreg;

[0138] Step S2: Cutting the prepreg and laminating it with the aluminum-based bottom plate, performing hot pressing at 20 MPa and 280 °C for 1.8 h, and cooling to obtain the high thermal conductivity aluminum-based copper clad laminate.

[0139] Performance detection

[0140] The thermal conductivity and breakdown voltage resistance performance of the aluminum-based copper clad laminates prepared in Examples 1-3 and Comparative Examples 1-4 were tested. The thermal conductivity test method was ASTM D5470, and the breakdown voltage resistance performance test method was IPC-TM-650 2.5.6. The test results are shown in Table 1 below:

[0141] Table 1 Thermal conductivity and insulation test of the aluminum-based copper clad laminates prepared in Examples 1-3 and Comparative Examples 1-4

[0142]

[0143] As can be seen from Table 1, compared with Comparative Examples 1-4, the aluminum-based copper clad laminates prepared in Examples 1-3 have more excellent thermal conductivity and insulation.

[0144] This specific embodiment is only an interpretation of the present application and does not limit the present application. Those skilled in the art can make modifications without creative contributions to this embodiment according to needs after reading this specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A high thermal conductivity aluminum-based copper clad laminate, characterized in that, It includes an aluminum-based bottom plate and a prepreg, and the prepreg is obtained by thermosetting a thermally conductive adhesive liquid and copper foil; The thermally conductive adhesive liquid is obtained by first subjecting a functional component and a modified thermally conductive filler to click addition and then chemically crosslinking with an epoxy resin; The functional component is first treated with a saturated aqueous sodium hydroxide solution by microcrystalline cellulose, then undergoes a nucleophilic substitution reaction with epichlorohydrin, and then continues to undergo a ring-opening esterification reaction with ricinoleic acid to obtain a hydroxyl monomer, and finally undergoes an esterification reaction with 2-mercaptonicotinic acid; The modified thermally conductive filler is first treated with an alkali solution to obtain hydroxyl boron nitride, and then undergoes an esterification reaction with 3,5-diaminobenzoic acid to obtain an amino monomer, and finally undergoes a ring-opening esterification reaction with octenyl succinic anhydride; 2. The high thermal conductivity aluminum-based copper clad laminate according to claim 1, wherein, The preparation method of the thermally conductive adhesive liquid includes the following steps: First step, prepare the following raw materials in parts by weight: 64-132 parts of bisphenol A epoxy resin, 16-30 parts of functional component, 8-18 parts of modified thermally conductive filler, 20-40 parts of organic solvent, 0.1-0.2 part of photoinitiator, 25-30 parts of curing agent, 1-5 parts of curing accelerator; Second step, add the functional component, the modified thermally conductive filler and the photoinitiator into the organic solvent, stir evenly, irradiate with ultraviolet light for 10-20 min, control the irradiation temperature at 50-56 °C, cool down to 25-30 °C, and then sequentially add bisphenol A epoxy resin, curing agent and curing accelerator, emulsify for 1.6-2.8 h, and stand for 5-7 h to obtain the thermally conductive adhesive liquid.

3. The high thermal conductivity aluminum-based copper clad laminate according to claim 2, wherein The preparation method of the functional component includes the following steps: Step A1, mix microcrystalline cellulose and saturated sodium hydroxide solution evenly, then add epichlorohydrin, heat up to 58-64 °C, continue to stir for 5.2-6.4 h, filter, and then add a mixed solution a of dropwise added ricinoleic acid, pyridine and anhydrous DMF, control to finish dropping within 30 min, heat up to 76-82 °C, continue to react for 4-6 h, after the reaction ends, filter, wash, and dry to obtain the hydroxyl monomer; Step A2, add the hydroxyl monomer, 2-mercaptonicotinic acid and phosphotungstic acid into anhydrous DMF, stir evenly, under nitrogen protection, heat up to 74-80 °C, stir and react for 9-12 h, after the reaction ends, carry out suction filtration, wash, and dry to obtain the functional component.

4. A high thermal conductivity aluminum-based copper clad laminate according to claim 3, characterized in that, In the said Step A1, the mass ratio of microcrystalline cellulose, saturated sodium hydroxide solution, epichlorohydrin and the mixed solution a is 0.6-1.0:64-76:2.4-3.0:32-34, and in the mixed solution a, the mass ratio of ricinoleic acid, pyridine and anhydrous DMF is 4:0.03-0.05:28-30.

5. The high thermal conductivity aluminum-based copper clad laminate according to claim 3, wherein, In the said Step A2, the mass ratio of the hydroxyl monomer, 2-mercaptonicotinic acid, phosphotungstic acid and anhydrous DMF is 1.6-2.2:0.4-0.6:0.01-0.02:40-60.

6. The high thermal conductivity aluminum-based copper clad laminate according to claim 1, characterized in that The modified thermally conductive filler is made by the following steps: Step B1, under nitrogen protection, add nano-hexagonal boron nitride into the alkali solution, heat up to 106-112 °C, stir and react for 36-42 h, after the reaction ends, precipitate, wash, and dry to obtain hydroxyl boron nitride; Step B2: Add hydroxyboron nitride, 3,5-diaminobenzoic acid and p-toluenesulfonic acid into anhydrous DMF, stir evenly, under nitrogen protection, heat up to 78 - 84 °C, stir and react for 12 - 16 h. After the reaction is completed, perform suction filtration, washing, and drying to obtain the amino monomer; Step B3: Add the amino monomer into anhydrous DMF, stir evenly, adjust the pH value to 8 - 9, dropwise add the mixed solution b of octenyl succinic anhydride and isopropanol, control the dropping to be completed within 10 min. After dropping, heat up to 72 - 76 °C, continue to stir and react for 6 - 12 h, then adjust the pH value to 6.4 - 6.8, wash, and dry to obtain the modified thermal conductive filler.

7. The high thermal conductivity aluminum-based copper clad laminate according to claim 6, characterized in that, In the said Step B1, the mass ratio of nano hexagonal boron nitride to the alkali solution is 3 - 5:600 - 700.

8. The high thermal conductivity aluminum-based copper clad laminate according to claim 6, characterized in that, In the said Step B2, the mass ratio of hydroxyboron nitride, 3,5-diaminobenzoic acid, p-toluenesulfonic acid and anhydrous DMF is 2.2 - 2.6:15.2 - 18.4:0.14 - 0.20:70 - 78.

9. The high thermal conductivity aluminum-based copper clad laminate according to claim 6, characterized in that, In the said Step B3, the mass ratio of the amino monomer, anhydrous DMF and the mixed solution b is 3 - 5:62 - 66:32 - 36. In the mixed solution b, the mass ratio of octenyl succinic anhydride to isopropanol is 4 - 6.8:

28.

10. A method for preparing a high thermal conductivity aluminum-based copper clad laminate according to any one of claims 1-9, characterized in that, It includes the following steps: Step S1: Coat the thermal conductive adhesive solution on the copper foil, control the wire speed of sizing to be 12 - 20 m / min, control the coating thickness to be 75 - 95 μm, and perform heat treatment at 230 - 260 °C for 2 - 4 min to obtain the semi-cured sheet; Step S2: Cut the semi-cured sheet and laminate it with the aluminum base plate, perform hot pressing at 20 - 25 MPa and 280 - 320 °C for 1.8 - 2.2 h, and cool to obtain the high thermal conductive aluminum base copper clad laminate.

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